Composite Material Research PDF

LEADING-EDGE COMPOSITE
MATERIAL RESEARCH
LEADING-EDGE COMPOSITE
MATERIAL RESEARCH
TOBIAS G. WOUTERS
Editor
Nova Science Publishers, Inc.

New York
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Library of Congress Cataloging-in-Publication Data
Leading-edge composite material research / Tobias G. Wouters (editor).

p. cm.
Includes index.
ISBN-13: 978-1-60692-745-8
1. Polymeric composites--Research. 2. Composite materials--Research. I. Wouters, Tobias G.
TA418.9.C6L379 2008
620.1'18--dc22
2007033917
Published by Nova Science Publishers, Inc. New York

CONTENTS
Preface vii
Expert Commentary 1
Commentary: Future Prospects for MMCs 3

Kelvii Wei Guo
Short Communication 7
Communication: Meso/Nanostructured Composites Based on Self-Assembled

Poly(styrene-b-ethylene oxide) Block Copolymer Matrices 9
A. Tercjak, J. Gutierrez, I. Garcia and I. Mondragon
Research and Review Studies 23
Chapter 1 Durability Aspects of Polymer Composites Used for Restoration

and Rehabilitation of Structures 25
Mariaenrica Frigione
Chapter 2 Smart Adhesively Bonded Composite Joints: Analysis and Design 73

Jinquan Cheng, Guoqiang Li and Su-Seng Pang
Chapter 3 Thermosetting Laminates Quality: From Fiber Waviness to

Fem Cure Modeling 149
Ch. Jochum and J. C. Grandidier
Chapter 4 Modelling of Multilayered Piezoelectric Composites 197

Claire David
Chapter 5 Cyclic Deformation of Discontinuously Reinforced Metal

Matrix Composites: A Review 255
Guozheng Kang
Chapter 6 Biodegradable Polymer Composites 293

Long Yu, Steven Petinakis, Katherine Dean and Ling Chen
vi Contents
Chapter 7 Composite Materials Studied at a Molecular Scale.

Use of Fluorescent Labels 315
Javier Gonzalez-Benito
Chapter 8 Thermal and Wear Studies of Polymer-Fullerene Composites 333

Aleksei O. Pozdnyakov and Klaus Friedrich
Chapter 9 An Approach for Welding Particle Reinforcement

Aluminum Matrix Composites: Transient Pulse-Impact
Liquid-Phase Welding 349
Kelvii Wei Guo
Index 373
PREFACE
This book presents new and significant research progress on composite materials which
are engineered materials made from two or more constituent materials with significantly
different physical or chemical properties and which remain separate and distinct on a
macroscopic level within the finished structure. Fiber Reinforced Polymers or FRPs include
Wood comprising (cellulose fibers in a lignin and hemicellulose matrix), Carbon-fiber
reinforced plastic or CFRP, Glass-fiber reinforced plastic or GFRP (also GRP). If classified
by matrix then there are Thermoplastic Composites, short fiber thermoplastics, long fiber
thermoplastics or long fiber reinforced thermoplastics There are numerous thermoset
composites, but advanced systems usually incorporate aramid fibre and carbon fibre in an
epoxy resin matrix.
Composites can also utilise metal fibres reinforcing other metals, as in Metal matrix
composites or MMC. Ceramic matrix composites include Bone (hydroxyapatite reinforced
with collagen fibers), Cermet (ceramic and metal) and Concrete. Organic matrix/ceramic
aggregate composites include Asphalt concrete, Mastic asphalt, Mastic roller hybrid, Dental
composite, Syntactic foam and Mother of Pearl. Chobham armour is a special composite used
in military applications. Engineered wood includes a wide variety of different products such
as Plywood, Oriented strand board, Wood plastic composite (recycled wood fiber in
polyethylene matrix), Pykrete (sawdust in ice matrix), Plastic-impregnated or laminated paper
or textiles, Arborite, Formica (plastic) and Micarta.
Composite materials have gained popularity (despite their generally high cost) in high-
performance products such as aerospace components (tails, wings , fuselages, propellors),
boat and scull hulls, and racing car bodies. More mundane uses include fishing rods and
storage tanks.
Chapter 1 - The acceptance of the fiber-reinforced polymers (FRP) in the strengthening
of civil and monumental structures is due to a combination of suitable properties and
manufacture/installation capability. With respect to traditional building materials, such as
steel and concrete, polymer composites offer high strength/weight ratio, good resistance to
fatigue, excellent chemical and corrosion resistance. The long term behavior of FRP subjected
to weathering is still not well understood. Environmental factors can have a crucial effect on
their performance in service. The various environmental factors that have been identified as
having a deleterious effect on the durability of FRP are: moisture, temperature changes,
freeze-thaw, alkaline environment, ultraviolet radiations. The durability in severe
viii Tobias G. Wouters
environments, however, is one of the key factor which has contributed to the acceptance of
polymer composites in demanding applications, such as the aerospace industry.
In this chapter, the properties of several FRP’s employed in civil engineering applications
are analyzed in relation to the environmental agents to which they can be exposed. Specific
interactions can be identified between the different external agents and the based materials
composing the FRP. Different thermosetting matrices and fibers, employed for restoration
and strengthening applications, are considered. Epoxy, vinyl ester and polyester matrices are
reviewed, evidencing the susceptibility of their mechanical properties and adhesive strength
to weathering. The performance of an FRP exposed to a harsh environment depends also on
the vulnerability of fibers towards the external agents. The fibers most commonly used in
FRP for structural reinforcements are based on three types of compounds: carbon, glass and
aramidic. Laboratory simulations of environmental agents are compared to natural exposure,
emphasizing advantages and limits when reproducing the weather conditions with laboratory
procedures. Some remarks and considerations are, finally, drawn.
Chapter 2 - Due to their inherent advantages over mechanical-fastening methods, the use
of adhesively bonded composite joints has been significantly increased in recent years for
joining composite beams, panels, tubes, etc., which are fundamental components in civilian,
military and aeronautic structures. Because the applied load in the adherends is always
transferred in the form of shear and/or peel stresses through the adhesive layer, the stress
concentration developed in the end regions at the adhesive bondline is the principal reason for
causing the premature and catastrophic failure of adhesively bonded joints. This has always
been a dilemma for the designers of such joints. In order to reduce the peel/shear stresses
concentration and improve the joint strength, some traditional mechanical methods have been
developed as practical solutions to reduce the stress concentration, such as rounding off sharp
edges, spewing fillets, and tapering adherends. These methods are passive in reducing stress
concentration, i.e., they are ineffective unless the pattern and magnitude of the applied loads
are fixed. Comparing to these traditional mechanical enhancement methods, an active smart
strength improvement method for adhesively bonded composite joint is introduced in this
chapter to adaptively realize the reduction of peel/shear stress concentration through the
integrated piezoelectric layers as sensor/actuator in the composite joint system. This type of
joint is smart because, on one hand, the integrated piezoelectric layers can serve as sensors to
monitor the joint system deformation; on the other hand, the piezoelectric layers also serve as
actuators to produce a counter-balancing force or moment. In such smart joints, counter-
balancing forces and moments can be adaptively produced by adjusting the applied electric
fields to the integrated piezoelectric layers based on the information as sensors. The
additional forces and moments can be controlled to act oppositely to those developed
internally by the payloads, thereby alleviating the stress concentration in the joint edges and
smartly improve the joint strength. In this chapter, the fundamental concept of the proposed
smart adhesively bonded composite joint method is firstly introduced, and then, the details in
designing and analyzing such joints under various loading conditions are systematically
discussed, including single-lap and single-strap smart composite joints subjected to tensile
loading, and smart composite pipe joints subjected to axial tension or bending.
Chapter 3 - This paper focuses on the problem of material quality and internal stress
encountered during the curing of structural thermosetting laminates. The first part presents
the relevant problem of internal stresses generated by the curing for both thin and thick
structural thermosetting laminates. Needs for accurate description of laminates properties and
Preface ix
internal stress state presented at the end of the curing is a strategic problem for high
performance application. Despite of numerous studies performed for internal stress
description and fiber waviness measurement, the way of cure modeling appears inevitable for
three dimensional composites structures analysis. The foundations of a thermal, chemical and
mechanical coupling model are developed in the second part of the chapter, within a
thermodynamically and viscoelastic framework and takes into account any coupling, namely
species diffusion. Then, on the basis of parametric studies provided by the coupling model, a
predictive internal stress coupling model is presented in the third part of the chapter and is
validated for three dimensional internal temperature prediction, -hence, exothermic effects,
and elastic internal stress level during the hot stage of the curing. Accuracy of thermosetting
matrix history description provided by the model was then successfully tested in the last part
of the chapter for the fiber waviness phenomenon.
Chapter 4 - The authors hereafter study the modelling of composite multilayered
piezoelectric plates. Their theory is based on an hybrid approach, where the mechanical and
electrical continuity conditions are satisfied, as well as the boundary conditions on the top and
bottom surfaces of the structure. The accuracy of the proposed theory is assessed through
investigation of significant problems, for which an exact three-dimensional solution is known.
The development of the so-called "smart-structures",e.g. made of piezoelectric
composites, require nowadays more and more precision in their design and sizing. The
importance of efficient models has, so far, led to numerous theories.
Chapter 5 - Discontinuously reinforced metal matrix composites (DRMMCs), such as
particulate reinforced metal matrix composites (PRMMCs) and short fiber reinforced metal
matrix composites (SFRMMCs) (especially aluminum alloy matrix composites) are currently
being used and will be used as major structural components in automobiles and aircrafts,
which are often subjected to a cyclic loading, in sooner future. The microstructures of the
composites become very complicated due to a shortened length and randomly oriented
distribution of short fibers and particulates, and then precise prediction for their mechanical
performances, especially for the cyclic deformation process is rather difficult. However, the
accurate prediction to such behaviors is extremely necessary to design and assess the structure
components made from such composites, and some progresses have been made by many
researches recently. Therefore, in this Chapter, recent progresses in the researches about the
cyclic deformation (including the ratcheting behavior produced in the asymmetrical cyclic
stressing) of DRMMCs are reviewed. The content of the review includes the state-of-arts in
experimental observations, numerical simulations and some constitutive models for
PRMMCs or SFRMMCs. The loading modes involved are uniaxial and multiaxial cyclic
straining and cyclic stressing, and the ambient temperature varies from room temperature to
high temperature. The effects of some time-factors on the cyclic deformation of the
composites are also considered. As a conclusion of the review, some suggestions are provided
for the future researches about the cyclic deformation of PRMMCs or SFRMMCs.
Chapter 6 - Like most conventional polymers, biodegradable polymers are rarely used by
themselves, because most of them have relatively poor mechanical and thermal properties,
and therefore reinforcement techniques using fibers or fillers are particular important.
Natural fibers (e.g. cotton, flax, hemp, jute) have been widely used in polymeric materials
to improve mechanical properties, and can generally be classified as bast, leaf or seed-hair
fibers. Cellulose is a major constituent derived from vegetable fibers, and applications for
cellulose fiber-reinforced polymers have again come to the forefront with the current focus on
x Tobias G. Wouters
renewable raw materials [1–3]. Hydrophilic cellulose fibers are very compatible with most
natural polymers. The reinforcement of starch with cellulose fibers is a perfect example of a
composite produced by polymers from renewable resources (PFRR).
The reinforcement of polymers using fillers is common in the production and processing
of polymeric materials. The interest in new nanoscale fillers has rapidly grown over the last
two decades, since it was discovered that a nanostructure could be built from a polymer and
layered nanoclay. These new nanocomposites have shown dramatic improvements in
mechanical properties at low filler content. Reinforcement with fillers is particularly
important for natural polymers, since most of them have the disadvantages of lower softening
temperatures and lower modulus. Furthermore, the hydrophilic behavior of most natural
polymers offers a significant advantage, since it provides a compatible interface with the
nanoclay. These new composites are extending the utilization of biodegradable polymers into
new value-added products.
Chapter 7 - Among other factors, properties of composite materials depend on the type of
adhesion between their constituents since they are a function of the ability to transfer loads
from the matrix to the reinforcement. There are many studies about surface modification of
reinforcements to improve their adhesion with matrices trough the creation of more or less
complex interphases. In fact, mechanical properties and ageing of composites can greatly
change as a consequence of the different structures and morphologies generated in the
interphase. There are several theories that try to explain the mechanisms responsible of the
composites performance; however, in most of the cases, the “interphases” are not enough
understood because it is experimentally very difficult to obtain information at a nanoscopic
and/or molecular scale; for instance: i) structural information; ii) dynamic behaviour and iii)
ageing phenomena.
Due to the difficulty in knowing this interfacial structure, most of the researchers have
focused their efforts to study the structure and properties either the polymeric matrix or the
reinforcement surface and, subsequently, they have related them to the behaviour in service of
the composites. However, although the nature of the reinforcement surface affects the final
structure of the interphase and therefore, the final properties of the composites, it is of great
interest to know how the coupling region interacts with the polymer matrix in order to acquire
the basics necessary to obtain in the future composites with tailor made interphases and
therefore controlled properties. Therefore, the necessity of optimizing experimental methods
to collect information at a molecular scale from specific sites like coupling regions and
interphases is evident. A possibility to overcome this is the use of fluorescent labels since, in
many cases, without modifying the properties of the system, it is possible to have enough
fluorescence signal importantly affected by the immediate surrounding (local polarity,
rigidity, pH …) of the label.
This work tries to summarise important aspects about the use of the fluorescent labels
chemically bonded to specific sites such as interfaces in composite materials to get
information about its molecular structure, its dynamics and the accessibility of small
molecules like water.
Chapter 8 - Numerous polymer-nanocarbon composite applications, e.g., electro-
luminescence, rheology, tribology, and thermal ignition are being continuously documented.
This provides firm impetus for studies of the structure and properties of such composites.
Their properties exhibit complicated relationships to electronic and vibrational subsystems of
the polymer matrices in presence of fullerene molecules. This chapter gives an example of a
Preface xi
comparative study of the thermal behavior of several polymers and their respective polymer-
fullerene C60 composites. The influence of fullerenes on macroscopic tribological behavior of
polyimide-fullerene composite is analyzed.
Chapter 9 - The aluminum matrix composite SiCp/ AlSi7Mg was welded by Transient
Pulse-Impact Liquid-Phase Welding (TPILPW), the effect of welding parameters on the
welded joint property was investigated, and the optimal welding parameters were put forward
ultimately. The microstructure of joint was analyzed by means of optical-microscope,
scanning electron microscope (SEM) and EPMA in order to study the relationship between
the macro-properties of joint and the microstructure. Results showed that during TPILPW: (i)
the interface state between reinforcement particle and matrix was prominently affected by the
transient pulse-impact; (ii) the initial pernicious contact-state of reinforcement particles was
changed from reinforcement (SiC)/reinforcement (SiC) to reinforcement
(SiC)/matrix/reinforcement (SiC); (iii) the harmful microstructure/brittle phase of Al4C3 was
restrained from the welded joint; (iv) the density of dislocation in the matrix neighboring to
and away from the interface in the matrix was higher than its parent composite; and (v) the
intensively mutual entwisting of dislocation was taking place. Studies illustrated that: (1)
deformation was mainly occurred in the matrix grain; and (2) in the deformation of rapid
thermal pressing, the matrices around SiC particles engendered intensive aberration offered a
high density nucleus area for matrix crystal, which was in favor of forming nano-grains and
improved the properties of the successfully welded composite joints. Such distinctly welded
composite joints gave: (i) a tensile strength up to 179MPa that was about 74.6% of the stir-
cast SiCp/ AlSi7Mg; and (ii) a corresponding radial deformation below 3% that conformed
well to the deformation specification of the welded specimens. Moreover, a prominent
characteristic of TPILPW was shorter welding time than that of the conventional welding
method. By physical simulation, it showed that the temperature in the weld would be
increased sharply to some extent under the effect of transient pulse-impact. Furthermore, the
length of solid/liquid phase state in the specimen was calculated, the result could be expressed
ΔT
as Δx = ξ L . Finally, powder metallurgy made aluminum matrix composites,
Tmax − T0
SiCp/6061Al, Al2O3p/6061Al, were welded by TPILPW. Results showed that Transient Pulse-
Impact Liquid-Phase Welding was suitable for application in joining particle reinforcement
aluminum matrix composites.
EXPERT COMMENTARY
In: Leading-Edge Composite Material Research ISBN: 978-1-60021-995-5
Editor: Tobias G. Wouters, pp. 3-6 © 2008 Nova Science Publishers, Inc.
FUTURE PROSPECTS FOR MMCS
Kelvii Wei Guo1

Department of Manufacturing Engineering and Engineering Management, City
University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Kowloon, Hong Kong
Abstract
Up to date, the objective of the MMCs has been developing composite materials that are
stronger than steel and lighter than aluminum required for automobile, aerospace industries,
structural components, and heat resistant-wearable parts of engines and many other key
industrial applications.
However, the large scale funding for MMCs work is mainly provided by the aerospace,
defense industry and related government bodies. The production of MMCs for daily life, such
as applications of automotive, bicycle, bridge structure, medical equipments, sports, is still on
the incipient stage.
MMCs Properties
At present the main research is related to development of mechanical properties for various
MMCs. The physical properties (expansion, specific capacity, conduction, electromagnet etc.)
of MMCs should be significantly studied entirely. Nevertheless, the enhancement of
mechanical properties will still be of major importance. Opportunities for further
advancement in this area include different reinforcement(s)/matrix (matrices) systems to
provide higher properties. Extensive researches are required to demonstrate these concepts on
a laboratory scale. If successful, significant investment will then be necessary for full scale
production, especially for nanocomposites materials, there exist serious obstacles to overcome
to develop the technology to permit inexpensive large scale production, but, its corresponding
offered promise makes them worthy of further investigations.
1
E-mail address: guoweichinese@yahoo.com (W. GUO). Tel.:+852-2784-4614 (Corresponding author)
4 Kelvii Wei Guo
MMCs Disadvantages
Control of reactions at the matrix reinforcement interface is still a major obstacle, preventing
more inexpensive MMCs production and more extensive its corresponding application.
Consequently, it is critical to study and establish the optimal interface for different
reinforcements/matrices systemically. A major emphasis should be therefore placed on
gaining a full understanding of the interface in MMCs resulted in good wetting established,
and maintain uniform dispersion of reinforcements (include shape, size and volume of
reinforcements) in the matrices.
MMCs Manufaturing
According to a realistic possibility, MMCs costs must be in a commercial usage. It is obvious
that MMCs are significantly more expensive than the metals from which they derive.
Moreover, it is difficult to convince that these higher materials costs will show lower
component function costs due to its higher performances for users. Simultaneously, high
volume production of MMCs should be improved to a larger step in the markets other than
those related to high performances or military applications with the innovative techniques.
Obviously, it is an urgent to reduce MMCs costs to a more attractive degree.
MMCs Processing
As a class of materials, it needs to develop corresponding technology for processing designed
components on a large scale. Joining technique plays a more important rule in MMCs
processing, especially welding. Although there are several welding techniques (solid-state
bonding, soldering, TIG welding, laser welding, EB welding etc.) currently available for
joining MMCs, there still exist quality problems due to (1) Distribution of particle
reinforcements in the weld. Usually, properties of welded joints are directly influenced by the
distribution of particle reinforcements in the weld. When particle reinforcements are
distributed uniformly in the weld, the tensile strength of welded joints is likely to reach 80%
(or even slightly higher) of that of the parent MMCs. When the particle reinforcements are
distributed in conglomeration or absent in the weld (viz. no-reinforcements-zone), the
properties of welded joints are degraded markedly that subsequently resulted in the failure of
welding. (2) Interface between the particle reinforcements and aluminium matrix. Generally,
the high welding temperature in the fusion welding methods (typically: TIG, laser welding,
electron beam etc.) is likely to yield various pernicious phases in the interface. Moreover, the
long welding time (e.g. several days in certain occasions) produced in the solid-state welding
methods (such as diffusion welding) normally leads to (i) low efficiency and (ii) formation of
harmful and brittle intermetallic compounds in the interface. Therefore, to alleviate the
problems incurred by the conventional welding processes in joining MMCs, the feasible,
easily-operated, innovative welding techniques, should be developed imminently to impel the
realistic development of MMCs in our daily life.
Future Prospects for MMCs 5
MMCs Developments
It’s well known that the advantage of technology in many cases is limited by the availability
and understanding of materials. Before these materials can be extensively used in commercial
systems, optimized cost effective material process must be developed. In developing these
processes and also after the materials are commercially available, extensive material
characteristics programs must be conducted to provide a database so that the end users of the
material will have confidence in the performance of the material. As an invaluable resources,
a wealth of information (whether online or not) related to MMCs should be provided in detail.
The involved developments in the MMCs field are listed as follows:
1 cheaper lower cost routes to MMCs manufacturing;

2 specialized, high volume production, good compatibility of reinforcements for MMCs;
3 physical metallurgy for MMCs processing;
4 unified testing criteria for MMCs materials and its components;
5 establishing a database of MMCs properties for engineering applications.
All of these are embodied in the field of:
a) Theoretical analysis;
b) Synthesis and processing;
c) Phase and structure analyses;
d) Characterization, properties, engineering and applications;
(1) durability;
(2) interfaces;
(3) interlaminar fracture;
(4) joints and adhesion;
(5) thermoplastics;
(6) wave propagation;
(7) non-destructive testing;
e) Welding/Bonding/Joining
f) Simulations and modeling;
g) Corresponding facilities;
etc.
MMCs Future Innovation

Ultimately, new MMCs in the future would be such materials which have the lowest
environmental footprint as so-called Green Composites. In the environmentally conscious
viewpoint, the impact of new MMCs on the environment should be considered during the
materials designing. Moreover, the environmental burdens must be evaluated in its
corresponding recycling. Due to critical global response to climate change, there would be a
push to make a new profitable market from the use of eco-friendly MMCs. Up to now, for
6 Kelvii Wei Guo
many automotive companies environmentally friendly alternatives to materials for production

have started to be considered. Reuse and recycling of end-of-life materials, such as avoiding
waste by improving product design, increasing the recycling and reuse of waste, will be
crucial in the coming future. Furthermore, new directions in MMCs must all be considered
before material wide-usage. On the basis of environmental criteria, the conventional criteria
for MMCs, such as ultimate mechanical properties, interfacial adhesion between
reinforcement and matrix, cost, physical/chemical properties etc, are also key parameters to
new MMCs with low energy consumption and biodegradability for the good environment.
The big challenge of designers concerning contemporary imperatives in so-called green
MMCs consumption, utilization and innovation, is that a century of attitudes towards
materials- the rare/special. The application of new MMCs therefore requires all efforts to
design/fabricate new MMCs with an active and predetermined standard image of the
environmental exploration to decrease our footprint/various wastes in the environment.
MMCs Future
It is clear that a substantial and long term commitment to MMCs development is necessary if
their true potential is to be fully achieved, whilst the present researchers are genuinely
enthusiastic about the long term future for MMCs. As a class of materials, MMCs are still
needed to investigate from various aspects. As a result, the ripe time for great industrial
changes relevant to conventional materials reformation are coming.
SHORT COMMUNICATION
MESO/NANOSTRUCTURED COMPOSITES BASED ON

SELF-ASSEMBLED POLY(STYRENE-B-ETHYLENE
OXIDE) BLOCK COPOLYMER MATRICES
A. Tercjak, J. Gutierrez, I. Garcia and I. Mondragon*

Escuela Politécnica. Grupo ‘Materiales + Tecnologías’. Dpto. Ingeniería Química
y M Ambiente. Universidad del País Vasco/Euskal Herriko Unibertsitatea.
Pza. Europa, 1. 20018 Donostia/San Sebastián (Spain)
Abstract
The main aim of this research was to study morphologies generated in
meso/nanostructured multifunctional materials using a block copolymer as matrix; which on
the one hand do not loss capability of block copolymers to form ordered structures on the
nanoscale and on the other hand still show good properties of the second component used as
modifier. Consequently, in this contribution, room temperature self-assembled poly(styrene-b-
ethylene oxide) (PSEO) block copolymers, prepared by two different methods, solvent casting
and spin coating, were used as the matrix for manufacturing of meso/nanostructured
composites modified with 4’-(hexyloxy)-4-biphenyl-carbonitrile (HOBC) liquid crystal or
with titanium tetraisopropoxide (TTIP) as titanium oxide precursor (TiO2). HOBC/PSEO
meso/nanocomposites were prepared by solvent-induced phase separation (SIPS) using
tetrahydrofuran (THF). Morphologies generated were analyzed by atomic force microscopy
(AFM). Monitoring of changes of the morphologies generated in the binary HOBC/PSEO
systems during 6 months allow to confirm that not any changes of the morphology where
detected during this time. Thus, self-assembly of HOBC/PSEO binary system can stabilize
well dispersed liquid crystal droplets against coalescence and hinder crystallization of liquid
crystal phase in these multifunctional systems, thus allowing preparation of multifunctional
meso/nanostructured materials.
Additionally, TiO2 nanoparticles were embedded into PSEO block copolymer matrix
using sol-gel technique. Good dispersion of these nanoparticles was obtained. The
morphology of generated nanocomposites changed from hexagonally-packed cylinders for
neat PSEO block copolymer to simple cubic spheres in the nanocomposites.
*
E-mail address: inaki.mondragon@ehu.es. Tel.: +34-943017271; fax: +34-943017140. (Corresponding author)
10 A. Tercjak, J. Gutierrez, I. Garcia et al.
Introduction
Ordered nanostructured materials attract a wide research and industrial interest in the fields of
materials and life sciences. Especially, materials based on supramolecular chemistry and self-
organization have been one of the primary research areas during the last few years. As it is
well known, self-organization is a powerful way to the “bottom up” fabrication of
nanostructured materials [1, 2]. The self-assembly of soft materials such as block copolymers
to form variety of nanoscale periodic patterns offers the potential to fabricate high-density
arrays [3-8] for the use in date storage, electronics, molecular separation and for
combinatorial chemistry and DNA screening, for example. Block copolymers are ideal
materials in this respect since, due to the connectivity of two chemically distinct chains, the
molecules self-assemble into ordered morphologies with a size scale limited to molecular
chain dimensions. In selective solvents diblock copolymers are able to form micelles of
various morphologies such as spheres, cylinders, vesicles, etc. [9]. In the bulk, micro-phase
separation occurs leading to various microstructures like spheres, hexagonally packed
cylinders, lamellae, and discontinuous phases [10-12].
Microphase-ordered block copolymers, as materials capable of spontaneously self-
organizing into a variety of periodic and non-periodic morphologies possessing a
characteristic length scale typically on the order of tens of nanometers, constitute excellent
example of nanostructured polymers under consideration for nanotechnology devices.
Meso/nanostructured nanocomposites materials composed of a self-assembled block
copolymers and nanoscale objects (low molecular weight liquid crystal, nanoparticles, carbon
nanotubes) with at least one characteristic length scale measuring on the order of a few to tens
of nanometers have received considerable attention due to their unique, and sometimes
unexpected, properties.
Taking into account the ability of block copolymers to self-assemble, the main aim of this
contribution was to study morphologies generated in meso/nanostructured multifunctional
materials containing a second component, which on the one hand do not loss capability of
block copolymers to form ordered structures at the nanoscale and on the other hand still show
good properties of the second component used as modifier. In this study, low molecular liquid
crystal (LC) able to switch from opaque to transparent state (based on their nematic/isotropic
transition) and TiO2 nanoparticles have been used as modifier. Specifically, low molecular
weight liquid crystals seem to be of interest from this point of view as they are thermo-
reversible materials suitable for optoelectronic applications such as flexible and projection
displays devices, optic shutters and switchable windows [13-16]. However, one of the
disadvantages of these materials is their drawback during switching from highly light
scattering state (OFF-state) to transparent state (ON-state). In order to solve this problem, in
the last decades, mostly polymer dispersed liquid crystals (PDLC) containing micron-size
liquid crystal (LC) droplets in the optically transparent polymer matrix, or polymer network
liquid crystals (PNLC) containing dispersed polymer network in LC have been extensively
studied in this research field [15-20]. Recently, a new family of PDLC has been developed
[20, 21], and it has also been demonstrated by our research group [22, 23], taking into account
our previous papers [24-29], that liquid crystal dispersed in a thermoplastic/thermoset system
can be used to prepare thermally reversible materials. In this case, the thermoplastic polymer
must have a refractive index matching that of the fully cured thermoset, and it should exhibit
Meso/Nanostructured Composites Based on Self-Assembled Poly… 11
a high compatibility with the liquid crystal and less compatibility with the thermoset
precursors if compared with LC. Here it should be pointed out, that recently, we have
published a new strategy [30] in order to obtain novel multifunctional thermally reversible
nanostructured thermosetting materials.
On the other hand, as it is well known, the preparation of meso/nanocomposites is an
important challenge of materials science. In this field, synthesis of nanostructured TiO2 thin
films has attracted attention due to their physical properties and applications in
photocatalysis, photovoltaics, gas sensing and lithium ion battery materials [31-35]. Their
optical and electrical properties are strongly dependent on the size and on the shape of the
dispersed nanoparticles. For semiconductor nanoparticles with sizes close to their Bohr
exciton radius (typically between 1-10 nm), the size-dependent band gap results in tunable
optical properties. Therefore the performance of materials in applications requires the control
over the size and the final morphology. To facility such a control of the size of the
nanoparticles, organic templates which self-assemble on the nanometric scale or patterning
inorganic architectures built from inorganic precursors to control nucleation and growth
process can be achieved.
Consequently, in this contribution, room temperature self-assembled poly(styrene-b-
ethylene oxide) (PSEO) block copolymers, prepared by two different methods, solvent
casting and spin coating, were used as the matrix for manufacturing of meso/nanostructured
composites modified with 4’-(hexyloxy)-4-biphenyl-carbonitrile (HOBC). Materials were
prepared by both solvent-induced micro-phase separation using tetrahydrofuran (THF) as
solvent and temperature induced phase separation (TIPS). Morphologies generated were
analyzed by atomic force microscopy (AFM). Monitoring of changes of the morphologies
generated in the binary HOBC/PSEO systems during 6 months allow to confirm that during
this time no changes of the morphology have been detected. Thus, self-assembly of
HOBC/PSEO binary system can stabilize well dispersed liquid crystal droplets against
coalescence also hindering crystallization of LC phase in these multifunctional systems. This
fact can open novel strategies to obtain multifunctional materials based on self-assembled
block copolymers. Thus, the possibilities to obtain different nanostructured architectures
based on combination of PSEO block copolymers and both low molecular liquid crystal or
TiO2 nanoparticles are abundant and therefore their possible applications can cover very
diverse fields.
Moreover, TiO2 nanoparticles were introduced into PSEO block copolymer matrices
using sol-gel technique. Good dispersion of TiO2 nanoparticles in the block copolymer has
been obtained.
Experimental Part
Materials and Sample Preparation
In the present study, an amphiphilic diblock copolymer of poly(styrene-block-ethylene oxide),

supplied by Polymer Source Inc., was used. Number-average molecular mass for PS and PEO
(11 wt %) blocks are 125,000 g mol-1 and 16,100 g mol-1, respectively, being the
polydispersity index 1.04. The low molecular weight nematic liquid crystal used was 4’-
(hexyloxy)-4-biphenyl-carbonitrile, supplied by Sigma-Aldrich. This liquid crystal exhibits a
nematic-isotropic (TN-TI) transition at about 76 ºC and a crystal-nematic (TC-TN) transition at

about 59 ºC [22, 23]. Additionally, titanium tetraisopropoxide (TTIP, 97 %) was purchased
from Aldrich. Titanium oxide precursor TTIP was used to generate good dispersion of these
nanoparticles in the self-assembled PSEO block copolymer matrix by applying the sol-gel
synthesis. This process is a way to make highly dispersed materials through the growth of
metal oxo-polymer in a solvent [36]. Isopropanol (IPA), hydrochloric acid (HCl, 37 %) and
tetrahydrofuran (THF) were supplied by Aldrich and used as received.
HOBC/PSEO blends containing 20 wt % HOBC as well as neat components were
prepared by solvent induced phase separation (SIPS) method from 5-10 wt % tetrahydrofuran
solutions. THF has been used as solvent on the basis of its different interactions with PS and
PEO blocks. Cast films were prepared in microscopy slides varying the evaporation time from
12 h to 6 month; traces of residual solvent were removed under vacuum at room temperature.
In the case of TTIP/PSEO inorganic/organic hybrids, the samples were prepared
according to the following procedure: 0.010 g PSEO and 1 mL tetrahydrofuran were mixed
together by stirring during 1 h, followed by the addition of the appropriate amounts of 37 %
concentrated HCl solution and TTIP. After complete addition the common solution was
stirred for 1 h. Films were prepared on Si wafers by spin coating for 120 s on a spin-coater®
(Model P6700 Series, from SCS) under ambient conditions (temperature, 26 °C; rotation
speed of 2000 rpm).
Techniques
The morphological behaviour of both HOBC/PSEO and TTIP/PSEO systems was

investigated by atomic force microscopy. AFM images were obtained operating in tapping
mode with a scanning probe microscope (Nanoscope IIIa, MultimodeTM and Nanoscope IVa,
Dimension 3100 both from Digital Instruments) equipped with an integrated silicon
tip/cantilever having a resonance frequency ~ 300 kHz, from the same manufacturer. Height
and phase images were recorded simultaneously during scanning. In order to obtain
repeatable results of the blend morphology, different regions of the specimens were scanned.
Similar images were obtained, thus demonstrating the reproducibility of the results. For
analysis of the observed surface structures, the Nanoscope image processing software was
used.
Results
Since self-assembled HOBC/PSEO and TTIP/PSEO binary systems as well as neat PSEO
were prepared at room temperature followed by solvent induced micro-phase separation by
both casting from THF on the glass slides or by spin coating, presented results refer to the
thin film behaviour of these systems. Morphologies of the neat PSEO and
meso/nanostructured composites based on self-assembled poly(styrene-b-ethylene oxide)
block copolymer matrices modified with low molecular weight liquid crystal, HOBC/PSEO,
or with titanium oxide precursor, TTIP/PSEO, have been analyzed by using AFM technique.
The representative morphologies generated in neat amphiphilic PSEO block copolymer after
12 h and 6 months are shown in Figure 1a,b and Figure 1c,d, respectively.
a) b)
c) d)
Figure 1. a) TM-AFM height image for PSEO block copolymer annealed 12 h at room temperature. The
inset shows two-dimensional Fourier transform power spectrum in a region of Figure 1a. b) TM-AFM
phase image corresponding to Figure 1a with higher magnification. c) TM-AFM height image for
PSEO block copolymer annealed 6 months at room temperature. The inset shows two-dimensional
Fourier transform power spectrum in a region of Figure 1c. d) TM-AFM phase image corresponding to
Figure 1c with higher magnification.
Under the annealing conditions used minority PEO-block micro-phase segregates at the
nanometric scale from the PS-block matrix into a quasi-hexagonally ordered structure. The
perpendicular orientation of the cylinders in respect to the surface plane, with the average
repeating distance around 61 and 47 nm, has been easily detected analysing height AFM
images of neat PSEO after 12 h and 6 months, respectively. Representative, two-dimensional
Fourier transform power spectra of the height AFM images of the neat block copolymer after
12 h and 6 months of annealing are shown as inset in Figures 1a and 1c, respectively. Taking
these two-dimensional Fourier transform power spectra into account, one can easily conclude
that they confirm the hexagonally ordered structure of the micro-separated PEO-block [37]. If
only the volume fraction of the PSEO block copolymer is taken into account, the equilibrium
state of the neat PSEO should be in the spherical region with the cubic packaging due to
strong segregation region. However, as it is well known, the morphology of asymmetric
amorphous-crystalline block copolymers depends on crystallization of the crystallisable
block. Consequently, the hexagonally-packed cylindrical morphology of PSEO is a
compromise between the micro-phase separation of PS and PEO blocks and the
crystallization of PEO-block.
Additionally, it should be pointed out that the PEO-block cylindrical micro-domains
appear black in the phase AFM images (Figure 1b, 1d) due to its glass transition temperature
(Tg), around -60 ºC, is significantly lower than the one for PS-block, at around 100 ºC. The
increasing of the average radius of cylinders from 19 nm after 12 h annealing to 30 nm after 6
months can be easily explained by crystallization of the PEO block during so long storage
time. Comparing the phase AFM images corresponding to neat PSEO annealed for 12 h and 6
months at room temperature, it is worth to note that PEO-block cylindrical micro-domains,
which become white in phase AFM images (compare Figure 1b to Figure 1d) confirm
crystallization of PEO-block in self-assembled block copolymer throughout 6 months of
annealing. It should be pointed out that crystallization of PEO-block does not disturb the
quasi-hexagonally ordered structure of the block copolymer, thus crystallization of PEO-
block results in increasing of the average radius of cylinders. Micro-phase separation of PEO-
block during self-assembly of the PSEO block copolymer hinders crystallization of PEO-
block and consequently after 6 mouths crystallization of PEO-block takes place in its micro-
separated cylindrical domains.
Morphological behaviour of neat PSEO block copolymer has been confirmed by
differential scanning calorimetry (DSC) measurements. DSC thermogram for neat PSEO
annealed for 6 months clearly shows the presence of the melting point, Tm, related to PEO-
block, at around 48 ºC, whilst the presence of the corresponding melting point of PEO-block
for neat PSEO annealed for 12 h does not appear in its corresponding thermogram.
Figure 2. DSC thermograms for PSEO block copolymer annealed 12 h and 6 months at room
temperature.
Morphologies generated in 20 wt % HOBC/PSEO mesocomposite annealed at room

temperature for 12 h, 48 h and 6 months by solvent induced phase separation (SIPS) are
shown in Figure 3. Good dispersion of low molecular weight HOBC liquid crystal in the self-
assembled PSEO block copolymer matrix has been obtained. HOBC appears black in phase
AFM images, thus confirming that HOBC phase is in its nematic state and shows the droplet-
like morphology.
a) b)
c) d)
Figure 3. a) TM-AFM phase image for 20 wt % HOBC/PSEO mesocomposite annealed 12 h at room

temperature. b) TM-AFM phase image corresponding to Figure 3a with higher magnification. The inset
shows two-dimensional Fourier transform power spectrum in a region of Figure 1b. c) TM-AFM phase
image for 20 wt % HOBC/PSEO mesocomposite annealed 48 h at room temperature. d) TM-AFM
phase image for 20 wt % HOBC/PSEO mesocomposite annealed 6 months at room temperature.
The average size of the droplets of the nematic phase of HOBC is 165 nm. Additionally,
as seen in Figure 3b, in this mesocomposite the microphase separated PEO-block retains the
almost perfect hexagonal order structure, confirmed by two-dimensional Fourier transform
power spectrum corresponding to the height AFM image of this sample (inset of the Figure
3b). The only difference if compared with morphology generated in neat PSEO prepared
under the same conditions is that cylinders of PEO-block in 20 wt % HOBC/PSEO
mesocomposites are both perpendicular and parallel oriented to the surface plane. The
average distance between PEO-block cylinders is 45 nm and the average radius of them is 30
nm. It seems that micro-phase segregation of the PEO-block provoked by solvent induced
phase separation leads to meso-phase separation of HOBC phase from PS-block matrix and
hinders coalescence process of the droplets of the nematic phase of HOBC. On the contrary,
for the 20 wt % HOBC/PSEO blends prepared by temperature induced phase separation
(TIPS), coalescence of the HOBC phase in the composites takes place as quickly as the
system is cold down to room temperature, as shown in Figure 4. Under these preparation
conditions PSEO block copolymer used as matrix does not retain the capability to self-
assembly.
Figure 4. TM-AFM phase image for 20 wt % HOBC/PSEO mesocomposite prepared by temperature

induced phase separation.
Monitoring of the changes of the morphology generated in 20 wt % HOBC/PSEO

mesocomposite (Figure 3b-d) by solvent induced phase separation at room temperature
during 6 months allows to conclude that self-assembly of PSEO block copolymer leads to
sub-micron separation of HOBC phase into nematic droplets, which are maintained more than
6 months. Thus PEO-block microphase separation hinders both coalescence and
crystallization processes of HOBC phase resulting in a multifunctional system which is
meso/nanostructured and can be switched from opaque to transparent state by applying
temperature gradients, as previously reported by us [22, 23, 30].
Morphology generated in the 20 wt % TTIP/PSEO prepared via sol-gel synthesis was

also studied by AFM. As seen in Figure 5, the whole sample surface is covered by uniform-
in-size TiO2 nanoparticles embedded in PEO-block of PSEO block copolymer.
TiO2 nanoparticles appear white in the AFM phase image since they show higher
stiffness compared to the PS-block matrix. It should be pointed out that good dispersion of
TiO2 nanoparticles with the average size of the nanoparticles around 24 nm in diameter has
been obtained. Additionally, interesting materials can be generated based on sol-gel synthesis
due to TTIP interacts selectively with PEO-block, what allows to control dispersion of TiO2
nanoparticles, based on the capability for microphase separation of PEO-block with TTIP
[38-41] from the PS-block matrix. Comparing final morphologies in neat PSEO and 20 wt %
TTIP/PSEO nanocomposite cast under the same condition, one can easily conclude that TiO2
nanoparticles induce changes in the morphology generated during self-assembly process
provoked by solvent induced phase separation. The morphology generated evolves from
hexagonally-packed cylinders structure (Figure 1a-b) for neat PSEO to simple cubic spheres
for nanocomposite (Figure 5). In order to confirm that white domains in Figure 5a correspond
to TiO2 nanoparticles, the organic part of the 20 wt % TTIP/PSEO nanocomposite has been
degraded by using UV. The AFM phase image of the surface of the nanocomposite after 6 h
of UV exposure, shown in Figure 5b, confirms that whole surface is covered by TiO2
nanoparticles, which are aligned on the surface of the silica wafer. The average size of the
radius of TiO2 nanoparticles after UV treatment is higher than that one without treatment,
thus confirming that nanostructured block copolymers can be used as templates to selectively
control the location of TiO2 nanoparticles in one of the blocks. Currently, electric force
microscopy (EFM, Nanoscope IVa, Digital Instruments) measurements are being used in
order to check if TiO2 nanoparticles into TTIP/PSEO nanocomposites still retain their
electrical behaviour.
a) b)
Figure 5. a) TM-AFM phase image for 20 wt % TTIP/PSEO nanocomposite annealed 12 h at room

temperature. b) TM-AFM phase image for 20 wt % TTIP/PSEO nanocomposite annealed 12 h at room
temperature and after 6 h of UV exposure.
Conclusions
Morphologies generated in neat PSEO block copolymer as well as in meso/nanocomposites
based on this amphiphilic block copolymer modified with low molecular weight liquid crystal
or with titanium oxide nanoparticles precursor via sol-gel synthesis have been studied by
means of atomic force microscopy. Good dispersion of HOBC or TiO2 nanoparticles in both
HOBC/PSEO and TTIP/PSEO binary systems, respectively, has been observed. In both cases,
obtained materials retain the capability of the neat PSEO block copolymer matrix to self-
assemble. PEO-block in HOBC/PSEO binary system shows hexagonally-packed order
structure. Additionally, microphase separation of PEO block provokes separation of HOBC
phase as droplets at the sub-micron scale and hinders coalescence and crystallization process,
thus allowing to obtain multifunctional meso/nanostructured materials. Moreover,
morphology generated in this meso/nanocomposite does not show significant changes even
after 6 months, which suggests several potential applications for this system.
On the other hand, PEO block modified with TTIP microphase separates from the PS-
block matrix as simple cubic spheres, thus changing the morphology generated in
nanocomposites if compared with that for neat PSEO block copolymer, and allowing to
obtain nanostructured materials with TiO2 nanoparticles confined in a controlled way in one
of the blocks.
Acknowledgments
This work was supported by a grant from Basque Country Government, “Programa de becas
postdoctorales de incorporación de doctores a la CAPV” for Dr A. Tercjak. Financial support
from Basque Country Governments in the frame of ETORTEK-NANOTRON project
(reference number: IE05-146) is also gratefully acknowledged. We would like to
acknowledge Sergei Magonov for fruitful discussion.
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RESEARCH AND REVIEW STUDIES
Chapter 1
DURABILITY ASPECTS OF POLYMER

COMPOSITES USED FOR RESTORATION
AND REHABILITATION OF STRUCTURES
Mariaenrica Frigione*
Department of Innovation Engineering, University of Salento, 73100 Lecce, Italy
Abstract
The acceptance of the fiber-reinforced polymers (FRP) in the strengthening of civil and
monumental structures is due to a combination of suitable properties and
manufacture/installation capability. With respect to traditional building materials, such as steel
and concrete, polymer composites offer high strength/weight ratio, good resistance to fatigue,
excellent chemical and corrosion resistance. The long term behavior of FRP subjected to
weathering is still not well understood. Environmental factors can have a crucial effect on
their performance in service. The various environmental factors that have been identified as
having a deleterious effect on the durability of FRP are: moisture, temperature changes,
freeze-thaw, alkaline environment, ultraviolet radiations. The durability in severe
environments, however, is one of the key factor which has contributed to the acceptance of
polymer composites in demanding applications, such as the aerospace industry.
In this chapter, the properties of several FRP’s employed in civil engineering applications
are analyzed in relation to the environmental agents to which they can be exposed. Specific
interactions can be identified between the different external agents and the based materials
composing the FRP. Different thermosetting matrices and fibers, employed for restoration and
strengthening applications, are considered. Epoxy, vinyl ester and polyester matrices are
reviewed, evidencing the susceptibility of their mechanical properties and adhesive strength to
weathering. The performance of an FRP exposed to a harsh environment depends also on the
vulnerability of fibers towards the external agents. The fibers most commonly used in FRP for
structural reinforcements are based on three types of compounds: carbon, glass and aramidic.
Laboratory simulations of environmental agents are compared to natural exposure,
emphasizing advantages and limits when reproducing the weather conditions with laboratory
procedures. Some remarks and considerations are, finally, drawn.
*
E-mail address: mariaenrica.frigione@unile.it
26 Mariaenrica Frigione
Introduction
Fiber reinforced polymers (FRP) are increasingly being used to rehabilitate and renew
damaged or overloaded structures, due to their excellent performance, particularly regarding
the combination of high strength with low weight, and to the possibility of modifying their
properties, though the choice of appropriate constituents, to suit a wide variety of
applications.
It is generally accepted that polymer composites are very durable materials, particularly
those designed for aeronautical applications. However, FRP materials used in civil
engineering applications are significantly different from those developed in the last 40 years
in the aerospace industry. The techniques used to process composites are also substantially
different in the civil engineering industry.
As previously experienced in other fields, the lack of durability data along with the need
for high safety standards has forced design engineers to use factors higher to ensure
satisfactory performance in service. This, however, not only increases the cost and the weight
of the composites but also reduces the capability of tailoring properties to specific needs.
The durability of a rehabilitated structure depends on the material chosen and the
processing technique used for this operation, the load regime and the kind and level of
environmental exposure. At the present time, only few data on durability of FRP in this
specific field are generally assured. Some data are contradictory, despite to the enormous
efforts carried out by several worldwide research investigations on the effects of
environmental agents on properties of composites in the course of their lifespan in service.
Moreover, durability data available in the literature are often presented devoid of details on
the materials and the processing techniques used (for instance the chemical formulations of
the matrix resins, temperature and time used for curing, and the time elapsed before the
execution of durability tests). This information, on the other hand, is fundamental for the
understanding of the effects of the external environment on properties of materials and, as a
consequence, for an accurate prediction of their behavior over their lifespan.
The aim of this chapter is to review the publications that have appeared in the last 15
years on the durability of FRP specifically designed for rehabilitation of civil infrastructures,
focusing on possible differences in results derived from similar studies and the long term
behavior of these materials when subjected to different environments.
Composites
The fairly wide use of polymers composites (FRP) in aerospace applications, where very low
levels of failure are allowed, suggests that their use in civil infrastructure should be totally
free of any problems. However, the composite materials used and processes used in the
aerospace industry are unlikely to find significant application in civil infrastructure, due to
their high cost and stringent processing requirements. Low temperature cured resins are often
used in civil engineering rather than high temperatures types. Moreover, the processes
conditions in which the resins set and harden are often not sufficiently controlled and kept
constant, unlike the factory fabrication conditions used for aerospace products.
Durability Aspects of Polymer Composites Used for Restoration… 27
These types of uncertainties strengthen the necessity for through investigations on the
behavior of composites specifically designed for civil engineering applications, especially
when exposed to common environmental conditions over long periods of time.
The long term durability of polymer composites depends intrinsically on the choice of
constituent materials, method and conditions of processing and surrounding environmental
conditions over their entire service lives. Although FRP composites do not corrode, they do
undergo physical and chemical changes, including oxidation and hydrolysis. Data from
laboratory studies, moreover, have revealed significant levels of degradation in FRP
composites when subjected to moist environments, at high temperatures and under
mechanical stresses [Karbhari, 2002, a)].
Effect of the Temperature and Thermal Cycles
Temperature can influence the properties of the composite in several ways. It can initially
promote the post-cure of the matrix and then cause its degradation; both of these will affect
the properties of the whole system. Thermal variations can result in micro-cracks at the
interface between FRP and concrete because of different thermal expansion coefficients,
seriously affecting the bond properties [Micelli and Nanni, 2004]. Moreover, the resins used
as the matrix for the composite soften when exposed to temperatures above the glass
transition temperature. An increase in temperature may, therefore, cause a large reduction in
the elastic modulus, which may even cause an increase in susceptibility to moisture
absorption [Tu and Kruger, 1996; Karbhari et al., 2003].
Repeated thermal cycles, at temperatures between 0 and 100°C, were performed on glass-
fiber composites based on a bisphenol-A epoxy matrix cured at 20°C [Rinaldi and Maura,
1993]. The tensile strength initially increased, during the first 20-30 cycles, then became
stable. This was explained in terms of completion of curing reactions. However, after 40
cycles, the impact strength decreased considerably, due to both the formation of micro-cracks,
generated by the thermal changes, and further hardening of the matrix, due to the
advancement of curing reactions.
An experimental study was conducted in order to identify the effects of different
environments on the tensile properties of three advanced polymer composites materials
(APC) [Hulatt et al., 2002]. For this purpose, a unidirectional woven carbon fiber reinforced
polymer (CFRP), a 0/90° biaxial woven fabric of glass fiber and a +/– 45° stitched glass fiber
reinforced polymer (GFRP) composites, employing two plies of prepreg each, were
manufactured. The matrix of the three composites was a “mild-cure” epoxy resin. Curing of
the composites was carried out for 16 hours at 65°C. After this curing cycle, the epoxy matrix
displayed a final Tg of 75°C. The coupon samples were, then, tested by tensile tests at three
different temperatures, i.e. 22°, 45° and 60°C. The results showed clear deterioration of
mechanical properties (longitudinal strength and stiffness) for all three composites when the
test temperature approached the glass transition temperature of the matrix resin. At 60°C, in
particular, the reductions in stiffness ranged from 10% to 30%. Similar decreases were also
measured for tensile strength at the same temperature. At 45°C, the influence of temperature
was apparent only for the +/– 45° GFRP specimens, which brought about a reduction in
modulus and strength in the region of 15% and 20%, respectively. In the latter systems the
properties of the matrix resin have a considerable influence on the general performance of
composites. When the fibers lie in the line of action of the load, on the other hand, the
properties of the CFRP and GFRP composites remained almost unaffected by moderate
changes in temperature. However, there was a large variability in the results, suggesting that
the quality of the laminates produced was rather poor.
In order to analyze the resistance of the bond strength between composite and stone after
numerous thermal cycles, a study was performed on a CFRP, based on a cold-cured epoxy
resin, applied to a calcarenitic stone [Rizzo et al., 2002]. A decrease in the bond strength
between the composite and the specimens of stone by about 10% respect the initial value, was
measured after repeated thermal excursions, from 5° to 70°C. This was explained in terms of
different thermal coefficients of the matrix resin of the composite and the stone. Failure took
place mainly at the interface between the composite layer and the calcarenitic substrate, with
a partial removal of material from the stone surface.
A wide study on the long term behavior under severe environments was recently
presented for different types of FRP laminates produced by wet lay-up technique
[Tavakkolizadeh and Saadatmanesh, 2004]. Composite specimens were produced using one
type of epoxy resin (i.e. a two component bisphenolic epoxy) and seven different types of
fabric (i.e. unidirectional and bidirectional fabrics of glass, carbon and hybrid glass-carbon
and glass-aramidic fabrics). A one layer fabric was always used to produce the composite for
this study. After the cure of the resin, carried out at ambient temperature for 7 days, the
samples were exposed to dry air at 60°C up to 27 months. The specimens were subjected to
uniaxial tension test after different exposure times, i.e. after 8, 16 and 27 months,
respectively. For comparison purposes, similar samples, obtained by using the same materials
and technique, were tested after being kept for 8 months in a controlled laboratory
atmosphere. The results showed that the laminates exposed to dry heat were only slightly
affected by this treatment. In particular, the ultimate strength of unidirectional and
bidirectional glass laminates decreased by about 11-12% after 16 months of exposure;
whereas the values of strain at failure of composite based on unidirectional glass fabric with
loose fibers sandwiched between two mats and of unidirectional and bidirectional glass
laminates were reduced by 6%, 18% and 16%, respectively. The mechanical properties of
carbon fiber based laminates remained totally unaffected by the thermal treatment received.
SEM observations were performed on commercial composite samples, based on a cold-
cured epoxy reinforced with carbon fibers and subjected to thermal treatments after 6 months
of cure at ambient temperature, revealed variations in the morphology of the specimens
relatively to the untreated material [Lettieri, 2005]. After 10 days at 50°C, the fracture surface
of the specimens, ruptured in liquid nitrogen in order to achieve a brittle fracture, showed the
same characteristics observed on untreated samples, i.e. a typical fracture of a composite
material, showing some fibers being pulled out and holes formed where the fibers were
removed. In the latter case, however, the fiber pulled-out length was short. Moreover, the
surface of the de-bonded fibers of the untreated specimens appeared essentially clean at
microscopic level, with only any traces of resin at the surface. This is evidence of a poor
interfacial bonding between the fibers and the polymer matrix [Abdel-Magid et al., 2003].
Fragments of resin matrix, on the other hand appeared around the fibers of specimens kept in
oven for 10 days. Both the shorter length of the pull-out fibers and the presence of residues of
resin on their surfaces, suggest that a stronger interfacial bond is obtained after the thermal
treatment. The samples kept at 50°C for longer time (i.e. 28 days) showed a similar behavior
in the internal region, where the fibers surface on the fracture plane is flat and a negligible
interface de-bonding is observed. The fibers placed externally, on the other hand, exhibited an
irregular fracture surface. This behavior revealed that the portion of the laminate affected by
the changes in morphology and properties induced by the treatment becomes thicker with
increasing the exposure time, progressively advancing toward the center of the specimen.
Similar observations were reported by other researchers on polyimide-based FRP [Berens and
Hodge, 1982]. Finally, the thermal treatment at 50°C produced an increase in the Tg of the
matrix resin, which became even higher by increasing the heating time. This result has
indicated that, although after curing times of about 5 months the Tg reached a constant value,
the resin matrix was still not fully cross-linked and that, when the resin is heated at 50°C, a
post-curing process takes place.
In a strengthening system specifically designed for fire resistance, the bond
characteristics of cold-cured (ambient temperature) epoxy based CFRP joined to concrete
blocks was studied within the context of fire situation [Gamage et al., 2006]. It was found that
the bond between the externally glued composite and concrete is considerably weakened
when the average temperature within the epoxy adhesive goes up to 70-80°C, irrespective to
the bond length of the joint. From this was concluded that, for applications susceptible to fire
risks, the temperature of epoxy adhesives should not exceed 70°C in order to maintain the
integrity of the adhesive layer between the composite and concrete.
A study on field and laboratory evaluations of E-glass/vinylester systems, was conducted
fairly recently [Zhang et al., 2000]. Two types of fabric were used for the composite, i.e. four
layer made of woven rowing and three layers of woven rowing sandwiched between
alternating layers of chopped strand mat. The matrix was a vinylester resin, capable of curing
in 45 minutes at ambient temperature to ensure a satisfactory performance. However,
composite panels, produced by wet lay-up, were allowed to undergo complete cure under
ambient temperature conditions at 60-70% R.H. for a period of two months. Based on a series
of temperature measurements performed over an extended period of time in Sidney,
experiment were carried out using simulated accelerated thermal cycles, up to 120 cycles,
with a minimum temperature of 15°C (i.e. the minimum temperature recorded at night) and a
maximum temperature of 100°C (i.e. lower than the Tg of the vinylester resin, which was in
the range of 100-116°C). The heating and cooling rates were set at 0.7°C/min and 0.2°C/min,
respectively. Tensile tests were performed to assess the extent of degradation. Thermal
cycling resulted in a decrease in tensile strength of approximately 11%, while the modulus
remained more or less unchanged. There was an increase of Tg of about 25°C, which was
attributed to the post-curing of the vinylester matrix as a result of the thermal treatment.
However, micro-cracking in the matrix and severe discolorations and erosions at the surface
were observed, resulting in a clear appearance of the fiber pattern.
A GFRP-confined concrete structure, produced by manual wet lay-up technique, showed
a significant loss of mechanical properties in terms of strength and ductility after exposure to
high temperature cycles [Corvaglia et al., 2006].
Effect of Moisture and Liquid Water
In a recent study it was found that the rate of degradation of a polymer composite exposed to
a fluid environment is related to the rate of sorption of the fluid and that sorption behavior, in
turn, depends on: the type and concentration of fluid, temperature, applied stress, damage
status, chemical structure of the matrix, fiber/matrix interface [Micelli and Nanni, 2004].
The primary effect of water present in a wet or moist ambient is its diffusion into the
matrix resin causing both irreversible (hydrolysis) and reversible (plasticization) degradation
of the properties. The water ingress can cause swelling of the polymeric matrix, which can
produce internal stresses. These are, in part, attenuated by plasticization effects. The moisture
can also penetrate along the fiber-matrix interface, causing deleterious effects to the fiber-
matrix bond [Rinaldi and Maura, 1993; Guo and Kagawa, 2000; Kueseng et al., 2001;
Karbhari, 2002 a)]. Micro-cracks can also result from water ingress and amplified at high
temperatures immersions [Abanilla et al., 2006 a)].
As a general rule for most thermosetting resin systems, the Tg is reduced by 10-20°C for
every 1% of absorbed water or moisture [Wypych, 1995; Pritchard, 2000]. A similar rule was
reported also for matrices in composites [McKague et al., 1978; Peyser and Bascom, 1981;
Abanilla et al., 2006 b)]. It, however, cannot be applied because the transport of water in a
composite will take place through both diffusion inside the matrix resin and transport along
the fiber-matrix interface. Therefore, the amount of the absorbed water will strongly depend
on the amount of fibers, the number and the disposition of layers in the composite, the void
content of the laminate, the quality of the bond of the matrix to the fibers [Bank et al., 2003].
On the other hand, the Tg measured on a composite refers only to the matrix polymeric resin
and it is influenced merely by the water absorbed by the resin itself.
Generally speaking, the behavior of FRP materials immersed in pure water is
approximately Fickian [Abanilla et al., 2006 b)], whereas a non-Fickian water diffusion
behavior has been observed in fiber reinforced thermosets. This is often attributed to the
heterogeneity of the structure. Initially, water diffuses mainly in the resin matrix; then, it
enters the composite via capillary action if voids exist near the fibers or along fiber-matrix
interface [Boinard et al., 2000]. In some cases, moreover, diffusion follows the Fickian
behavior only at the beginning of the sorption process [Silva, 2007]. Thereafter, an
equilibrium amount of moisture was not reached since the matrix resin could be physically
damaged [Micelli and Nanni, 2004].
At elevated temperatures, saturation was reached substantially earlier, with a water
uptake occurring with higher rates and associated with an accelerated mechanisms of
deterioration [Abanilla et al., 2006 a)]. The presence of micro-cracks and bubbles increases
the diffusion rate of water and the saturation limit. The associated hydrostatic dilatation which
takes place in the matrix produces internal stresses and more micro-cracks, effects partially
attenuated by the plasticization of the matrix [Rinaldi and Maura, 1993].
Since micro-voids are randomly dispersed in FRP structures for civil engineering
applications, due to the manual wet lay-up techniques normally used, the effects of water
transport on the mechanical properties of the composites can vary considerably. Therefore,
the results reported by different researchers must be considered only in a qualitative way.
The presence of hydrophobic units, for instance aromatic rings, in curing agents
employed to cross-link a bisphenolic DGEBA resin at room temperature, leads to a superior
behavior of the relative glass fiber composite after a prolonged period of immersion in water
[Rinaldi and Maura, 1993]. The mechanical (tensile and flexural) strength of the composite
were entirely unchanged after four months of immersion in water.
The durability of Carbon Fiber Sheet (CFS) composites, based on epoxy primer and
adhesive and manufactured from single-ply unidirectional fibers by hand lay-up, was
analyzed after prolonged immersion in water [Frigione et al., 2004]. Curing procedure of
primer and adhesive was carried out for 20 days at ambient temperature (23°C). The results of
tensile tests performed on CFS samples, after different time spans in distilled water up to 25
weeks, revealed insignificant influence of this treatment on the properties of the composite.
Within experimental errors, the tensile modulus, the strength and strain at break did not
change after prolonged immersions in water. These results proved that the mechanical
properties of composite materials in the fiber direction basically depend on the properties of
the fibers which are not affected (in the case of carbon fibers) by the presence of water.
Seven different types of FRP laminates were manufactured using the wet lay-up
technique, employing a two part cold-cured epoxy, and immersed up to 27 months in distilled
water at neutral pH [Tavakkolizadeh and Saadatmanesh, 2004]. The laminates consisted of
one layer of fabric using different fibers (carbon, glass, hybrid glass/carbon and
glass/aramidic) and weave mixed patterns (loose or sticky string fibers sandwiched between
two mats, unidirectional and bidirectional mats, respectively). The epoxy matrix of all
composites was assumed to be cured after 7 days at ambient temperature. Uniaxial tensile
tests were performed on untreated and immersed specimens in controlled water environment
for 8 months. Water was found to have no significant effects on the modulus of elasticity of
all the laminates. The carbon and glass/carbon laminates were almost unaffected by the
immersion treatment in water, showing an insignificant decrease in ultimate strength and
strain at failure, irrespective to the weave patterns. On the other hand, the effect of water was
considerable in the case of laminates manufactured with glass or hybrid glass/aramidic
fabrics. The highest reduction in both mechanical properties (almost 50%) was found for the
laminate made with unidirectional glass fabric manufactured with loose fibers. The decreases
in ultimate strength and strain was general higher with immersion times.
Samples of a commercial composite, based on a cold-cured epoxy reinforced with carbon
fibers and cured for 6 months at ambient temperature, were either immersed in distilled water
or exposed to different levels of humidity [Lettieri, 2005]. The amount and the rate of water
absorbed during the immersion was similar to that measured on samples exposed to a
saturated water vapor atmosphere (i.e. at 100% R.H.); this as a consequence of the fact that
the chemical potential of water in the liquid state and at 100% R.H. is the same. The
immersion in water not only produced a decrease in Tg, due to plasticization effects, but
caused also a progressive reduction in the residual heat of reaction. This suggests that the
absorbed water can reactivate the cross-linking reactions in the epoxy matrix. SEM
examinations of the specimens subjected to hygrometric treatments and fractured in liquid
nitrogen showed some differences in morphology of the fracture surfaces from those observed
on the untreated systems. The samples immersed in water for 10 days exhibited a fibrous
fracture mode similar to that observed for the control samples. On the other hand, the
examination at a higher magnification of the layers closer to the surface reveals that the action
of the absorbed water brings about an incipient loss of contact between fibers and matrix,
evidenced by the presence of visible gaps at their interface. The SEM examinations of the
samples subjected to 28 days immersion in water revealed the presence of two distinct zones.
The internal area of the specimens showed a fibrous fracture mode, with a moderate fiber
pull-out similar to that experienced by the untreated samples. In contrast, a ductile fracture
surface was observed on the surface layers, which did not display the presence of fibers
embedded in the matrix. However, the most salient features were found in the region where
the fracture changes from brittle to ductile mode, located at around 50 – 60 μm from the
surface of the specimen. In this zone, the SEM examinations revealed the presence of gaps
between fibers and matrix, similar to the morphology observed in the surface layers of the
samples immersed in water only for a short time (i.e. 10 days). It was hypothesized that the
first stage of the degradation caused by the absorbed water takes place in this intermediate
zone. This damaged layer progressively advances from the surface toward the center of the
sample, resulting also in a gradual increase in the amount of water.
A broad durability study was undertaken on a wet lay-up composite, based on a two-part
epoxy cured at 23°C reinforced with carbon fibers, in the form of unidirectional laminates
[Abanilla et al., 2006 a); Abanilla et al., 2006]. The effect of immersion in deionized water
for up to 100 weeks at 23°C was analyzed. Before immersion, the composite samples were
cured at ambient temperature for 48 hours and were then preconditioned at 23°C and 30%
R.H. for 30 days. Several thermal and mechanical tests were performed on the specimens
after different immersion times. The immersion in deionized water produced a progressive
decrease in glass transition temperature, varying from 92°C for unexposed laminate to 67°C
after a 100 weeks immersion. The Tg values were measured by dynamic-mechanical thermal
analysis. The reduction in average tensile strength due to immersion in water depended
mainly on the number of layers used to produce the laminates. In particular, the decrease in
strength was less than 1% for the 2-layer thick specimens and about 32% for the 6-layer thick
samples. The results were explained by assuming that the most of deterioration took place
between the adjacent layers of fabric. This appeared to be supported by SEM examinations. A
100-week immersion period caused a reduction in stiffness of 5% for the 2-layer systems and
12% for 6-layer specimens. Flexural tests on the same samples often showed an initial drop in
flexural strength after different immersion times, which was followed by steady behavior. The
stepped response was believed to be a characteristic of the deterioration of the interface and
interlayer as a consequence of moisture uptake. After the 100 weeks immersion period,
flexural strength was found to decrease by about 27% for the 2-layer samples and by 31% for
the 6-layer specimens. The overall level of observed degradation has suggested that the
moisture uptake has resulted in a predominance of interlaminar yielding as a failure
mechanism. Minor deteriorations were found with respect to flexural modulus, being less than
10% irrespective to the thickness of the specimens. This confirms the relatively low influence
of the number of layers on stiffness. Interlaminar properties, and all those intrinsically
dependent on the resin characteristics and therefore more influenced by moisture, were
measured on the different laminates after the same periods of immersion in water. It was
found that the immersion resulted in a drop in both SBS and in-plane shear strength. The
deterioration again was found to increase with immersion time. In the case of SBS tests,
degradation was more rapid in the first few weeks of immersion, reaching a constant level at
intermediate time. In the case of in-plane shear tests, on the other hand, the degradation never
appeared to reach a plateau, in so far as the strength continued to decreased, even with an
increased rate, before reaching the end of the immersion period. After the 100-week period of
immersion, the decrease in SBS strength was about 26% for the six-layer laminates and 29%
for the twelve-layer composites. The same immersion time produced a decrease in in-plane
shear strength of about 31% for the two-layer systems and 18% for the 6-layer specimens. An
initial increase of this property was observed for the two-layer specimens, which was
explained by the authors in terms of a combined effect of post-cure of the matrix resin and
relief in internal stresses induced during curing. A decrease in the “in-plane modulus” was
also registered, of about 26% for the two-layer thick samples and 20% for the six-layer
specimens at the end of the 100-week period of immersion. Finally, the immersion in pure
water resulted in an increase in the interlaminar fracture toughness for the 6-layer thick
specimens, amounting to an increase of about 35% after 32 weeks of immersion. The
moisture uptake caused plasticization of the matrix resin and resulting in a ductile fracture.
The blunting of interfacial cracks and the fiber-matrix debonding both have contributed to
increase the toughness. The authors concluded that the changes in properties due to
immersion in pure water generally increase with the immersion time and the number of layers
in the composite sample. These results suggest the importance of the design of an optimum
number of fabric layers that satisfy the requirements for impregnation, handling,
strengthening and durability.
The results of tensile tests performed on CFRP composite samples at different time
intervals in distilled water, up to 25 weeks, showed no significant effect on the tensile
mechanical properties of the composite which was based on cold-cured epoxy primer and
adhesive and unidirectional carbon fibers and consisted in one-layer fabric [Frigione and
Sciolti, 2006]. Within the experimental errors, tensile modulus, maximum strength and
ultimate strain remained constant after prolonged immersion periods in water.
The effect of water immersion on the aging characteristics of a commercial GFRP
laminate was illustrated in a recent paper [Silva, 2007]. The GFRP laminate was produced
using a cold-cured epoxy resin, with a initial glass transition temperature of 66°C, and based
on a woven unidirectional E-glass fibers, containing small amounts of aramidic fibers in the
transverse direction. GFRP coupons were immersed up to one year in water at 22°C and
subsequently tested in tensile mode in the fibers direction. It was found that water immersion
at low temperatures did not cause noticeable degradation of the GFRP laminates along the
direction of the fibers in so far as both stiffness and strength displayed negligible changes
after aging in water. In particular, the mechanical properties were slightly reduced at short
immersion times, then increased at intermediate times and subsequently regained the initial
values after a one-year immersion.
Unidirectional E-glass fiber reinforced composite panels, based on a vinylester resin,
were immersed in water and the changes in properties monitored at different immersion times
in deionized water, up to 18 months [Karbhari et al., 2002 b)]. The composite panels were
manufactured by wet lay-up, followed by a vacuum bagging process at 24-27°C and 45-55
R.H.. Panels were fabricated in configurations of 2, 4 and 8 layers of fabric with the mat side
facing the same direction, i.e. towards the mold surface. The samples were cured at ambient
conditions for one month before aging. Other samples were kept under controlled conditions
(23°C and 55% R.H.) for the same time and tested after the same time periods. The Tg of the
unaged composite was about 123°C. Tensile tests were conducted in the primary warp
direction for each specimen. The immersion in deionized water produced a gradual reduction
of strength with increasing immersion time. At the end of the 18 months immersion, the two-,
four- and eight-layer samples showed reductions in tensile strength of about 13%, 31% and
31%, respectively. An increase in tensile strength was, however, measured on unimmersed
specimens kept in controlled atmosphere for 18 months, corresponding to 8%, 15% and 10%
with respect to the initial values for the two-, four- and eight-layer samples. This suggests that
completion of the cure process took place in the samples during this time. Fiber matrix
debonding was observed on specimens immersed in deionized water. Microscopic analysis
revealed that the fibers from samples immersed in deionized water showed some surface
roughness and pitting, as compared to fibers from unexposed specimens.
The mechanical response of ambient cured E-glass/vinylester composite immersed in

water for up to 18 months was evaluated in another study [Wu et al., 2002]. Composite
specimens were fabricated using wet lay-up with the application of vacuum throughout the
cure. The reinforcement consisted of two layers of a quadriaxial glass fabric, laid up
symmetrically about the midplane with the bias (±45) plies toward the center. The cure of the
vinylester resin was conducted at ambient conditions of 22-24°C and 50% R.H.. The samples
were then preconditioned at 23°C and 55% R.H. for three months prior to immersion in
neutral deionized water at 23°C (pH equal to 6.95). Some control samples were kept under
controlled conditions at 23°C and 55% R.H.. The immersion in pure water caused an initial
decrease in Tg over the first 3 months of immersion. The Tg, measured by dynamic-
mechanical thermal analysis, was 119°C and decreased to 115°C after immersion. At longer
immersion time, i.e. 6 months, it increased to values similar to that measured for un-immersed
specimens. Then, it continuously decreased again, up to 105°C after 18 months of immersion.
This behavior was explained in terms of competitions between the effects of plasticization
and hydrolysis, both caused by immersion in water, and those of the completion of curing
reactions, as demonstrated by a substantial decrease in the residual heat of reaction. However,
the Tg measured on samples removed from water after 18 months of immersion, and then
dried for one year at 23°C and 55% R.H. was around 110°C, that is lower than the value
measured on un-immersed specimens. This result confirmed the occurrence of irreversible
changes caused by hydrolysis and curing during immersion in water. Mechanical tensile tests
and interlaminar shear tests were performed on specimens immersed in water for different
time spans, up to 12 months, as well as on unexposed specimens. Immersion in pure water
produced a slow continual decrease in tensile strength, being up to 11% lower than that
measured on un-immersed samples after one year of immersion. A similar trend to that
observed for the Tg was found for the tensile modulus, i.e. an initial decrease after one month
of immersion followed by a new increase during the next five months. The final value of the
modulus after one year of immersion in deionized water was, however, still slightly lower
(about 5%) than that measured on un-immersed specimens. It was suggested that the diffusion
of water through the resin, and the resulting wicking along cracks and fiber matrix debonding,
caused degradation of the resin in regions between layers and brought about a decrease in
both modulus and strength. Moreover, examination of fabrics after 12 months of immersion
showed the initiation of damage at the fiber level through localized pitting and
circumferential cracking. Interlaminar shear properties of GFRP after different immersion
times were measured by short beam shear tests (SBS). The effect of immersion in pure water
on SBS strength was found to be similar to that observed for tensile strength, i.e. a continuous
decrease up to 19% after a one-year immersion. However, the samples recovered a large part
of the reduction in SBS strength after drying for one year. Finally, since a steady level in both
tensile and short beam shear strengths was not reached over the immersion times examined, it
was concluded that such studies can give only short term indications of the behavior of
composite samples immersed in water.
The effect of short term immersion in deionized water of E-glass/vinylester composites,
as function of composite thickness and fabric architecture, was assessed [Karbhari and Zhang
2003]. The composites, produced using the resin infusion process at ambient conditions
(24°C and 56% R.H.), consisted of oriented layers of unidirectional yarn bound to one
another using stitching thread. The architectures considered were: uniaxial, biaxial and
triaxial non-woven fabrics. After infusion, the panels, which were fabricated in thicknesses of
two and four layers of each of the fabric type, were allowed to cure for 24 hours at 23°C and
56% R.H., after which, they were post-cured at 93°C for two hours. Specimens for both
tensile and short beam shear tests were cut form composite laminates in the warp direction
(i.e. along the primary unidirectional yarn) as well as in the fill direction (i.e. perpendicular to
the primary unidirectional yarn). They were then immersed in deionized water at 23°C for up
to 57 weeks. For comparison purposes, reference specimens were kept for the same time in
controlled conditions (24°C and 56% R.H.) and tested along with the immersed ones.
Immersion in pure water at ambient temperature caused a gradual decrease in both tensile
strength and modulus. At the end of the 57 week period of immersion, the reductions in
tensile strength for the 4-layered uniaxial laminate, tested in warp direction, and in tensile
modulus for the 2-layered triaxial laminate, again tested in warp direction, were about 62%
and 23%, respectively. It was also observed that the reduction in tensile strength after
immersion was much higher in the warp direction than in the weft direction, even for
unidirectional laminates. This indicates that the changes were not merely associated with
plasticization and hydrolysis of the resin but also with degradation of both the fiber-matrix
interface and the individual fibers. Referring to the two-layered biaxial specimens, for
instance, the coupons tested in the warp direction showed a lower percentage of strength
retention (i.e. 73%) than those tested in the fill direction (i.e. 88%). However, the effects due
to the test direction are particularly significant in the case of uniaxial specimens, in which the
warp direction is associated with the fiber dominated direction and the fill direction is clearly
resin dominated. The analysis of results throughout the immersion period suggested that
residual cure of the vinylester resin took place during the first stage of immersion in
deionized water. After an initial decrease in the first few weeks of immersion, in fact, the
strength generally increased to levels even higher than those measured on un-immersed
specimens. The results were confirmed by the measurements of the residual heat of reaction
that substantially decreased by increasing the immersion time. It was shown that damage took
place through interface degradation, as well as fiber pitting and cracking. Each of these
effects resulted in additional moisture uptake. Short beam shear tests, conducted on 4-layered
specimens, showed a significant retention of strength. The samples did not reveal any sign of
delamination at microscopic level between the different layers. The only exception was for
uniaxial specimens tested in the fill direction, for which the SBS strength deteriorated by
more than 50% at the end of the 57 week period of immersion. This result was related to the
lack of fibers in the transverse direction and the presence of either debonded areas or
longitudinal cracks along the fibers in the longitudinal direction. This lies perpendicular to the
span of the short beam shear specimen, thereby creating a number of weak zones for
transverse cracking to take place during the test. Finally, the 57 week period of immersion in
water produced a drop in the glass transition temperature of about 5-8°C from the initial Tg of
the laminate in the region of 108-110°C, as measured by dynamic-mechanical thermal
analysis.
Effect of Freeze and Freeze-Thaw Cycles
The effect of cold climates on FRP based on cold-cured matrices is of particular concern, as
demonstrated by different researchers [Lord and Dutta, 1988; Karbhari and Pope, 1994;
Karbhari et al., 2000; Zhang et al., 2001; Karbhari et al., 2001; Karbhari, 2002 b); Abanilla et
al., 2006 a)]. They showed, in fact, that freeze and freeze-thaw conditions, with and without
immersion in aqueous environments, can lead to degradation of the composite through matrix
micro-cracking and fiber-matrix debonding, bringing a reduction in strength and stiffness, and
also a higher level of brittleness of the matrix. The embrittlement of the matrix resin of the
composite can, in turn, produce further crack growth through the matrix, leading to an
accelerated penetration rate of water. During the thawing regime, the properties of the matrix
resin and the fiber-matrix bond can be affected even further by moisture penetration.
Different wet lay-up composites, based on a cold-cured epoxy reinforced with E-glass,
aramid fibers and E-glass fibers, respectively, were evaluated from durability point of view
after exposure to freeze conditions [Zhang et al., 2001; Karbhari et al., 2001]. The freeze
condition was performed by exposing the specimens to a temperature of -26°C for 6 months
and 12 months. For comparison purposes, blank samples were produced and stored in
controlled conditions (23°C, 55% R.H.) over the same time periods. These latter samples
were found to be curing further, with an increase in Tg from 68°C to 72°C for the first system
and from 73°C to 75°C for the second. The exposure to freeze condition is likely to inhibit
further curing, with aged systems showing a Tg slightly lower than that measured on un-
exposed specimens. Sustained exposure to -26°C, on the other hand, had only limited effects
on tensile and interlaminar shear properties. The modes of failure observed were
predominantly brittle, indicating the stiffening of the matrix resin at sub-zero temperatures.
Exposure of freeze-thaw conditions (between -10 and 23°C, at the rate of one cycle per
day) performed on wet lay-up carbon fibers/cold-cured epoxy composite resulted in a
decrease in tensile strength of up to 31% after 100 weeks of exposure, together with the
separation of fiber surfaces from the surrounding matrix resin [Abanilla et al., 2006 b)]. The
exposure to freeze-thaw cycling initially causes tensile elastic modulus to increase, due to
further curing of the matrix resin. Then a slight deterioration in stiffness was measured,
resulting in a very small overall change over an extended period of time. A low level of
deterioration was measured with respect to flexural properties, being the flexural strength
reduced by about 13% and the modulus by about 9% after 100 weeks of freeze-thaw cycles.
The exposure to freeze-thaw cycling affected to a minor extent also the SBS strength
[Abanilla et al., 2006 a)]. The authors explained that the loss of this property caused by the
debonding between the fibers and the matrix was probably offset by the stiffening of the
matrix resin. The authors stressed the significance of these results, since the whole period of
exposure employed in their research resulted in 700 freeze-thaw cycles, i.e. substantially
higher than the number that would be achieved in most locations over a decade. The
exposition to freeze-thaw cycles, on the other hand, produced a certain decrease to in-plane
shear strength, even thought this did not exceed 20%. Microscopic analysis of fracture
surfaces revealed the brittle nature of the fracture as well as the presence of voids. Finally, the
interlaminar fracture toughness tests showed a progressive deterioration increasing the
number of cycle, resulting in a maximum decrease of about 31%. The glass transition
measured on the composite after a 100 week period of exposure to freeze-thaw conditions
seemed to be slightly affected by this agent, since the final decrease in Tg was in the range of
5°C. The results were in agreement with the previous work performed on carbon vinyl ester
systems [Rivera and Karbhari, 2002].
The effect of freeze-thaw cycling on reinforced concrete beams externally strengthened
with different FRP sheets, was presented in two papers [Green et al., 1998; Bisby and Green,
2002]. Even if not explicitly specified in the papers, the trade name of the products evaluated
suggests that wet lay-up process was used to apply al least three kinds of FRP plates on four
on concrete beams, two based on carbon fibers and an epoxy matrix, the third on E-glass
fibers and an epoxy matrix. On the other hand, the forth FRP, based on carbon fibers and an
epoxy matrix, was a pultruded sheet, bonded with a cold-cured epoxy adhesive. All the FRP
laminates were bonded only over a short length at each end of the beam, in order to promote a
debonding failure mode rather than tensile rupture of the FRP material. Once plated, all the
strengthened beams were subjected to repeated freeze-thaw cycles (from 0 to 300 cycles),
consisting of freezing in air at -18°C for 16 hours followed by thawing in water at 15°C for 8
hours. They were, then, tested to failure in four-point bending. The results of flexural tests
found for the first CFRP analyzed indicated that, by increasing the number of freeze-thaw
cycles, the ultimate load and midspan deflection were somehow decreased The results were
explained in terms of an excessive stiffening of the epoxy adhesive layer as a consequence of
the severe exposure with reductions in benefits carried out with the strengthening achievable
with the application of a FRP plate. On the other hand, the bond strength was not adversely
affected by the exposure and may even be improved by freeze-thaw cycles, according to the
results showing an increased average bond strength. The exposure of concrete beams plated
with the second CFRP to freeze-thaw regime has led again to small decreases in fracture load
and midspan deflection along with a decrease in average bond strength. Similar results were
found for concrete beams plated with GFRP laminate. The results suggested that the FRP-
concrete bond might be damaged by exposure to freeze-thaw cycles. In the last two cases,
moreover, the damage observed after 50 freeze-thaw cycles was apparently greater than after
200 cycles. The authors hypothesized that, by increasing the number of cycles, the epoxy
adhesive used to apply the FRP plates to concrete had more time to complete the curing of the
resin. The failure mode observed for concrete beams plated with both CFRP laminates
essentially consisted of a total debonding of the composite plate at the epoxy-concrete
interface, with a very thin layer of concrete remaining bonded to the FRP. The failure surface
of the CFRP-concrete bond changed with increasing the number of freeze-thaw cycles. The
failure surface of the control specimens was extremely coarse, with some of the substrate
concrete pulling away from the beam and remaining bonded to the FRP sheet. By increasing
the number of freeze-thaw cycles, the failure surface became much smoother, with little or no
substrate concrete remaining bonded to the CFRP plate. The authors hypothesized that a
change in the elastic properties of the CFRP epoxy matrix, as consequence of freeze-thaw
exposure, caused some redistribution of load at the CFRP-concrete interface, thus reducing
the effect of stress concentrations in the substrate concrete and moving the failure surface into
the adhesive layer. In the case of concrete beams plated with GFRP laminate, two failure
modes were observed: the first consisting of total debonding of GFRP at epoxy-concrete
interface, similar to the failure displayed by CFRP plated beams. The second, consisting of
partial debonding at GFRP-concrete interface accompanied by complete tensile failure of the
FRP at midspan, becoming more prominent by increasing the number of freeze-thaw cycles.
Since the average bond stress at failure was found to decrease by increasing the number of
freeze-thaw cycles, the authors suggested that the exposure reduces the strength of the
composite sheet itself, causing rupture of the GFRP component prior to debonding. The
failure at interface between GFRP and concrete, moreover, changed with increasing the
number of freeze-thaw cycles in a manner similar to the CFRP plated concrete beams.
Commercial CFRP, based on a cold-cured epoxy resin, were applied to bricks in order to
analyze the resistance of the bond strength between composite and brick after numerous
thermal cycles, including a freeze condition [Briccoli Bati and Rotunno, 2002]. Any cycle,
composed by 6 hours at 50°C followed by 6 hours at -8°C, was repeated up to 96 times. The
parameters analyzed were the number of cycles performed and the width of the composite
stripes applied (from 1 cm to 8 cm). It was found that the effect of the number of cycles
performed was irrelevant only when the smallest composite layer was applied, i.e. that with a
width of 1 cm. By increasing the width of the composite layer applied, the effect of the
thermal excursion became more and more severe by increasing the number of cycles. The
mechanical tests revealed a noticeable decrease in the bond strength also for the specimens
having a 2 cm width. In most of the cases, the rupture took place at the interface between the
composite layer and the brick, with a partial removing of the brick surface. In particular, it
was not possible to measure the strength of the joint using layers with a 8 cm width after 68
cycles, since a complete loss of the adhesion between composite and brick occurred. The
mentioned results suggest that the harsh effects of thermal cycles can be attributed to the
different coefficients of thermal dilatation of composite and bricks, since the influence of the
variations in temperature is more relevant by increasing the contact interface between these
two different materials.
Carbon fiber and E-glass fiber reinforced vinyl ester composites, fabricated by the wet
lay-up process using three layers of unidirectional carbon or E-glass fibers and cured at
22.5°C and 50% R.H., were exposed to different exposure conditions for an overall exposure
period of 100 days, in order to evaluate the effect of these severe conditions on the behavior
of composites [Rivera and Karbhari, 2002; Karbhari et al., 2002 a)]. The environmental
conditions chosen were as follows: a) exposure to a constant temperature of -10°C (freeze
condition); b) exposure to freeze-thaw cycles (from -10°C to 22.5°C, repeated every 24
hours) at low humidity levels (i.e. 20% R.H.); c) exposure to freeze-thaw cycles (as before)
with immersion in deionized water at 22.5°C. For comparison purpose, some specimens of
CFRP and GFRP were stored at 22.5°C and 50% R.H. as reference samples. Measurements of
tensile properties performed on flat composite panels showed that exposure to a constant
temperature of -10°C results only in a minor increase in both strength and modulus for CFRP
(less than 3%). The same exposure for the glass reinforced composite samples showed
slightly higher increases in both stiffness and strength (i.e. up to 6% for modulus and from
9% after 30 days and to 3% after 100 days of exposure for strength). This trend was related to
the hardening of the polymeric matrix at temperatures well below its Tg, which was and
confirmed by the results of dynamic mechanical analysis. However, failure observed for the
CFRP system was found to occur in a catastrophic manner, through a brittle mode with
considerable fragmentation. In contrast, all the freeze-thaw exposure regimes have resulted in
a small reduction in tensile strength (never exceeding 10% for both composites) and modulus
(up to 5% and 7% for GFRP and CFRP, respectively). This was attributed to matrix micro-
cracking and fiber-matrix debonding. Exposure to aqueous environments magnifies the effect
of the “dry” freeze-thaw causing also a loss of resin in the interfacial regions, as indicated by
micrographic analysis and confirmed by studies of moisture absorption. The latter, in
particular, showed a loss in weight through an intermediate peak in weight increase. All the
exposures performed, finally, resulted in a decrease in the glass transition temperature for
both composite systems, measured by dynamic-mechanical thermal analysis. The maximum
reduction in Tg for both CFRP and GFRP was measured after exposure of 100 days to freeze-
thaw cycling in deionized water, being about 10°C and 6°C for CFRP and GFRP,
respectively. This was explained as a plasticization effect on the vinylester matrix as a result
of moisture absorption.
However, freeze-thaw cycles produced less severe effects for wet lay-up commercial
thermosetting FRP systems relatively to other kind of aging, such as high temperature cycles
and saline environment [Corvaglia et al., 2006]. Major concerns were reported with respect to
the reduction of compliance, due to the stiffening of matrix resin. In particular, it was
observed a higher reduction in ductility of GFRP-confined concrete cylinders when
increasing the number of freeze-thaw cycles.
Similar results were previously found by other researchers, i.e. freeze-thaw cycling
reduces significantly the strength and ductility of FRP wrapped concrete cylinders, in
comparison to specimens kept at room temperature [Soudki and Green, 1997; Toutanji and
Balaguru, 1998]. It must be emphasized, however, that wrapped cylinders exposed to freeze-
thaw regimes showed a significant increase in strength respect to unwrapped cylinders
exposed to the same environment. That is to say that adequate FRP wrapping still remains an
effective remedy for restoring the strength of a freezed-thawed cylinder up to its initial value,
i.e. the value relative to unwrapped concrete element kept in a controlled atmosphere.
Effect of Aqueous Solutions and Chemicals
The performance of FRP strengthened structures in an alkaline or acid environment depends

on the intrinsic resistance of both matrix and reinforcing fibers to these agents. It is well
known, in fact, that, although moisture absorption, in itself, causes degradation of composites,
the actual effects are largely dependent on the nature of aqueous solution. The presence of
salts such as NaCl, for instance, can have the following effects: a) reduce the maximum
moisture content (at “saturation” condition); b) cause deviation from Fickian behavior in the
process of absorption; c) induce an earlier onset of irreversibility [Jones and Dickson, 1984;
Soulier, 1988].
The durability of FRP materials used in construction are, therefore, related to the
conditions prevailing within the concrete, in additions to external factors. In the case of
GFPR, when alkaline solution penetrates the composite, it can produce an embrittlement of
the glass fibers and a damage at the fiber/resin interface, due to the growth of hydration
products. Although the use of a polymeric matrix as a binder around the glass filaments
provides protection to the fiber, there is still concern related to the diffusion of alkali solutions
in the bulk the resin towards the fiber surface. All the mentioned effects lead to loss of tensile
strength and interlaminar transverse properties [Phillips, 1983; Nanni et al., 1998; Zhang and
Karbhari, 1999]. Another concern is related to the effect of the degradation of the adhesive
resin, causing a loss of bond with concrete [Bank et al., 1998].
Micelli and Nanni have examined the durability in alkaline environments of different
commercial pultruded carbon fiber reinforced plastic (CFRP) rods based on two mild-cured
thermosetting matrices, i.e. an epoxy/vinyl ester modified resin and an epoxy resin, and glass
fiber reinforced plastic (GFRP) based on a polyester resin, all used to replace steel
reinforcement in structural concrete [Micelli and Nanni, 2004]. The Tg of the three resins
were: in the range of 75-85°C for the epoxy/vinyl ester modified matrix, in the range of 85-
100°C for the epoxy matrix, and 70°C for the polyester resin. FRP specimens were exposed to
simulated alkaline concrete pore solution at two temperatures, 22°C and 60°C, in order to
quantify the possible acceleration effects of moderate temperatures. The measure of tensile
and transverse mechanical properties, calculated on the specimens before and after the
exposure to the selected agent, gave indications on the effects of the alkaline solution on the
FRP performance. The tensile properties of CFRP were not affected by the immersion in the
simulated concrete pore solution in the case of rods based on epoxy matrix. FRP based on
epoxy/vinyl ester modified matrix, on the other hand, experienced a 8% reduction after a 42
days exposure in the alkaline solution at 60°C. The latter effect was explained in terms of
degradation of the matrix resin rather than fiber damages. On the other hand, exposure to
alkaline solution affected more significantly the GFRP rods, their tensile ultimate strength
showing reductions of 30% after a 21 days exposure and of 40% after a 42 days one, both
performed at 60°C. Similar results were also found in another study on GFRP rebars based on
polyester resin (Tg = 70°C) and E-glass fibers [Micelli and La Tegola, 2004], i.e. reductions
in tensile strength of about 15% and 20% after 20 and 40 days of exposure to alkaline
solution at 50°C, respectively. FRP rods based on an epoxy matrix, on the other hand, showed
almost unaffected properties. FRP systems based on epoxy/vinyl ester modified matrix were
moderately affected by the diffusion of alkaline solution, especially at a moderate
temperature. The immersion in simulated concrete pore solution at 60°C, in fact, caused a
reduction in the transverse properties of about 20% and 35% after 21 and 42 days,
respectively. GFRP specimens based on a polyester matrix, previously exposed to alkaline
solution for 42 days at 60°C, displayed extensive damage before testing, which was attributed
to fluid penetration. Accordingly, the residual transverse properties measured in this case
were found to be only about 10% of the initial value. Finally, SEM examinations of epoxy
matrix based rods showed the integrity of fiber/matrix interface, explained with the good
quality of the epoxy resin used. On the other hand, in the epoxy/vinyl ester modified resin
based bars, damage at the fiber/resin interface was observed after the conditioning treatment.
However, carbon fibers did not show weakness towards alkaline solutions, even if fluid
penetration occurred. Extensive cracking in the matrix of GFRP bars were well visible after
the conditioning procedure. SEM examinations revealed a significant damage of the fibers,
due to alkaline fluid penetration. The authors concluded that the use of a polyester resin as
matrix for GFRP composites is not recommended for the construction industry, since this
resin did not provide adequate protection of the glass fibers, as they were strongly damaged
by the penetration of alkali ions.
After a prolonged immersion (up to 5 months) in an acid solution (1 molar hydrochloric
solution) at room temperature, the strength of a glass reinforced bisphenolic epoxy composite
(initial Tg = 76°C) was reduced by more than 70%. The same degradation in strength was
measured when the composite system was immersed in an alkali solution (5 molar NaOH
solution) but at elevated temperature, i.e. 60°C [Kajorncheappunngam et al., 2002].
Moreover, the acid caused less damage at 60°C than at room temperature, showing that not
always a higher temperature environment accelerates the degradation process. The
mechanical characteristics of the glass reinforced composite were approximately unaffected
by the aging in the presence of saturated salt solution (30g/10 cc NaCl) and moderately
affected by distilled water (reductions in maximum stress and strain about 25% at ambient
temperature, reaching 50% at 60°C). The very high reduction in ultimate strength of the
samples after 5 months of immersion in hydrochloric acid was explained as the result of
degradation of the glass fibers or the fiber/matrix interface, since the epoxy matrix contributes
very little to the total composite strength. In the case of water immersion, fiber pull out was
observed, with the surface of fibers essentially clean, indicating that adhesive failure occurred
at interface.
The effects on E-glass/vinylester composites of concrete-based and derived solutions,
were reported by Karbhari, Murphy and Zhang, [Karbhari et al., 2002 b)]. Glass fiber
reinforced composite panels were manufactured by wet lay-up technique using unidirectional
fibers. The lay-up process was followed by vacuum bagging at 24-27°C and 45-55 R.H.. The
Tg measured for the vinylester based composite was around 123°C. Configurations of 2, 4
and 8 layers of fabric with the mat side facing the same direction, i.e. towards the mold
surface, were used to fabricate the panels. After further cure at ambient conditions for one
month, each coupon was immersed in the appropriate solution and tested at different time
intervals, up to 18 months. For comparison purposes, control samples were kept under
controlled conditions at 23°C and 55% R.H.. Different solutions directly derived from
concrete extracts were employed, rather than artificially prepared from combinations of
various alkaline salts and minerals. The solutions were derived form old cured (ten years) and
new cured (28 days) Portland concrete, by placing concrete disks in deionized water, or
directly from cement extracts. The properties of specimens immersed in these solutions were
then compared to those obtained for unimmersed and immersed in deionized water samples.
Tensile tests, conducted in the primary warp direction, were performed on all the specimens.
The increase in tensile strength (8-15%) measured for the control specimens has indicated
that the samples continue to cure during exposure. For the degradation of the samples it was
found that the two and four layer samples exposed to the cementitious extract showed the
highest level of strength reduction, i.e. 31% and 46%, respectively, with respect to control
specimens cured for 18 months. For the eight layer samples the effects due to the different
solutions exposure were comparable, with reductions in the range 33-37%. The stronger
effects of the cementitious extract solution were attributed to the greater concentration of Ca+
ions available in this solution, able to diffuse rapidly in the thinner specimens reaching the
glass fibers in the form of calcium hydroxide. The degradation was found to occur at the
fiber-matrix interface and at the fibers. Optical and scanning electron microscopy revealed
that alkali salts migrate by diffusion through the composite and by wicking along the fiber-
matrix interface into the composite, thereby producing pitting of the fiber surface. Fiber
matrix debonding was observed in all specimens, while the extent of debonding was again
highest for samples exposed to the cementitious extract solution. In some cases, partial
interfacial debonds coalesced to form continuous macro-cracks across the cross-section. The
debonding and deformation of matrix integrity were accompanied by significant degradation
of the fiber-matrix interface area, pitting, notching and cracking of individual fibers. The
effect of immersion in a concrete based alkaline solution was always more severe than the
effect of immersion in deionized water.
Two and four layered laminates of E-glass/vinylester composite were immersed in a high
pH level environment and their properties evaluated over 57 weeks of exposure [Karbhari and
Zhang, 2003]. The E-glass laminates, in non-woven fabric form with uniaxial, biaxial and
triaxial architectures, were produced by resin infusion process in ambient conditions (24°C
and 56% R.H.). The cure of the vinylester resin was carried out at 23°C and 56% R.H. for 24
hours; the laminates were, then, post-cured at 93°C for two hours. Specimens were cut, and
subsequently tested, from composite laminates in both the primary warp (i.e. along the
primary unidirectional yarn) and the fill (i.e. perpendicular to the primary unidirectional yarn)
directions. After immersion at 23°C for different times up to 57 weeks in a KOH based buffer
(pH 10), were performed tensile and short beam shear tests on both immersed and control
specimens, kept in controlled conditions (24°C and 56% R.H.). The reductions in tensile
strength and modulus measured on specimens exposed to the high pH environment were
substantially lower than those found in samples immersed in pure water at ambient
temperature, never exceeding 30% reduction in both tensile strength and modulus at the end
of the 57 week exposure. The highest reductions in tensile strength were found for 2- and 4-
layered uniaxial specimens, irrespective to the test direction. On the other hand, the modulus
showed the highest reduction in laminates tested the warp direction. As already registered for
specimens immersed in deionized water at ambient temperature, the decrease in strength,
during the first few weeks of immersion, was followed by a new increase, sometime above to
the value measured initially on un-exposed specimens. This observation suggested that
residual cure of the vinylester resin took place along with degradation due to the exposure to a
severe environment. Referring to the damage observed on the exposed specimens, the
degradation due to the high pH environment appeared to be predominantly in the fibers. After
short period of exposure (i.e. 26 weeks), local fiber fracture and pitting was seen, similar to
the damage observed on specimens immersed in pure water at ambient temperature. At the
end of the exposure period, on the other hand, extensive degradation was observed in the
form of fiber degradation through longitudinal splitting, close to the fiber-matrix interface, as
well as fiber-matrix interphase degradation, with cracks penetrating transversely through the
fiber. Regarding the short beam shear strength, a good retention of this property was
confirmed for these conditions, with biaxial specimens showing the highest retention of
interlaminar shear strength. As for immersion in pure water at ambient temperature, uniaxial
specimens tested in the fill direction showed a high level of degradation, even though the
exposure to a high pH environment was less detrimental than the immersion in water. The
glass transition temperature of the GFRP, finally, decreased with respect to that measured on
un-exposed specimens as a consequence of the exposure; however, the decrease at the end of
the 57 week exposure was comparable to that measured as consequence of immersion in
water, ranging from 5° to 8°C.
Since a considerable number of deteriorating structures are located near the sea (coastal
structures) and other reinforcing structures can be exposed to saline environments in the form
of de-icing salts (bridges in cold regions), several studies have addressed the evaluation of
degradation occurring in composites exposed to these types of environments. Different results
have indicated that a saline solution is more aggressive than fresh water [GangaRao and
Vijay, 1997; Saadatmanesh and Tannous, 1997; Sasaki et al., 1997; Steckel et al., 1998].
Investigations carried out on glass FRP structural composites under salt exposure conditions
showed a reduction in strength and stiffness up to 50%. Aramidic FRP systems showed the
same behavior, while the performances of carbon FRP’s was found to be superior than both
GFRP and AFRP.
In order to investigate the effects of severe environmental exposure on the mechanical
properties of FRP laminates, uniaxial tension tests were performed on specimens exposed to
different chemical solutions [Tavakkolizadeh and Saadatmanesh, 2004]. A saline solution
with pH equal to 7.25 was used in order to simulate exposures to marine environments, while
saturated calcium hydroxide, Ca(OH)2, solutions with pH of 10 and 12.5 were used to
simulate exposures to hydrating cement and other alkaline environments. Acidic solutions,
using hydrochloric acid at pH of 2.5, was employed, on the other hand, to simulate exposures
to solutions in sewer pipes and wastewater treatment plants. Finally, exposure to alkaline soil
containing microorganisms was reproduced by exposure of laminates to compost soil with

25% moisture content and active microorganisms. Composite laminates were produced by
wet lay-up technique using different fibers and weave patterns. In particular, laminates, made
of one layer of fabric, were made using unidirectional glass woven fabric, with loose fibers
sandwiched between two mats or sticky string, and carbon fabric; unidirectional hybrid
glass/carbon fabric; bidirectional glass fabric; bidirectional hybrid glass/carbon and
glass/aramidic fabrics. The matrix was in all cases a cold-cured two-part bisphenolic epoxy.
The cure of the resin was performed at ambient temperature for 7 days, according to the
suppliers recommendations. Some control specimens were kept in controlled conditions and
mechanically tested after 8 months. Alkaline solutions, at both pH values, did not affect the
modulus of elasticity of the laminate. The effect of these solutions on the other tensile
properties of carbon based laminates was also insignificant. Glass based laminates, on the
other hand, lost significant portion (even higher than 50%) of their tensile stress and strain
when exposed to alkaline environments. Moreover, the laminate manufactured with
unidirectional glass fabric with loose fibers sandwiched between two mats showed the highest
reduction in both mechanical properties (up to 69% after 27 months of exposure at the highest
pH value). The reduction in ultimate strength and strain at break generally increased with
immersion time and with the pH of the solution. Similar results were found for laminates
immersed in acidic solution and simulated seawater, i.e. unaltered values of modulus of
elasticity for all laminates, an insignificant variation in other tensile properties for carbon
based laminates and a large reduction in both strength and strain at break of glass based
laminates. Finally, in the case of exposure to moist soil with microorganisms, all laminates,
with only one exception, displayed minor changes in their tensile properties. The laminate
manufactured with unidirectional glass fabric with loose fibers sandwiched between two mats
showed, also in this case, a notable reduction in both tensile strength (about 20%) and fracture
strain (up to 30%).
Degradation of two E-glass/vinylester composites after exposure to salt solution, was
analyzed in another paper [Zhang et al., 2000]. The two fabric forms used were a four layer
made of woven rowing and a three layers of woven rowing sandwiched between alternating
layers of chopped strand mat. The composite panels, based on a vinylester resin, were
manufactured by wet lay-up technique. The composite panels produced were allowed to cure
under ambient temperature conditions at 60-70% R.H. for a period of two months before
testing or exposure. They were, then, immersed in a 2.5% NaCl aqueous solution up to 11
months. Tensile tests were performed on the samples immersed in salt solution at different
time intervals and also on control samples. A reduction in properties was generally observed,
with the reduction being the maximum in the first three months of exposure. The leveling off
of the values of tensile properties measured after a 11 months exposure indicated the
attainment of an equilibrium related to degradation kinetics. After 11 months of exposure, the
reductions in strength and modulus for the woven roving composite were about 25% and
15%, respectively; whereas those for the composite formed by a combination of chopped
strand mat and woven roving were 14% and 10%, respectively. The authors suggested that in
the latter case the presence of chopped mat layers on the surface acted as a barrier to initial
internal moisture induced degradation, with the moisture diffusion through the thickness
being retarded by the resin rich surface provided by these regions. These layers effectively
serve to hinder penetration of the NaCl solution into the woven roving and the degradation of
the composite through fiber-resin debonding. The mechanical performance of composites
after absorbing the equilibrium amount of moisture was compared to that measured on
composites after subsequent drying. The complete recovering of properties on drying was
found to take place if there was no irreversible changes in the resin and there was neither fiber
matrix debonding, nor matrix micro-cracking and degradation of fibers. The results of tensile
tests performed on composites dried at 25°C for one month following the 11 month
immersion in salt water solution showed only a partial regain of properties, i.e. both strength
and stiffness reached the values attained after the three months exposure period. The effects
of immersion were, therefore, irreversible to a certain extent, due to degradation of the matrix
by hydrolysis. It was noted, moreover, that the regain of properties was greater in the case of
the composite where there were alternating layers of chopped strand mat, which initially also
showed lower degradation due to the protection provided by the outer layers of the mat.
Changes in Tg were also observed after exposure, with the highest reduction recorded for the
composite with chopped strand mat and woven roving i.e. that with the lowest fiber volume
fraction. The effect of the immersion in salt solution on the Tg of the matrix was attributed to
chemical attack on the ester linkage causing hydrolysis, as seen through the reduction in the
peak height of the loss modulus curve obtained in dynamic-mechanical thermal analysis of
the exposed samples. An analysis of the degradation of the properties was made through
optical microscopy on the surface and through the thickness of the composite specimens.
Immersion in salt solution has caused considerable surface degradation of the resin, resulting
in the formation of crack-lines along the glass fibers. In the resin rich areas, was observed the
effect of resin swelling due to moisture absorption, producing a more visible pattern which
suggested greater fiber-resin debonding and plasticization.
The effects of actual and simulated sea water on properties of an E-glass/vinylester
composite were assessed in a similar work [Wu et al., 2002]. Glass fiber reinforced composite
panels were manufactured by wet lay-up technique. Configurations of two layers of a
quadriaxial fabric, laid up symmetrically about the midplane with the bias (±45) plies toward
the center, were used to fabricate the panels. The lay-up process was followed by vacuum
bagging at 22-24°C and 50% R.H.. All samples were preconditioned by storage at 23°C and
55% R.H. for three months before any exposure. The Tg of the vinylester based composite,
measured by dynamic-mechanical thermal analysis after this period, was 119°C. The coupons
were immersed in different saline solutions, i.e.: synthetic seawater at 23°C; sea water at
23°C collected from some distance away from the shore of La Jolla shores (California,
U.S.A.) (pH equal to 8.24). A set of samples were also immersed in sea water for 12 hours,
followed by drying in air at 23°C for 12 hours, in order to simulate the condition of
alternating high and low tide levels. All the exposed specimens were, then, tested after
different times, up to 18 months. The short term exposure (up to 6 months) to seawater,
irrespective to the solution used, did not have an appreciable effect on the glass transition
temperature of the vinylester based composite. At longer immersion times, on the other hand,
a monotonical decrease in Tg was registered for both synthetic and true seawater. The lowest
Tg value was registered for samples immersed in true seawater, i.e. 98°C after 18 months of
immersion. As for the case of immersion in pure water, it was suggested that two competitive
phenomena took place during immersion in seawater, i.e. plasticization and hydrolysis on one
hand, which cause a depression of the Tg, and the completion of the curing reactions, which
produces an increase in the Tg. It seems that the two processes would take place in the same
order of magnitude in the first period of immersion, while plasticization and hydrolysis would
prevail at longer immersion time. Moreover, the Tg measured on samples removed from both
solutions after 18 months of immersion and, then, dried for one year at 23°C and 55% R.H.
only increased by about 4-5°C relative to that measured at the end of the 18 months
immersion in both solutions, confirming the partial irreversibility of the effects of saline
environments. Mechanical tensile tests and interlaminar shear tests were performed on
specimens immersed up to 12 months in the different solutions, as well as on un-immersed
samples, kept for the same period under controlled conditions at 23°C and 55% R.H..
Immersion in both true seawater and synthetic seawater produced an initial reduction in
tensile strength after one month immersion, followed by an increase after three months, and a
new reduction after longer immersion time, which became more prominent with increasing
the immersion time. This has indicated that a steady condition was not achieved. At the end of
the immersion period, the tensile strength was reduced for both solutions by about 13% with
respect to that measured on un-immersed specimens. The process of cycling in seawater
resulted in the lowest decrease in strength, i.e. about 8% after 12 months of immersion, but
also the highest level of scatter in the results, explained by the high incidence of longitudinal
micro-cracking, as a result of the continuous change from a wet to a dry regime. The tensile
modulus was found to decrease after one month of immersion or cycling in a saline
environment, irrespective to the solution employed. An increase was, then, observed in all
cases, which can be attributed to additional curing, up to 6 months exposure, after which the
modulus reached the initial value. During the following 6 months, a new decrease in tensile
modulus was measured for all saline exposures, indicating the dominance of moisture-related
degradation over residual cure effects. At the end of the immersion or exposure period, the
final modulus value was in all cases slightly lower (not exceeding 13%) than that of un-
immersed specimens. A similar trend was observed also for SBS strength, a decrease during
the first three months of immersion or exposure to saline environments, followed by a new
increase after six months and a subsequent continuous decrease. The reductions in SBS
strength for samples after one year were about 15% and 16% for immersion in synthetic and
true seawater, respectively. Slightly lower reductions were noted for samples subjected to the
cycling regime in seawater, i.e. 11%. The latter exposure condition, on the other hand,
resulted in the greatest permanent reduction in SBS strength, which did not recover even after
drying for one year. Contrary to this, the samples immersed in both seawater solutions
recovered in large part the reduction in SBS strength after drying for one year. Finally, by
comparing the effects of the saline environments on the mechanical characteristics of the
composite with those of deionized water, reported in the same study, it was found that the
immersion in pure water caused slighter higher reductions in interlaminar shear properties
while seawater had the greatest effects on tensile properties.
In order to simulate a sea water environment, wet lay-up carbon fiber/vinyl ester
composites, cured at 22.5°C and 50% R.H., were immersed in a 5% NaCl content in water
solution up to 100 days [Rivera and Karbhari, 2002]. For comparison purposes, the same
materials were immersed for the same period in deionized water. The maximum moisture
content measured in the case of immersion in salt water was much lower (by 50-80%) and
occurred much faster respect to that measured for the immersion in water. On the other hand,
the attainment of this maximum value was followed by a loss of weight, attributed to a
combination of hydrolysis and removal of polymeric matter from the interfacial level.
Samples of wet lay-up carbon fibers composite, based on two part cold-cured epoxy were
immersed in simulated salt water (5% NaCl solution) as well as in alkaline solution (pH =
12), in order to simulate a solution formed by transport of water through concrete [Abanilla et
al., 2006 a); Abanilla et al., 2006 b)]. Very little difference in water uptake was found for
samples immersed in salt solution, compared to samples immersed in deionized water. On the
other hand, higher values of water uptake were measured on samples exposed to alkaline
solution, which is explained by a higher level of deterioration caused by the alkaline
environment both in the fiber/matrix interphase regions and within the bulk of the resin.
Similar Tg values were found for specimens of composite immersed in the two solutions
compared to immersion in pure water. The decrease in Tg was in all cases between 24°C and
26°C. The similarity was attributed to the decrease in Tg being associated with plasticization
and hydrolysis of the bulk resin rather than by chemical reactions with the salts in alkaline
solutions. The average tensile strength and stiffness were somehow reduced after immersion
in the same solutions. The reductions in tensile modulus, in particular, were 12% and 17% for
immersion in salt water and alkaline solution, respectively, with respect to the value measured
on un-immersed samples. The reduction in flexural strength due to the immersion in salt
water was less severe than that in both pure water and alkaline solution. In the latter cases, in
fact, the decreases in strength were 25% for immersion in pure water and 33% for immersion
in alkaline solution, with respect to control specimens. The decrease in flexural modulus was
about 9% and 13% for the 6-layer specimens immersed in salt water and alkaline solution,
respectively, relative to un-immersed samples. The results of both short beam shear tests and
in-plane shear tests demonstrated that immersion in deionized water, salt and alkaline
solutions resulted in almost indistinguishable behavior of strength with time of exposure,
suggesting that its reduction was primarily driven by the moisture uptake. After a 100 week
period of exposure to the three different environments, on the other hand, a slightly greater
effect of alkaline solution (the reduction in SBS strength being about 33% and in in-plane
shear strength about 26%) was observed than for both deionized water and salt solution (with
reductions never exceeding 30%). This was explained in terms of a greater degree of
hydrolysis and of chemical degradation caused by the high pH value. The effect of the
different solutions was greater on in-plane shear modulus, with reductions of about 20, 52 and
60% after the 100 week period of immersion in deionized water, salt solution and alkali
solution, respectively. The initial rate of deterioration over the first 4-7.5 weeks was found
much faster in the latter two solutions. Microscopic examinations showed an increased
incidence of microcracks and smoother resin surfaces in specimens immersed in salt and
alkali solutions, as compared to those kept in deionized water, indicating an increased
delamination between plies with opposite angles in presence of saline or alkaline ions. Small
decreases in interlaminar fracture toughness were measured after a 100 week period of
immersion in salt solution and alkali solution, i.e. 7 and 10%, respectively, which was
explained in terms of severe chemical degradation effects resulting from immersion in these
solutions. The mentioned results corroborate the fact that, although carbon fibers are inert to
the most environmental agents, carbon/epoxy composites can deteriorate due to attack in the
the resin and at the fiber-matrix interface.
GFRP-confined concrete, based on thermosetting cold-curing resins, showed a significant
deterioration of mechanical properties in terms of strength and ductility after exposure to
saline environment [Corvaglia et al., 2006].
The degradation due to an aggressive environment of Reinforced Concrete (RC) beams
strengthened by FRP, was evaluated in another work [Delpak et al., 2002]. The external
strengthening of RC elements was performed by applying two overlapping layers of Kevlar
(Aramidic fibers) fabric to the tension side of the concrete beam. The impregnation of fibers
and the adhesion of AFRP to concrete was assured by two different two-part cold-cured
epoxy, i.e. a primer and an adhesive (saturant). For reference a number of both strengthened
and un-strengthened beams were tested in a four-point loading configuration up to failure.
The same tests were also conducted on FRP strengthened and un-strengthened elements
immersed for 19 months in sulfuric acid (pH = 2) and subsequently kept in laboratory for 15
months. This artificial exposure would simulate that arisen as consequence of the burning of
fossil fuels. The load carrying capacity of RC members was found significantly enhanced by
the use of FRP, even in the case of structures subjected to an acidic environment. In
particular, the strengthened beam exposed to the aggressive ambient exhibited an increase in
ultimate load of about 79% relative to the control un-strengthened RC element.
Effect of Radiations
Another environmental factor giving rise to irreversible decay of some fiber-reinforced

plastics is the ultraviolet component of solar radiation. The wavelengths of light lie in the
range 290-400 nm. Generally speaking, polymers have dissociation energy much greater than
this value. However, inside their molecular structure there are units, such as double bonds or
peroxy groups, which will break at energy levels close to the wavelength of light. The
degradation of properties of composites due to UV rays is known to concentrate in the matrix
resin, causing breakage of the resin molecules, due to surface oxidation, with consequent
embrittlement of the matrix, thus affecting the stiffness and the impact strength of the whole
composite [Rinaldi and Maura, 1993; Silva, 2007]. The direct result of UV incidence on
laminates is superficial and the radiations cannot penetrate deep into the laminates; its effect,
therefore, is the initiation of micro-cracks at the surface. However, those micro-cracks, in the
presence of other environmental agents, can accelerate the degradation process by allowing
easier penetration of agents into the interior of the laminates and triggering fracture at stress
levels well below those required for un-exposed material [Karbhari et al., 2003].
Carbon reinforced FRP are reported to be generally not affected by ultraviolet rays.
Aramidic and glass fiber reinforced FRP, on the other hand, show significant reductions in
tensile strength as consequence of exposures to radiations, resulting in the loss of
performance of the strengthened system [Larsson, 1986; Tomosawa et al., 1998].
By reproducing the effect of solar radiations by UV laboratory devices, several careful
procedures must be followed, since the effect of UV exposure strongly depend on equipment
used, the age of the lamps, heterogeneity of radiation due to differences with respect to the
chambers used [Silva, 2007]. All these parameters must be carefully considered, particularly
when generalizing and extrapolating results from laboratory to real life weathering.
Notable reductions in impact strength of a glass-fiber composite, based on cold-cured bis-
phenolic resin, after exposure to UV radiations, were found by Rinaldi and Maura [Rinaldi
and Maura, 1993]. They were explained in terms of photooxidative actions of UV radiations,
responsible for the breakdown of bonds in the polymer chains.
The effects of ultra violet radiations on prepregs of unidirectional carbon fiber reinforced
polymer (CFRP) and two fiber orientations of glass fiber reinforced polymer (GFRP)
composites, were also analyzed more recently [Hulatt et al., 2002]. The matrix selected to
produce the two plies composites was a mild-cured epoxy resin. The composites were
manufactured using a curing cycle of 16 hours at 65°C under a vacuum of 1 atm. After
curing, the Tg of the resin was 75°C. The samples of the three composites were, then,
exposed to radiations on each side of the specimens for 2000 hours. After exposure, they
were loaded to failure under a tensile stress. The results showed that the mechanical
properties of all the composites remained largely unaffected after UV exposure, with only
minor changes in longitudinal modulus. Slight reductions in the modulus were found for the
GFRP composites. In the case of unidirectional CFRP, the increase in stress was about 16%
and in stiffness about 4%. Discoloration of the matrix resin was evident, particularly in the
case of GFRP composites.
In order to investigate the effects of sunlight exposure on mechanical properties of wet
lay-up composites, different FRP laminates were produced and exposed to ultraviolet
radiations [Tavakkolizadeh and Saadatmanesh, 2004]. Seven one-layer fabric laminates, all
manufactured using the same cold-cured two part epoxy (curing cycle: 7 days at ambient
temperature) but different fibers (carbon, glass, hybrid glass/carbon and glass/aramidic) and
weave patterns (with loose fibers sandwiched between two mats or sticky string,
unidirectional and bidirectional), were compared in terms of preservation of uniaxial tension
properties. 15 Watt Black Light Fluorescent tubes were used to simulate ultraviolet radiations
between 300 and 400 nm, with a peak of 340 nm and intensity of 30 x 10-6 W/cm2. For
comparison purposes, control specimens were also produced, by keeping them in a controlled
ambient for 8 months, and tested together with aged samples. The results showed that UV
radiation did not cause any degradation in the mechanical tensile characteristics of laminates,
irrespective to the fiber and the weave patterns. On the contrary, in some case a slight
increase in stiffness and strength was measured on exposed specimens, suggesting that the
radiations could have promoted post-curing of the epoxy matrix of the composites.
Effect of Combined Agents
In several durability studies, the effect of warm water on FRP composites was analyzed. The
use high temperatures was intended to enhance the effect of water, often trying to reproduce a
long term response of the composite to this environmental agent.
As a first example, in order to assess the efficiency of different coupling agents on the
durability of E-glass/epoxy composites, the composites were exposed to a fairly severe and
accelerated environments for a prolonged period [Zhang et al., 2003 a)]. Composite
specimens were fabricated by wet lay-up process using E-glass plain weave fabric, with
approximately 95% of the fibers in the warp direction and 5% in the weft direction. Three
different commercial silane based sizes/finishes were used. Specimens using eight layers of
sized fabric were fabricated in the form of cylinders. The fibers were impregnated with a
bisphenolic epoxy cured with an aliphatic amine under ambient conditions. The specimens
were, then, placed in water at 60°C over a total period of 12 months. The kind of exposure
selected in the study represented a severe environment, used for purposes of accelerated
testing rather than for simulation of the actual environmental conditions. After different
periods of immersion, standard specimens were cut from the central portion of the cylinders
and ring burst, SBS and compression tests were performed on them. The immersion in water
at 60°C caused in any case a discoloration of the composite with visible deterioration of the
surface resin-rich layer and the appearance of fiber rowing. The severe environment exposure
caused notable reductions in tensile strength in the hoop direction, while hoop modulus
remained more or less unaffected. At the end of the 12-month immersion period, reductions in
strength ranging from 31% to 62% were registered. The differences were found to depend on
the sizing system used. However, no specific information on the chemical nature of the three
sizing systems was given to be able to provide explanation for the different behavior of the
three systems. In all cases most of the loss in strength occurred within the first six months.
The latter results were explained in terms of the use of appropriate tailored sizings able to
significantly reduce the level of degradation through development of a protective coating on
the fiber, which also served to enhance bonding, as a result of interactions between adsorbed
moisture and the functional groups of the sizing. Some specimens showed significant fiber-
matrix debonding and an increase in the level of interphase failure within the first period of
exposure, which resulted in further moisture adsorption through wicking along the interface.
A change in failure mode was observed in other systems, from the interface-dominated mode
for unexposed specimens to one involving fiber fracture and splitting with the level of
fracture increasing with exposure time. On the other hand, it was noticed that the interface
between fiber and matrix was not degraded and micrographs viewed in cross section showed
the development of a stronger and more uniform bond. The results of compression tests, using
specimens with fibers oriented in the stress direction, revealed a general decrease in strength
over immersion time. Similar results were also found from SBS tests, performed on coupons
having fibers aligned in the span direction. The reductions in strength ranged from 23% to
40%, again depending on the sizing system used. Finally, the glass transition temperature was
only slightly affected by the severe exposure and it partly recovered after drying the
specimens for one week at 27°C.
The effect of warm water on a wet lay-up unidirectional carbon fiber laminates, based on
two part cold-cured epoxy, was recently presented in two papers [Abanilla et al., 2006 a);
Abanilla et al., 2006 b)]. Samples of composite, previously cured at ambient temperature for
48 hours and, then, preconditioned at 23°C and 30% R.H. for 30 days, were immersed in
deionized water at 37.8° and 60°C up to 100 weeks and removed from water for testing at
intermediate periods. The immersion in warm deionized water produced a rapid drop in the
glass transition temperature, which was more pronounced at the higher immersion
temperatures. However, the final decrease in Tg, measured at the end of 100 weeks of
immersion, was by about 27°C irrespective to the immersion temperatures chosen, from an
initial Tg value of 92°C. The reduction in average tensile strength, on the other hand, was
found to depend on the immersion temperature. For 2-layer thick specimens it was less than
12% and 19% at the 37.8°C and 60°C, respectively, after immersion. Most of the
deterioration took place both at the fiber/matrix interface and in the bulk of the resin, as
observed by SEM examinations. As a consequence, a greater reduction in tensile strength
were measured for the 6-layer thick specimens, i.e. about 39% and 42% for immersion
temperatures of 37.8°C and 60°C, respectively. A 100 weeks immersion period resulted also
in a reduction in tensile stiffness in the region of 12% and 27% for the 2-layer specimens at
37.8°C and 60°C immersion temperatures, respectively, and 22% and 27% for the 6-layer
specimens immersed at 37.8°C and 60°C, respectively. This effect was generally confirmed
for flexural properties, measured in samples immersed in cold water (23°C), i.e. a reduction
in flexural strength after different immersion times was observed, depending on immersion
temperatures and number of layers, till a constant value was achieved. The influence of
thickness of specimens was minor also in the case of immersion in warm water; at the end of
the immersion period, the 2-layer specimens showed a decrease in flexural strength of about
42% and 65% for immersion temperatures of 37.8°C and 60°C, respectively. The decreases in
strength for the 6-layer specimens were about 40% and 54% for immersion temperatures of
37.8° and 60°C, respectively. Conversely, the flexural modulus was more influenced by the
number of layers, with a decrease in stiffness that was lower for the thinner specimens (about
13%) than for thicker ones (with reductions up to 28%). The decay of interlaminar
characteristics, i.e. SBS and in-plane shear properties, already observed in specimens
immersed in cold water, was even higher when the immersion temperature was increased.
The maximum levels of deterioration of SBS strength, reached after the 100 weeks period of
immersion, were: 46% and 50% for the six-layer composites immersed in deionized water at
37.8°C and 60°C, respectively; and 58% and 62% for the twelve-layer composites immersed
in deionized water at 37.8°C and 60°C, respectively. At the end of the 100 week period of
immersion, the loss in in-plane shear strength for the two-layer specimens was 41% and 50%
at 37.8°C and 60°C, respectively. The reduction in in-plane shear strength was slightly lower
for the 6-layer thickness, i.e. 31% and 48% after immersion in deionized water at 37.8°C and
60°C, respectively. Reductions of in-plane modulus were similarly registered. At the end of
the 100 week period immersion, the modulus decreased by 36% and 45% for the two layer
thick samples immersed in deionized water at 37.8°C and 60°C, respectively; whereas the
corresponding values for the six-layer specimens were 43% and 48%, respectively. The
observed large decrease in in-plane modulus, previously found also in samples immersed in
cold water, was justified with the deterioration of the composite taking place at both the inter-
ply and the fiber matrix interphase levels. Immersion in water, irrespective to the immersion
temperature, on the other hand, resulted in an increase in the interlaminar fracture toughness,
with maximum increases reached for the 6-layer thickness specimens after 32 weeks
immersion, which was about 59% and 65% at 37.8°C and 60°C, respectively. By comparing
all the results obtained after immersion in deionized water at different temperatures, it was
concluded that the changes in properties due to immersion in pure water generally increase
with immersion time, temperature and number of layers. An increase in immersion
temperature, in particular, caused the destruction of fiber fiber-matrix adhesion, as
demonstrated by the microscopic analysis, and an increased level of degradation of the resin-
rich layer between layers of fabric.
The effect of heat and moisture on tensile properties of seven different FRP laminates
was investigated by Tavakkolizadeh and Saadatmanesh [Tavakkolizadeh and Saadatmanesh,
2004]. The laminates, consisting of one layer of fabric, were produced by wet lay-up
technique, using a two-part cold-cured epoxy and different type of fibers (carbon, glass,
hybrid glass/carbon and glass/aramid) and weave patterns (short loose fibers sandwiched
between two mats or “sticky string”, unidirectional and bidirectional fabrics). After a period
of 7 days at ambient temperature, indicated by suppliers as adequate to achieve the complete
cure of the matrix resin, the laminates were contemporarily exposed to heat and moisture
(50°C and 95% R.H.). Uniaxial tension tests were performed on both treated specimens and
controls, kept in ambient laboratory conditions for 8 months. The only relevant change in
mechanical properties resulting from the exposure was found for glass fibers based laminates.
In particular, the ultimate strength values of both unidirectional and bidirectional glass
laminates were reduced by about 15% after the 27 months thermo-hygrometric treatment. The
strain at failure of unidirectional glass fabric with short loose fibers sandwiched between two
mats, unidirectional and bidirectional “sticky string” glass fabric laminates decreased by 7%,
15% and 18%, respectively, after 27 months of exposure to heat/humid environment. The
carbon based laminates again displayed a superior resistance to hostile ambient.
A different study seems to confirm these results [Aiello and Sciolti, 2005; Frigione and
Sciolti, 2006]. Tensile tests performed on CFRP sheets based on an cold-cured epoxy resin
(Tg around 45°C) showed a negligible influence after about six months of a thermo-
hygrometric treatment (i.e. 40°C and 90% R.H.) on both their tensile strength and elastic
modulus. Within experimental errors, the modulus of elasticity and tensile strength retained
almost the value calculated on controls. The kind of rupture, however, was significantly
influenced by the treatment. Debonding was the more frequently observed behavior. The
results of tensile mechanical tests performed on GFRP composite samples after the same
treatment, on the other hand, displayed a slightly larger influence on the properties of the
composite. In this case, the presence of glass fibers are expected to influence to a greater
extent the final properties of the composite due to their susceptibility to water. The results
confirmed that the mechanical properties of a composite, measured in the fibers direction,
basically depend on the properties of the fibers.
The effect of short term immersions in warm (60°C) deionized water on E-
glass/vinylester composite, was analyzed by Karbhari and Zhang [Karbhari and Zhang, 2003].
Resin infusion in ambient conditions (24°C and 56% R.H.), was employed to produce two-
and four-layered laminates from non-woven fabrics, with uniaxial, biaxial and triaxial
architectures. The curing process was also performed in ambient conditions (23°C and 56%
R.H.) for 24 hours, followed by a post-cure at 93°C for two hours. Specimens for both tensile
and short beam shear tests were produced in the primary warp direction (i.e. along the
primary unidirectional yarn) as well as in the fill direction (i.e. perpendicular to the primary
unidirectional yarn). They were then immersed in deionized water at 60°C for up to 57 weeks,
in order to accelerate the degradation caused by water. Control specimens, kept for the same
time in controlled conditions (i.e. 24°C and 56% R.H.), were tested along with the immersed
ones. Higher levels of tensile strength and modulus degradation were found relative to that
found for samples immersed in pure water at ambient temperature, due to the greater
absorption of moisture by increasing the water temperature. At the end of the 57 weeks
exposure period, reduction in tensile strength greater than 50% was always found for
laminates tested the warp direction. Slightly lower decreases were measured in the fill
direction. Immersion in warm water, moreover, has also increased the rate of degradation of
tensile strength and has more than offset the beneficial effects of residual cure of the
vinylester resin used as the matrix. Short beam shear tests confirmed the results of tensile
tests, i.e. greater reductions in SBS strength when compared to those observed for samples
immersed in water at ambient temperature. The higher immersion temperature, finally,
determined also an higher decrease in Tg of about 11-16°C after 57 weeks of immersion.
The mechanical properties of glass FRP rebars, based on a polyester resin (Tg = 70°C)
and E-glass fibers after immersion in water were investigated by Micelli and La Tegola
[Micelli and La Tegola, 2004]. The authors tried to simulate the effect of long-time exposure
by employing a high immersion temperature, i.e. 50°C, following a procedure previously
experimented for fibers immersed in concrete [Litherland et al., 1981]. The results showed
small reductions in tensile strength, i.e. about 22% after 40 days exposure to water at 50°C,
while the tensile stiffness remained almost unaffected. Retained transverse properties were
also high, according to the small amount of absorbed water in GFRP rebars.
Boiling water and ultraviolet radiation were used to study the structural degradation of
steel reinforced concrete (RC) beams strengthened with CFRP and GFRP fabrics [Li et al.,
2002]. The short term accelerated conditioning tests, i.e. obtained at a high temperature and
high moisture content environment, were performed in order to predict the long term behavior
in an common ambient environment. Boiling water was selected to represent the wettest
environment at the highest temperature achievable in practice. UV radiation was used to
enhance the damaging effect of temperature and moisture on structural degradation of FRP
strengthened RC beams. In order to simulate a real service condition for the repairing of a
damaged concrete element, unidirectional CFRP and GFRP fabrics were bonded to the
tension face of pre-cracked concrete beams. Only one layer of fiber tow was applied to each
damaged beam using the commercial adhesive provided for both composites. Although not
explicitly specified in the papers, the trade name of the products analyzed suggests that a
cold-cured epoxy resin was used as matrix and adhesive for both composites. After seven
days curing at ambient environment, the FRP plated concrete beams were immersed in
boiling water for one week and irradiated by UV rays, in a wavelength ranging from 280 to
320 nm. The beams were placed to ensure that the FRP fabrics were directly exposed to the
UV light. During the conditioning period, the UV lamp was turned on for 30 minutes and
after the water was drained out on the seventh day, the UV lamp was turned on for another
hour. Conditioned specimens, as well as unexposed beams used as reference, were tested in
four point bending mode. Referring first to un-exposed samples, the results showed that even
one ply of GFRP or CFRP is able to significantly increase the load carrying capacity of pre-
cracked concrete beams. When the FRP’s elements are subjected to a harsh environment, they
can still display a certain strengthening ability, even when their structural degradation is very
significant. It was found, in fact, that the elastic modulus, used to represent the degradation of
FPR concrete layers, was reduced by 43-48% after the exposure to the harsh environment,
and the strengthening efficiency of GFRP and CFRP was reduced to 76% and 57%,
respectively, after conditioning. The severe degradation observed was partly attributed to
penetration of water and partly to UV radiation, leading to fiber-matrix interfacial debonding
and matrix cracking. Although the durability of carbon fiber based composites is well known
to be much higher than that of glass fiber based composites, the conditioning used had similar
dramatic effects on both composites. The authors suggested that the degradation of both
FRP’s was due to the deterioration of the matrix resin, while the fibers seemed to play only a
secondary role. This was confirmed by the observation for the change in color of composites,
light before and dark after conditioning. Failure of all the FRP strengthened concrete beams
occurred by a crushing effect at the compression zone, leaving the FRP layer unaffected. This
implies that the ultimate strength of the FRP was not reached, even for the aged FRP layers.
Wet-dry and freeze-thaw cycles, using different conditions of temperature, degree of
humidity, or immersion in different water solutions, have often been employed to simulate
actual environmental conditions. Since all the mentioned agents act concurrently under
normal service conditions, it is necessary to evaluate their combined effects.
Freeze-thaw cycles were performed on wet lay-up composites previously immersed in
salt solution, and their properties were compared to those of reference specimens kept in
controlled conditions (23°C, 55% R.H.) [Zhang et al., 2001; Karbhari et al., 2001]. Two
different composites were produced, both based on a cold-cured epoxy and reinforced with E-
glass plus aramid fibers and E-glass fibers, respectively. Freeze-thaw cycles were carried out
for up to 6 months and one year of exposure at temperatures between -26°C and 23°C, by
performing 90 and 180 cycles consisting of 24 hours at the sub-zero temperature, followed by
24 hours at ambient temperature. Prior to freeze-thaw exposure, the specimens were
immersed in a 5% NaCl solution for a period of five weeks to simulate moisture absorption
including that arising from salt spray. Freeze-thaw exposure after salt soak showed a
significant detrimental effect, resulting in reductions in both tensile strength and interlaminar
shear strength. The exposure to freeze-thaw cycles, however, provided alternate periods of
exposure wherein cure could progress. An increase in Tg was, in fact, registered for both
composites after the whole exposition. By comparing these final Tg values with those
registered for un-exposed specimens kept in a controlled environment over the same period, a
lower increment in this property was found for both materials, indicating a possible
degradation of the matrix resin due to the severe exposure conditions.
The durability in different environments of an unidirectional carbon (CFRP) and two
fiber orientations of glass (GFRP), i.e. a 0/90° biaxial woven fabric and a +/– 45° stitched
fiber, composites were investigated by Hulatt and co-workers [Hulatt et al., 2002]. A mild-
cured epoxy resin, with a final Tg of 75°C, was used for all the composites. A curing cycle of
16 hours at 65°C under a vacuum of 1 atm, was performed in all cases. The coupon samples
were exposed to different wet-dry cycles, employing both water and a saturated salt solution
(sodium chloride), in order to reproduce the likely environments found on road. The
procedure followed in both cases was to: immerse the specimens for five days in each
solution; dry the surface; store them in an environment of 22°C and 50% R.H. for two more
days, repeating the cycle to a total of 2000 hours of immersion, corresponding to 17 weeks
total cycle. Before exposure, the samples were loaded to 40% of their ultimate failure load to
introduce a degree of matrix cracking into the material. The exposure of the three composites
to wet-dry cycles performed in water caused only slight reductions in their tensile properties.
In particular, failure stress of unidirectional CFRP and 0/90° GFRP composites decreased
only by 3.8% and 16.9%, respectively, while the strength of +/– 45° GFRP composite
increased by 8.8%. The reductions in strength were explained in terms of water permeating
along the surface of the fibers and weakening the bond between the fibers and the matrix,
while the increase in the case of +/– 45° GFRP composites was attributed to internal stress
relief by absorbed water. No adverse effects were recorded for the longitudinal modulus after
wet-dry cycles were performed in water, with only a small increase recorded for all the
composites. The exposure to wet-dry cycles employing simulating road salt solution was
found even less detrimental than wet-dry cycles performed in water. Only for the 0/90° GFRP
composite a reduction in stiffness of 3% was measured, and increases in failure stress of
about 3%, 4% and 13.5% were found for unidirectional CFRP, 0/90° GFRP and +/– 45°
GFRP composites, respectively. However, the authors affirmed that the observed changes in
property is within the experimental error owing to the variable quality of the materials.
The effect of common environmental agents, reproduced in laboratory, on the properties
of CFS (Carbon Fiber Sheet) composite, based on an epoxy primer and adhesive, was
analyzed by Frigione and co-workers [Frigione et al., 2004]. The authors examined the effect
of dry-wet cycles (24 hours in oven at 35°C followed by 24 hours in water at 23°C, for 28 and
35 cycles) on composite mechanical characteristics. The composite, consisting of a single
layer sheet, based on unidirectional carbon fibers, was manufactured by hand lay-up
technique. Curing of the matrix resin, before exposure to wet-dry cycles, was over 20 days at
ambient temperature (23°C). The results of tensile tests performed on CFS samples showed
that, after 36 wet-dry cycles, both the elastic modulus and the tensile strength decreased by
about 10%, while no changes resulted from this treatment on the strain to failure. Since the
flexural tests performed after repeated dry-wet cycles on samples of epoxy primer and
adhesive in isolation showed that this treatment had a significant effect on the maximum
strength for both resins, it was confirmed that the tensile properties in the fiber direction of
the CFS composite, consisting of the assembly of the two resins plus the fibers, depend
primarily on the properties of the fibers. Carbon fibers, on the other hand, are known to be
very resistant to thermo-hygrometric treatments.
Commercial pultruded carbon fiber reinforced plastic (CFRP) and glass fiber reinforced
plastic (GFRP) rods were analyzed under severe environmental conditions [Micelli and Nanni
2004]. The CFRP’s were based on a modified epoxy/vinyl ester resin (Tg = 75-85°C) and an
epoxy resin (Tg = 85-100°C), using carbon fibers characterized by a high modulus (in the
case of the CFRP manufactured with the epoxy/vinyl ester matrix) or a high strength (in the
case of the CFRP’s manufactured with the epoxy/vinyl ester and the epoxy matrices). The
GFRP was made from a polyester resin (Tg = 70°C). The specimens were subjected to
combined environmental cycles in a controlled chamber. The cycles consisted of: a) freeze-
thaw cycles (between -18°C and 4°C), in order to simulate winter effects; b) moderate
temperature cycles (from 16°C to 49°C), in order to simulate summer effects; c) high relative
humidity cycles (in the range 60-100% R.H.), in order to simulate high humidity rain in
summer; and d) UV radiations, in order to simulate sunlight exposure. Each sample was
subjected to alternated cycles, for a total of 200 freeze-thaw cycles, 480 humidity cycles and
600 moderate temperature cycles. Mechanical tests were performed on the initial FRP
samples and on specimens exposed to the combined cycles. The retained mechanical
properties were used to quantify the influence of the external environment. All the CFRP and
GFRP specimens analyzed displayed a good retention of both tensile strength and transverse
properties after the environmental cycles performed, irrespective to the choice of matrix and
fibers.
Two different FRP systems, i.e. a 50% weight glass fiber hand lay-up reinforced
unsaturated isophthalic polyester resin laminate and a 70% weight E-glass fiber reinforced
vinyl ester resin laminate manufactured using the Seamann Composites Resin Infusion
Molding Process (SCRIMP), both cured at room temperature, were subjected to different
programs of aging in water and air [Boinard, et al., 2000]. The initial glass transition
temperatures, measured by dynamic mechanical analysis, were: 88°C for polyester resin and
110°C for vinyl ester resin. A first group of both systems were aged in an air circulated oven,
measuring the loss of low molecular weight material. Once the samples had reached a
constant dry weight, they were immersed in distilled water. Other samples were directly
exposed to distilled water and, once they had reached equilibrium, were placed in an air
circulated oven for drying. Two temperatures were used for both programs and both
expositions (air and water), i.e. 30 and 60°C. For the polyester based composite the results
have shown that hydrolysis of the resin has produced soluble matter which gave greater loss
of weight after exposition to water, when compared to that measured after the aging in air.
The loss in air was attributed to the loss of unreacted monomer. Monomers residues were
initially present inside the resin and were able to act as plasticizer in the laminate. During
aging in both media, the residues leached out of the laminate, leading to a subsequent increase
in Tg. The lower dynamic modulus in the plateau precluded the occurrence of a post-cure
process. The decrease of the high temperature modulus was also explained in terms of loss of
bonding between resin and fibers in the laminate during aging, which became more prominent
when the aging temperature was increased. More encouraging were the results obtained on
the vinyl ester based laminate. No degradation process, such as hydrolysis, seemed to occur
during aging. The losses were similar for both exposures. As for the polyester laminate,
monomer residues acted as plasticizers. The increased the Tg was explained again in terms of
leaching of monomer residues during aging. Since the modulus of the laminate at high
temperature did not change with aging, it was assumed that no debonding occurred.
CFRP and GFRP based on a vinyl ester matrix were exposed to freeze-thaw conditions
with immersion in salt solution for an overall exposure period of 100 days [Rivera and
Karbhari, 2002; Karbhari, et al., 2002, a)]. The composites were fabricated by wet lay-up
process, using three layers of unidirectional carbon fibers or E-glass fibers, and allowing the
vinylester resin to cure at 22.5°C and 50% R.H.. The specimens produced were, then,
exposed to freeze-thaw cycles (from -10°C to 22.5°C, with the cycle being repeated every 24
hours) with the thaw stage consisting in an immersion in a 5% NaCl water solution at 22.5°C.
Tensile tests were performed on flat composite panels of un-exposed (i.e. stored at 22.5°C
and 50% R.H.) and exposed specimens, in order to evaluate the effect of the harsh treatment.
The loss of strength for both CFRP (around 16%) and GFRP (about 13%) due to freeze-thaw
cycles performed in the salt water environment was consistently more severe than that due to
freeze-thaw exposure in pure water. In the case of the glass reinforced composite, also the
decrease in tensile modulus (about 10%) was higher when the freeze-thaw cycles were
performed in a saline environment. The diffusion of moisture and NaCl through the resin and
the wicking along cracks and fiber-matrix debonds was recognized as the reason for the salt
causing an increased level of interfacial debonding and crack extension during each freeze-
thaw cycle. The reduction in the glass transition temperature measured for both composites
was similar to that calculated in the case of exposure to freeze-thaw in pure water, as reported
before.
In order to evaluate the effects of de-icing chemicals on concrete beams, externally
reinforced by the application of FRP under wet-dry and freeze-thaw conditions, a pioneering
experimental study was conducted by Chajes and co-workers [Chajes et al., 1995]. Three
types of fabric were used, i.e. plain-weave aramid fabric, crowfoot satin-weave E-glass and
plain-weave graphite fabric. All fabrics comprised fibers oriented at 0° and 90°. In all cases,
only one layer of fabric was applied to small-scale steel reinforced concrete beams. A two
component construction grade room-temperature curing epoxy resin (high modulus/high
strength) was used to bond the fabric to the tension face of the concrete beams. The epoxy
based FRP used to reinforced the concrete beams were allowed to cure under vacuum for one
day and then for two more days, after removing from the vacuum bag. The beams were then
exposed to freeze-thaw and wet-dry cycling in a calcium chloride solution. For the freeze-
thaw cycling, the specimens were placed in airtight containers and covered with a 4%
aqueous calcium chloride solution. The beams were, then, subjected to repeated freeze-thaw
cycles, up to 100 cycles; each cycle consisted of 16 hours at –17°C followed by a 8-hours
thawing at room temperature. The same concentration of calcium chloride solution was used
for the wet-dry cycles, conducted at room temperature up to 100 cycles. A single wet-dry
cycle consisted of immersing the beams in the solution in airtight containers for 16 hours. The
beams were, then, allowed to dry at room temperature for 8 hours. Additional beams were left
in a laboratory environment and used as controls. The specimens subjected to harsh
environments, as well as the unexposed ones, were tested in flexural four point bending
mode. The effects of chloride exposure during freezing and thawing or wetting and drying,
were evaluated by varying the number of cycles prior to testing. The results of unexposed
specimens indicated that significant enhancement of the flexural properties were achieved by
bonding composite fabrics on the tension face of reinforced concrete beams. The beams
reinforced with aramid fibers displayed the greatest stiffness and strength increases with
respect to unwrapped ones. The chloride exposure in both freeze-thaw and wet-dry
environments caused considerably degradation of the beams strength, which became
increasingly more severe at longer exposure times. The wet-dry condition had a slightly worst
effect on the ultimate strength of the externally reinforced beams than did the freeze-thaw
cycling. This was especially true for the aramid reinforced beams, which lost only 9% of their
original strength after 100 freeze-thaw cycles and 36% after 100 wet-dry cycles. The GFRP
reinforced beams degraded the most as a result of both environmental exposures, which
reduced the strength by 27% after 100 freeze-thaw cycles and by 36% after only 50 wet-dry
cycles. Of the three types of fabric investigated, the carbon reinforced FRP proved to be the
most durable, losing around 20% of strength after 100 cycles of each exposure and still
remaining much stronger than its unreinforced counterpart. The failure mode of the E-glass
reinforced beams was the same irrespective of the environmental conditions, i.e. the
specimens always failed as a result of the tensile failure (tearing) of the fabric. A similar
situation was found for the beams reinforced with carbon and aramid fabrics, i.e. the
environmental conditions did affect significantly the mode of failure. After exposure to both
freeze-thaw and wet-dry cycling, degradation of the bond between concrete and fabric was
often observed for both composites, evidenced by the reduced adherence of concrete to the
fabric.
The long term durability of concrete beams externally bonded to FRP sheets and exposed
to harsh environments, was analyzed by other authors [Toutanji and Gómez, 1997]. In
particular, these authors have investigated the effect of wet-dry cycles using salt water on the
performance of FRP-bonded concrete beams and on the interfacial bond between the
composite and the concrete. Different types of FRP sheet were used: two carbon fibers based
and two glass fibers based laminates. Different two-part epoxies were used as matrices for the
composites. One layer of each FRP sheet was bonded to the tension side of the concrete
beams. All specimens were left at room temperature for al least three days before exposure.
Each wet-dry cycle consisted of an immersion in salt water (using 35 g of salt in one liter of
water) for 4 hours, for the wet regime; the dry stage was in hot air at 35°C and 90% of R.H.
for 2 hours. A total of 300 wet-dry cycles were performed, taking 75 days. For comparison
purposes, bonded concrete beams were kept in a controlled ambient (20°C) for 75 days. All
the samples were tested in a four point bending mode. The results showed that, even if
exposed to the harsh environment, the beams exhibited a significant increase in load capacity
when FRP sheets were externally bonded on the tension face. Moreover, laminates
strengthened with carbon fibers always performed better than those reinforced with glass
fibers, even thought the wet-dry exposure caused a general decrease in ultimate strength.
None of the specimens subjected to the flexural tests failed within the FRP, and in most cases
debonding occurred between the FRP sheet and the concrete interface. Therefore, the
reduction in strength was attributed to a deterioration of the interface. The kind of epoxy used
to bond the fibers to the concrete element determined in some way the extent of decrease of
bond strength. The highest reduction in strength, from 19% to 33%, was found for a modified
amine/epoxy system. The lowest, between 3% and 8%, for a bisphenolic epoxy cured with a
mixture of polyoxypropylene diamine, isophorne diamine and aliphatic amine. No further
details were reported on these epoxy systems, in particular their Tg, to be able to provide an
explanation for the difference in behavior exhibited by the different epoxies.
The effect of wet-dry conditions on reinforced concrete beams externally strengthened
with unidirectional carbon fiber laminates, was evaluated by Beaudoin and co-workers
[Beaudoin et al., 1998]. The trade name of the CFRP analyzed suggests that wet lay-up
process was used to apply the plates, based on an epoxy matrix, to the tension face of
concrete beams using a cold-cured epoxy adhesive. After manufacture, the systems were
allowed to cure under laboratory conditions for 12 days. The strengthened beams were, then,
subjected to wet-dry cycles, consisting in immersion in water at 21°C for five days, followed
by a two-days drying at 27°C. After exposure, the beams were tested to failure in a four-point
bending mode. The results of flexural tests revealed a small reduction (about 10%) in the load
carrying capacity of plated beams subjected to 13 wet-dry cycles. In the case of beams
exposed cycles, this reduction was explained in terms of a change in failure mode, from
tensile rupture of the sheet, observed for control specimens, to peeling of the sheet before
tensile failure of the sheet. The ultimate failure strain was also reduced by the performed
exposure.
The durability of strengthened concrete reinforced with CFRP laminates was evaluated
by exposure to simulated marine environments [Sen et al., 1999]. These authors used two
different types of carbon fibers, i.e. bidirectional woven fabric and unidirectional carbon fiber
prepreg sheets, and five different commercial, as well as experimental, epoxy systems. The
carbon fiber sheets, as single layer or double layer, were applied to the surface of concrete
elements by hand lay-up technique. Wet-dry cycles in 15% salt water and combined wet-dry
and hot/cold (60°C – room temperature) cycles in 5% salt water were used to simulate marine
environments. Both types of exposure were carried on for 17 months, with additional six
month outdoor exposure before testing. Control samples were kept in air-conditioned
laboratory along the aged ones, and were tested in both shear and in uniaxial tension mode.
The results showed that there was some deterioration of the FRP/concrete bond in specimens
exposed to both wet-dry cycles. However, by comparing these results with those reported for
similar samples outdoor exposed for 23 months, it was found that bond strength degradation
occurring after wet-dry cycles was greater than that experienced after outdoor exposure. The
latter observation suggested that the extreme temperature range and humidity to which the
specimens were subjected were far more severe than those reasonably expected under normal
service conditions. In spite of this, bond degradation was minimal, especially when the
samples were properly manufactured.
In a similar study, the effects of harsh environmental conditions, such as wet-dry cycles
using sea water and high humidity, on the compressive strength, stiffness and ductility of
concrete cylinders wrapped with different FRP sheets, were analyzed [Toutanji, 1999].
Concrete cylinders were confined by wrapping them two unidirectional FRP layers, i.e. with a
configuration of 0° orientation. Four types of FRP sheets were selected, two carbon based and
two glass based. They were applied with two types of epoxy resins, the first hardened with a
modified amine, the second with a polyxypropylenediamine. After manufacturing, the
specimens were left at room temperature for at least 7 days before they were subjected to wet-
dry conditioning. The wet step, lasting 4 hours, was carried out by exposing the specimens to
a saline water environment (using 35 g of salt in one liter of water) in a specially constructed
environmental chamber. Hot air at 35°C was used for the dry step, with a duration of 2 hours,
over 300 cycles which correspond to a total of 75 days exposure. For comparison purposes,
control samples were kept at room temperature for 75 days. All the aged and unexposed
specimens were, then, subjected to compression tests to determine their strength, stiffness and
ductility. The results showed that the confinement through GFRP or CFRP sheets, based on
one of the two epoxy systems, produced similar results to the unconditioned specimens, in
terms of strength, ductility and failure behavior. Both epoxy systems, in fact, remained
effective up the final rupture; a thin layer of concrete glued to the innermost composite layer
was always observed on the failed specimens. Ultrasonic pulse velocity measurements,
performed every 30 wet-dry cycles on specimens, showed no cracks or delamination in the
specimens. Concrete specimens wrapped with GFRP sheets using the epoxy hardened with
the polyxypropylenediamine experienced no reduction in strength or ductility after the wet-
dry exposure. Samples wrapped with GFRP based on the epoxy hardened with the modified
amine experienced reductions in both strength (10 and 18%, depending on the fiber taw used)
and ductility (20 and 42%, depending on the fiber taw used) as consequence of the exposure
to this harsh environment. Specimens wrapped with CFRP, regardless of the type of epoxy
used, exhibited a good durability, evidenced by an insignificant reduction in strength (less
than 5%) and ductility after exposure. The latter even increased to some extent (5-15%). The
loss in strength of the GFRP based on the epoxy hardened with the modified amine was
attributed to a degradation of the epoxy matrix, through the penetration of the saline water.
The polyxypropylenediamine cured epoxy, on the other hand, may have formed a more
durable barrier for the protection of the fibers. However, in the case of CFRP, even though
the wet-dry cycles were able to cause damage of the epoxy matrix cured by the modified
amine, this exposure had no significant effect on the durability of CFRP.
In order to reproduce the long term behavior of GFRP under tropical climate, accelerated
weathering tests were conducted in an environmental chamber on both GRFP laminates and
concrete plates bonded with GFRP sheets [Liew and Tan, 2003; Tan and Liew, 2005]. The
authors examined two E-Glass composite systems, with different fiber weave configurations
(unidirectional and bidirectional woven rowing for the first and the second configurations,
respectively) and matrix resins (two part epoxy for the first, unsaturated polyester for the
second). The bond strength of GFRP was also evaluated by pull-apart tests on concrete plates
bonded with GFRP laminates. The cure of the matrix and of the adhesive resins for both
composites was performed in laboratory for more than 2 weeks. The accelerated weathering
was done by exposure to UV-A radiation, through wet/dry cycles at high humidity levels.
This was performed in an environmental chamber to simulate the natural weathering effect of
a tropical area, such as that of Singapore. The GFRP specimens were taken from the chamber
every 15 days, measuring the changes in their tensile properties, up to 60 days. The bonded
GFRP plates were subjected to the same accelerated weathering and bond tests were
performed after one week, 1, 3 and 6 months of exposure. The results showed that the tensile
strength and bond strength of both GFRP laminates decreased with exposure time. The initial
bond strength value was dominated by the type of the matrix resin used and was higher in the
case of the epoxy matrix. However, the bond strength measured for both composites,
decreased at the same rate throughout the accelerated weathering period.
The effects of several simulated harsh environments on the mechanical properties of a
commercial GFRP laminate and of reinforced concrete (RC) columns reinforced with an outer
shell of the same GFRP, were evaluated by Silva [Silva, 2007]. The composite was produced
using a cold-cured epoxy resin, with a initial glass transition temperature of 66°C, and a
woven fabric of unidirectional longitudinal E-glass fibers with a thin transverse distribution of
aramidic fibers. Tensile tests along the direction of the alignment of the glass fibers were
performed after submitting the specimens to low-high humidity cycles, salt-fog cycles and
low-high temperature cycles. Moisture cycles were performed by changing the relative
humidity every 12 hours from 20% to 90%, keeping a fixed moderate temperature of 40°C.
Salt fog spray cycles consisted of 8 hours in salt fog at 35°C and 98% R.H., followed by 16
hours drying at room temperature. The temperature cycles were performed by keeping the
specimens at 20°C for 12 hours and at 50°C for the subsequent 12 hours, at the fixed
humidity of 80%. All cycles were performed for up to 10000 hours. Finally, standard coupons
for tensile tests were subjected to UV radiation cycles, using a xenon bulb equipped with a
filter, creating an average radiation density of 550 W/m2. The UV cycles consisted of an
irradiation period of 102 minutes in dry atmosphere at 45°C, followed by 18 minutes of water
submersion. The cycles were performed for up to 1000 hours. The results of tensile tests
performed on samples exposed to moisture cycles showed a continuous slow degradation of
mechanical strength, up to a decrease of 11% after 10000 hours. The ultimate failure strain
experienced an initial reduction of 7.3% after 2000 hours, and remained at the same level at
longer exposure times. Salt fog effects were more severe, even at short exposure times.
Fluctuations in average tensile strength values were observed in this case, and was attributed
to some heterogeneities in the material. They generally decreased, however, with increasing
the exposure time. After a 10000 hours exposure, the final decrease in strength was 12%. This
was explained in terms of the degradation induced by the absorbed seawater, degrading first
the resin matrix, then the interface between matrix and fibers and, finally, attacking the glass
fibers themselves. In the case of salt fog exposure, moreover, a lowering of approximately
4°C in the initial Tg of the epoxy matrix was recorded, which is in agreement with the
decrease in ultimate strength measured. Thermal cycles of a small amplitude at moderate
temperatures produced an insignificant loss of strength (i.e. less than 5%) after 10000 hours
exposure. The tensile stiffness, as measured by the Young modulus, experienced a decrease of
about 11% between 3000 to 5000 hours exposure and a further negligible decrease. It was
concluded that dry-wet cycles caused higher degradation than the thermal cycles. The
combined effects of UV radiations, moisture penetration and moderate temperature (45°C),
has led to a 8.5% loss in strength after 1000 hours exposure. In this case, the surface damage
of the matrix produced by UV radiations increase the rate of moisture penetration, leading to
a decrease of the ultimate strength of the laminate at short time. Aging at moderate
temperatures, on the other hand, leads to further curing of the matrix resin, with a slight
increase in strength. At longer times, surface cracks occurred extensively over the laminate,
causing degradation due to water sorption process. Finally, it was found that the effects of the
same environmental conditioning on confinements of concrete with GFRP jackets are much
less severe than those found on the mechanical properties of the GFRP alone.
Other authors have analyzed the effect of dry-wet cycles on the bond strength developed
between CFRP, based on a cold-cured epoxy resin, and bricks [Briccoli Bati and Rotunno,
2002]. The cycles consisted of an immersion of the specimens in water (at 15°C) for 20
minutes followed by a 12 hours exposition in air. These cycles were repeated from 6 to 96
times. A progressive reduction of the resistance of the bond strength was registered by
increasing the number of cycles. The decrease measured after 96 cycles was by about 24%.
The observation of the samples after the mechanical bond tests evidenced that rupture
occurred almost always at the interface between the composite and the brick, suggesting a
loss of adhesion of the matrix resin due to the presence of water.
Effect of Natural Exposure
Monitoring the actual properties of a material is the only reliable way to establish the true
effects of service conditions on the material. Simulated laboratory exposures are often more
severe than field exposure, and can provide, therefore, different mechanisms of degradation in
materials. Conversely, considering the enormous number of different composites that can be
manufactured and the wide variability of climatic conditions that they can be encountered
during natural weathering, field exposure is too expensive and time consuming to be
considered the only reliable method to estimate the durability of composite materials.
The effects of a rather polluted urban environment on the properties of a glass-fiber
composite, based on a bisphenolic epoxy matrix cured at 20°C, was analyzed at short
exposure times (six months) [Rinaldi and Maura, 1993]. A first very dry period (July-
September) was followed by a humid rainy season (October-December). The maximum
measured temperature was 36°C and the minimum was 3°C. After this period, the maximum
measured decrease in tensile strength was by about 10%. Even though this result is rather
encouraging, the reference period was considered to be too short and, therefore, not
representative of the long term behavior of the composite exposed outdoor.
A wet lay-up composite, made by a two-part epoxy, cured at ambient temperature in the
field, and an E-glass woven fabric, with fibers primarily in the warp direction and aramid
tracers in the weft direction, was exposed to a field environment by Zhang and co-workers
[Zhang et al., 2003, b)]. At the end of the research programme, i.e. after a 20-month period,
the composite showed a reduction in tensile strength of about 21%, which appeared to be
continually decreasing with exposure time. This was accompanied by a decrease in short-
beam-shear strength of about 10%. The initial glass transition temperature, measured by
dynamic mechanical analysis as 87°C for unexposed samples, decreased to a final value of
81°C. The reduction in Tg and the deterioration of mechanical properties were attributed to
plasticization effects due to absorption of atmospheric water. The results showed that
degradation was dominated by resin and interface deterioration mechanisms, induced by the
moisture uptake.
In order to assess the durability of E-glass/vinylester composites, produced by the wet
lay-up process, a number of laminates was exposed to actual outdoor weathering [Zhang et
al., 2000]. Two different types of composites were manufactured, the first consisting of a
four-layer woven rowing, the second of a three-layer woven rowing sandwiched between
alternating layers of chopped strand mat. A cold-cured vinylester resin was used as the
matrix. The composite panels were cured at ambient temperature and at 60-70% R.H. for a
period of two months before testing or exposure. Natural weathering exposure was conducted
by placing composite specimens in the open without constrains in Sidney, Australia, for a
period of 17 months. Over this time period, the average temperatures in spring, summer,
autumn and winter were 25°C, 35°C, 28°C and 15°C, respectively. The maximum
temperature measured in summer was 39°C and the lowest in winter 4°C. Tensile tests were,
then, performed on both exposed and unexposed specimens. The combined effect of
temperature variations, moisture/water presence, UV exposure resulted in minor reductions in
mechanical properties over those measured for unexposed specimens. Deterioration of
performance was seen to be greater for the composite made by a combination of chopped
strand mat and woven roving, resulting in a reduction in strength of about 5%. From a
microscopic analysis of the fractured surface, it was evaluated that natural weathering has
caused a severe degradation at the surface level, due to the combined effects of shrinkage
stresses, due to differences in coefficients of thermal expansion of the E-glass reinforcement
and the resin, and swelling of the resin upon water ingress. After a 17-month exposure to
natural weathering a clear pattern of deep cracks was observed in the resin rich areas,
providing an easy path for the ingress of moisture and subsequent degradation of the fibers.
The degradation of resin rich areas was also attributed to UV exposure. The effect of
weathering was more severe in resin-poor areas where erosion of the matrix up to the
reinforcement can be seen in discrete areas. Discrete cracking in the resin perpendicular to the
fibers was observed, with some fiber-matrix debonding, emphasizing initiation of fiber level
degradation. Natural weathering in a reasonably dry climate resulted in an slight increase of
Tg (6-8°C) attributed to a post-cure. Finally, the comparison of results found for samples
naturally weathered and those resulting from immersion in salt solution or from thermal
cycling showed that levels and rates of degradation of outdoor exposed samples were always
significantly less and slower than those recorded for specimens exposed to simulated severe
environments. On the other hand, from a microscopic analysis of the degraded surfaces it was
found that the effects are similar or even more severe for outdoor weather relatively to
simulated harsh environments, once the surface of the composite was degraded. The authors
suggested, therefore, to protect the specimens from weathering effects, in order to avoid a
rapid degradation through the thickness.
Two E-Glass composite laminates, with different fiber weaving configurations
(unidirectional and bidirectional woven rowing for the first and the second configurations,
respectively) and matrix resins (two part epoxy for the first, unsaturated polyester for the
second), were analyzed by Liew and Tan [Liew and Tan, 2003; Tan and Liew, 2005]. Tensile
specimens for both composites were produced and allowed to cure in the laboratory for more
than 2 weeks. Small-scale reinforced concrete beams were also produced by plating with a
GFRP laminate. All the specimens were weathered outdoor (in the Singapore area),
measuring every 3 months the changes in tensile properties up to one year. The results
showed that the ultimate tensile strength of both GFRP laminates decreased with exposure
time when subjected to tropical outdoor climate. On the other hand, under the same outdoor
exposure, the variation in ultimate stain and modulus was found to be dependant on the type
of matrix resin used. In particular, the ultimate strain of the epoxy based GFRP decreased
considerably, while its modulus was only slightly reduced. The decrease in ultimate strain for
polyester based laminate specimens was relatively small compared to the decrease in
modulus. The failure modes observed for both GFRP laminates were unaffected by exposure
time. The epoxy based GFRP specimens generally ruptured with longitudinal splits between
unidirectional fiber rowing; whereas the polyester based laminates failed with cracks
perpendicular to the direction of tensile load. Finally, the failure mode of GFRP-strengthened
beams changed with the duration of the weathering exposure from concrete crushing to
rupture of the GFRP system. This is the failure mode more frequently observed at longer
exposure time.
The durability of strengthened concrete reinforced with CFRP laminates was evaluated
from outdoor exposure by other authors [Sen et al., 1999]. Bidirectional woven fabric and
unidirectional carbon fiber prepreg sheets were applied to the surface of concrete elements by
hand lay-up technique using five different commercial or experimental epoxy systems. The
samples were exposed outdoor up to 23 months. For comparison purposes, some control
specimens were kept in a controlled laboratory ambient. Shear and tensile tests were
performed on all specimens. Outdoor exposure was found to deteriorate the bond between the
FRP and concrete element only to a minor extent.
In Canada, field applications that use FRP for the strengthening and the rehabilitation of
civil engineering infrastructures date from 1995 [Neale and Labossière, 1998; Rizkalla and
Labossière, 1999]. Thus, only very few field data on the long term behavior are available.
Nevertheless, to date the performance of the FRP field applications have proven to be very
successful [Neale et al., 2001].
The effect of natural weather was analyzed by monitoring the temperature changes and
the deformations taking place in different unidirectional CFRP systems applied for the
strengthening of a bridge deck slab in the North of Portugal [Silva et al., 2005; Juvandes et
al., 2006]. The CFRP laminates were based on different commercial epoxies and were applied
at ambient temperature (in the field). The maximum temperatures registered in the inner face
and on the upper face of the deck slab were 37 and 47°C, respectively, i.e. fairly close to the
glass transition temperatures of the matrix resins of each composite. Very important,
however, were also the differences in temperature measured between the deck slab upper face
and bottom face. The authors attributed an harmful increase in stress level across the slab to
this thermal gradient. The variations in the strain at break of CFRP systems due to
temperature changes were found to be about 60% of the initial value. However, during a
period of almost three years, no significant change in the behavior of the CFRP systems was
registered.
Conclusion
Several applications of FRP based strengthening methods have already been reported
worldwide for buildings and bridges. However, precise knowledge of the long term behavior
of the strengthened elements is still very limited. Whilst the technical and economical
advantages of using FRP materials for strengthening and upgrading concrete structures are
universally recognized, there are still serious concerns about the long term durability of such
materials. Therefore, the main challenge of the researchers in this area for the forthcoming
years is to determine a more complete understanding of the degradation process, which takes
place in different environments.
From the analysis of the recent scientific literature focused on durability of FRP
specifically designed for civil engineering applications, several questions arise:
• From the different durability studies performed on different types of FRP, are there
common trends which can be reliably used to predict their long term behavior?
Referring to the effect of environmental agents on performance of composites, it is noted

that temperature can affect the properties of FRP composites in several ways. Thermal
variations can induce the softening of the matrix in approaching the glass transition
temperature. It can promote the post-cure of the matrix itself, resulting in the stiffening of the
composite. It can also cause debonding and form micro-cracks at the interface between FRP
and concrete, as a consequence of differences in thermal expansion coefficients. Most of
these effects are permanent and irreversible.
The effect of water, in the liquid or vapor state, on composites depends on several
parameters, namely the kind of matrix resin and fibers used, the configuration of fabrics
(number and disposition of plies), the direction of application of load. Different experimental
studies have proved that tensile mechanical properties of a single ply composite in the fiber
direction are highly dependent on the properties of the fibers. In the case of carbon fibers,
therefore, absorption of water has hardly any effect on properties. In the case of laminates
manufactured with glass fibers, on the other hand, water can cause deterioration of
mechanical properties (stiffness and strength), which worsens with increasing immersion
time and temperature. When using laminates composed of several plies, the role of interface
between the adjacent layers becomes crucial. Since the matrix resin is responsible for the
adhesion between plies and it is generally more susceptible to degradation by water, greater
reductions in tensile strength are found for thicker specimens composed by a large number of
plies. Generally, interlaminar properties are also intrinsically dependent on the resin
characteristics, and undergo similar deteriorations. An increase in the interlaminar fracture
toughness, however, can take place as a result of the immersion in pure water, which cause
plasticization of the matrix resin. Referring to the influence of the nature of the matrix, epoxy
and vinyl ester resins are deemed to be more resistant to the action of water. In polyester
based composites, on the other hand, hydrolysis of the resin can take place during immersion,
causing severe damage.
Freeze-thaw exposure generally causes severe degradation in composite properties due to
the stiffening and embrittlement of the matrix resin at temperatures below their Tg, with the
consequent formation of micro-cracks. Fiber-matrix debonding and a local loss of adhesion
strength towards substrates may take place due to the difference in coefficients of thermal
expansion. Possible accelerated penetration of water and other solutions during the thaw
regime is another cause of degradation of properties. Reductions in tensile strength and
interlaminar fracture toughness are generally observed after freeze-thaw cycles. The loss in
strength is even more severe when the thaw regime is performed in saline environments.
Exposure to freeze-thaw cycling was found to affect to a minor extent the flexural strength,
short beam shear strength (SBS) and the in-plane shear strength of the FRP. All the
mentioned effects are generally magnified by increasing the number of freeze-thaw cycles
and are almost independent of the kind of matrix resin and fibers used. The permanence at a
sub-zero temperature, on the other hand, has shown to have only a limited influence on the
mechanical properties of an FRP.
The durability of a composite in saline or acid solutions depends on the resistance of both
the matrix and the reinforcing fibers to these agents. Immersion in simulated seawater,
alkaline and acid solutions is particularly harmful for AFRP and GFRP composites,
producing damage at the fiber/resin interface for both kinds of FRP and the degradation of the
glass fibers for GFRP. The tensile properties of CFRP are generally not affected by
immersion in either simulated concrete pore solutions or any usual saline and acid solutions
used for reproducing aging. The flexural and interlaminar characteristics of carbon fiber
based composites, on the other hand, appear more susceptible to exposure to alkaline and salt
solutions as compared to immersion in pure water. The results are attributed to a greater
degree of hydrolysis and to chemical degradation caused by a high pH and/or by the presence
of saline ions over longer time periods. Regarding the matrix resins, epoxies have shown to
be more resistant to alkaline environments than vinyl esters and polyesters. A certain decrease
in Tg generally occurs after prolonged immersion in any solution analyzed, which is
attributed to plasticization and hydrolysis of the matrix resin caused by immersion in a

aqueous solution rather than to chemical interactions between the resin and the specific
constituents of the solution. Drying even over prolonged periods of time specimens after
immersion not always results in the complete regain of the initial performance, which
indicates that such agents generally cause irreversible changes and damages in composites.
Finally, it must be emphasized that different chemicals solutions, although aimed at
simulating the same aggressive environment, do not have equal levels of chemicals
concentration and are sometime even different in constitution. Hence, they are liable to
produce different and unreliable results.
Ultraviolet radiations affect mainly the surface and consequently degrade only the matrix
of an FRP, causing decomposition of the resin molecules. The consequent embrittlement of
the matrix produces micro-cracks at the surface, which in the presence of other environmental
agents, can accelerate the degradation process by allowing easier penetration of fluids into the
interior of the laminates. Exposures to UV produce a limited reduction in fracture resistance
(impact and tensile strength) of aramidic and glass fiber reinforced FRP, whereas CFRP does
not appear to be affected at all. The fibers are likely to absorb all the UV radiations, thereby
providing a very effective protection of the matrix. In some cases, the exposure to radiations
is even able to produce a slight increase in stiffness and strength of laminates through the
post-cure of the matrix resin.
In order to simulate true environmental conditions, in which more than one
environmental agent is present, FRP are often exposed to a combination of different
conditions of temperature, degree of humidity, or immersion in different water solutions.
Exposure to acid or salt solutions in both freeze-thaw and wet-dry environments have been
found to cause severe degradation of the mechanical and adhesive properties of FRP. Most of
the deterioration in bond strength is located at the interface level, i.e. the bond between FRP
and substrate, which degrade as a consequence of the exposure. There is some indication that
cyclic regimes, including periods of wet and dry exposure, cause a greater permanent
reduction in performance than simple immersion in the same solution. High temperatures are
often employed to accelerate the effect of other environmental agents. This general rule,
however, is not always reliable. Elevated temperatures can, in some cases, cause further
curing of the matrix resin.
Natural exposure of fiber reinforced polymers generally has the following effects: a) a
minor reduction in mechanical properties of FRP caused by plasticization of the matrix resin
by atmospheric water uptake; b) severe degradation of the surface in the resin rich areas,
mainly attributed to UV exposure, which creates cracks and provide an easy path for ingress
of moisture, which can then cause degradation of the fibers; c) possible slight increases in Tg
of the matrix resin, due to post-cure. Comparison of properties measured on samples
weathered naturally with those measured after accelerated laboratory exposures, generally
indicates that levels and rates of degradation of outdoor exposed samples are significantly
lower than those recorded for specimens exposed to simulated environments. In addition,
outdoor exposure tests have demonstrated that deterioration of the bond between FRP and
concrete substrate is only very marginal.
From comparisons of different types of FRP’s in relation to their resistance against
environmental agents, carbon fiber based composites are proved to be the most durable in any
harsh environment. Neither exposure to liquid water and moisture, nor thermo-hygrometric
treatments and exposures to chemical solutions and UV radiations have any significant effect
on the mechanical properties measured in fiber direction of the composite. Carbon based
composites are considered, therefore, better suited for applications involving harsh exposures.
Glass fiber laminates, on the other hand, show the lowest durability in chemical solutions,
especially alkaline ones. The reduction in their tensile stiffness is generally small, while both
ultimate strength and strain at break are significantly reduced by exposure to either water or
simulated seawater and acidic and alkaline solutions. The durability of GFRP generally can
be improved by using hybrid glass-carbon fabrics.
The orientation of fibers in fabrics and its weave pattern can affect the durability of
composites in harsh environments. Unidirectional laminates, with the fibers lying in the
direction of the load, have a better performance than bidirectional ones tested in tensile mode.
In bidirectional fabrics, the resin matrix has a greater influence on the mechanical properties
than in the case of unidirectional laminates. Moreover, the matrix is more affected by
environmental agents than do fabrics. As already stated, the behavior of the matrix resin is
more influential on the mechanical properties measured in the off-axis direction and when the
load distribution is dominated by the fiber-matrix bond.
Referring to the influence of the weave pattern of fibers in laminates, the use of tightly
stick fibers enhance the durability of composite, by hindering the penetration of water and
other aqueous solutions inside the laminate. Similarly, the presence of layers of chopped
strand mat on the surface of a laminate, consisting of woven roving plies, can act as a barrier
to moisture diffusion through the thickness, hindering the penetration of aqueous solution into
the woven roving core.
It must be emphasized, finally, that in several studies conducted on durability of FRP for
structural strengthening not sufficient details are reported on the kind of matrix used and on
the curing conditions used before any environmental exposure of the specimens. In some
durability studies, which are not included in this review, generic “FRP” laminates are
reported to be used as reinforcement for concrete elements, without specifying whether the
matrix is hot- or cold-cured, and whether the composite was previously produced by an
industrial process employing controlled high-temperature curing cycles or manually applied
by wet lay-up at a “uncontrolled” ambient temperature. Obviously, the durability in harsh
environments of polymeric composites manufactured by different techniques could be
significantly different. This observation can partly justify the discrepancies observed in some
durability studies.
• Do the durability procedures employ universal methods and procedures or are they
performed on the base of the experience and the skill of the researchers?
Many of the experiments on durability aspects are conducted according to standard

procedures which are not appropriate for the particular systems, due to the lack of specifically
designed standards for polymers used in civil engineering applications. For instance, the
standard frequently employed for water absorption tests [ASTM D 570-81, 1988]
recommends that before immersion in distilled water, a sample must be subjected to a
conditioning procedure in order to assure the complete dryness to samples. This stipulates that
the sample is dried in a vacuum oven for 24 hours at 50°C and then cooled in a desiccator.
The described conditioning procedure performed on cold-cured resins which are not fully
cross-linked can be regarded as a thermal treatment that can influence the properties of the
adhesives.
As already pointed out, some of the reported experimental studies do not give enough
information on the conditions before the execution of the aging experiments. Ideally, one
should ensure the attainment of a “stable” system, i.e. a system completely cured at the same
temperature of the aging experiments, in order to separate and analyze the effects that can be
totally attributed to the environmental conditions.
• Do standards for durability tests specifically designed for composites based on cold-
curing thermosetting resins exist?
The answer is obviously: no!

Due to several different considerations, it is likely that the well studied hot-cured
thermosetting adhesives and matrices cannot be used in the specified applications. Thus,
although standards and data from previous investigations in many areas (aeronautical,
aerospace, etc.) can be useful, they are not directly applicable. There is a urgent need,
therefore, to develop durability standards and guidelines pertinent to these specific
applications and exposure conditions [Bank, et al., 2003; Karbhari et al., 2003].
• Can the accelerated tests be useful to predict the long term behavior of systems
exposed to different environments?
Accelerated tests are usually performed by exposing the materials to environments more
aggressive than those generally encountered in practice, i.e. very high temperatures,
prolonged immersion and higher loads. This procedure, whilst reducing test time, may give
unrealistic failure modes which may not take place under service conditions. Therefore, any
accelerated weathering condition must be selected to give the highest possible level of
accelerating effects, but the conditions selected must produce degradation mechanisms which
are as near as possible to the way the specific material would degrade in natural conditions.
The final conclusion is that accelerated tests are reliable only if a precise correlation exists
between the data obtained from accelerated aging and the performances of the materials
exposed for long time to environment. At the present time, the results of the accelerated aging
should be regarded as qualitative indicators and used as a reference limit value.
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Chapter 2
SMART ADHESIVELY BONDED COMPOSITE

JOINTS: ANALYSIS AND DESIGN
Jinquan Cheng*, Guoqiang Li and Su-Seng Pang

Department of Mechanical Engineering, Louisiana State University,
Baton Rouge, LA, 70803
Abstract
Due to their inherent advantages over mechanical-fastening methods, the use of
adhesively bonded composite joints has been significantly increased in recent years for joining
composite beams, panels, tubes, etc., which are fundamental components in civilian, military
and aeronautic structures. Because the applied load in the adherends is always transferred in
the form of shear and/or peel stresses through the adhesive layer, the stress concentration
developed in the end regions at the adhesive bondline is the principal reason for causing the
premature and catastrophic failure of adhesively bonded joints. This has always been a
dilemma for the designers of such joints. In order to reduce the peel/shear stresses
concentration and improve the joint strength, some traditional mechanical methods have been
developed as practical solutions to reduce the stress concentration, such as rounding off sharp
edges, spewing fillets, and tapering adherends. These methods are passive in reducing stress
concentration, i.e., they are ineffective unless the pattern and magnitude of the applied loads
are fixed. Comparing to these traditional mechanical enhancement methods, an active smart
strength improvement method for adhesively bonded composite joint is introduced in this
chapter to adaptively realize the reduction of peel/shear stress concentration through the
integrated piezoelectric layers as sensor/actuator in the composite joint system. This type of
joint is smart because, on one hand, the integrated piezoelectric layers can serve as sensors to
monitor the joint system deformation; on the other hand, the piezoelectric layers also serve as
actuators to produce a counter-balancing force or moment. In such smart joints, counter-
balancing forces and moments can be adaptively produced by adjusting the applied electric
fields to the integrated piezoelectric layers based on the information as sensors. The additional
forces and moments can be controlled to act oppositely to those developed internally by the
payloads, thereby alleviating the stress concentration in the joint edges and smartly improve
the joint strength. In this chapter, the fundamental concept of the proposed smart adhesively
bonded composite joint method is firstly introduced, and then, the details in designing and
analyzing such joints under various loading conditions are systematically discussed, including
*
To whom correspondence may be addressed, e-mail: hitcjq@hotmail.com
74 Jinquan Cheng, Guoqiang Li and Su-Seng Pang
single-lap and single-strap smart composite joints subjected to tensile loading, and smart
composite pipe joints subjected to axial tension or bending.
1. Introduction
Owing to the restriction of manufacturing technology and complicated structural
configuration, it cannot be avoided that structural components must be joined together to form
an integrated structure, including beams, plates, rods, pipes, etc. Typical joint methods can be
mainly categorized into three types: (1) mechanical fastening; (2) welding; and (3) adhesively
bonding. Among these joining methods, there are several prevailing advantages associated
with adhesively bonded joints, such as more uniform distribution of stress, lighter weight,
water tightness, and better fatigue properties. Therefore, the adhesively bonding method has
been in the center of the scene due to its ease of fabricating large and integrated structures.
Recently with the advancement of adhesive material science and bonding technology, the
adhesively bonding method has been increasingly used in engineering applications, especially
in aeronautics, automotive, and civilian structures, due to the continuously increasing use of
composite materials in these sectors.
However, since the loads are transferred in the form of shear and/or peel stresses through
the adhesive layer between the adherends, the failure of such joints always occurs
prematurely under extreme loading conditions in cohesive failure mode (inter-adhesive failure
mode) or adhesive failure mode (adherend-adhesive interfaces mode), due to the inherent
stress concentration at the adhesive interfacial bondline in the end regions. Therefore, how to
improve the traditional adhesively bonded joint strength and further develop long-term
durable joints is critical to modern civilian, military and aerospace structures. In order to
better understand and design the various adhesively bonded joint systems, more accurately
anatomizing the peel/shear stress distribution in the adhesive layer and further reducing the
stress concentration become a crucial task in improving the ultimate capacity of such a
bonded joint. Up to date, a number of predicting works have been conducted to theoretically
and numerically analyze the stress distribution within the end regions of the adhesive layer [1-
26]. One of the earliest such works cited in the literature was the work of Goland and
Reissner [1]. They assumed the adhesive layer to be a relatively flexible patch, and further
obtained a two-dimensional, elasticity based, analytical solution for assessing the stress
distribution in a lap joint. Following this pioneer work, several researchers continued
developing various more sophisticated and more capable theoretical models and numerical
methods for evaluating the stresses distribution in various beam/plate-like joints (e.g., Cornel
[2]). Some further considered the nonlinear response of adhesives and adherends and its effect
on the stress distribution (e.g., Allman [3]). With the introduction of more complicated
analytical models, the governing differential equations became exceedingly complicated and
difficult to solve analytically [4-11]. As a result, the numerical models, including finite
element method (FEM) and finite differential method (FDM) were incorporated as an
effective tool to consider the more complicated geometries and configurations, and also to
validate the existence of stress concentration in the edges of the adhesive layer by several
researchers [12-20]. Unlike the adhesively bonded beam and plate joint systems that have
been investigated by many theoretical, numerical and experimental works as mentioned
above, only a few studies have been conducted to investigate the adhesively bonded pipe joint
Smart Adhesively Bonded Composite Joints: Analysis and Design 75
system [21-32]. Most of the works were focused on the analyses about the pipe joint system
subjected to torsion loading [21-28], others were mainly about the pipe joint system subjected
to tensile loading [29, 30] or bending loads [31]. Practically, the pipe system may be over the
ground or embedded under the ground, which means that the applied external loading is more
complicated than the previous research works and should include the internal pressure and
other external loading (i.e. axial tension, torsion or bending etc.). Thus, theoretically studying
the stress distribution of the pipe joint system under the combined loading is of necessary and
importance. Recently, Lees [32] started a work to use a simple beam model to evaluate the
tubular joint subjected to the combined internal pressure and axial extension loading.
From these previous theoretical and numerical analyses, and, experimental studies, it is
revealed that in the adhesively bonded joint systems, the stress concentration would always
exist and occur in the ends of the interfacial bondline, ultimately inducing failure of the
adhesive joints in cohesive mode or adhesive mode. Therefore, joint designers have to seek
high-performance adhesives and resort to the design of different joint systems to reduce the
stress concentration. Fortunately, some theoretical analyses also found that the stress
distribution in the adhesive layer can be redistributed by adjusting the thickness, length,
material properties of the adhesive and adherends, as well as the applied moments and forces,
as discussed by Hart-Smith [20], Roberts [5], and, Cheng, Chen and Shi [6]. Thus, except for
the choice of adherends and adhesive materials and joint surface preparation and handling,
some traditional improvement methods have been developed to enhance the efficiency of
such joints, including: rounding off the sharp edges, spewing fillets, using fiber reinforced
adhesive, and tapering the adherends etc. [5,6, 20, 33-35]. Recently, using reinforcing patches
to reduce the stresses concentration effect on the adhesive layer was also proposed [36]. For
composite pipe joint system, Pang, Li and their colleagues have made their efforts to use UV
curing FRP composites to develop fast joining method and improve the joint strength of
composite pipes [37-39].
Obviously, most of these improvement methods are traditionally based on the mechanical
fastening methods. They cannot adaptively adjust the stress distribution. In order to smartly
and efficiently improve the joint strength, recently Cheng and his-coworkers have firstly
introduced a smart joint concept into the traditional adhesively bonded joint by using the
smart piezoelectric materials and further confirmed its integrity by relevant experiments [40,
41]. As is well-known, smart materials have some specific and excellent thermal-electro-
mechanical coupling effects, e.g. piezo-effect of piezoelectric materials and thermo-
mechanical induced shape memory effect of shape-memory alloy. Thus, they have been
extensively applied in engineering structures as high performance sensors/actuators. Due to
the high electro-mechanical coupling performance of piezoelectric materials, the piezoelectric
ceramics patches and piezoelectric particle/fiber/wire reinforced composites have been
successfully designed as sensitive and active sensors/actuators for a broad application in
practical engineering structures, as reported by Crawley etc. [42]; Lee and Moon [43]; Cheng
et al. [44]; Wang and Wang [45]; Wu et al. [46]; Vel and Batra [47] and Cheng, Wang and
Du [48, 49]. Based on the previous successful application of the piezoelectric materials in the
single-lap joint system, Cheng and his co-workers further developed the smart adhesively
bonded single-strap joint and pipe joint [50-53]. In the developed smart adhesively bonded
joint system, the piezoelectric patches/composite layers were surface bonded or integrated
into the adherends and served as sensors/actuators. When serving as sensors, the
bonded/integrated piezoelectric patches/layers can detect the external mechanical loading
induced structural deformation by inherent sensitive electro-mechanical coupling effect; when

serving as actuators, the stress concentration in the joint end region can be smartly controlled
and reduced by adjusting the applied external electric field. In order to clearly describe the
working principle of the developed smart composite joint systems, this chapter focuses on
designing and analyzing the various adhesively bonded smart beam-like and pipe composite
joint systems. In the following sections, the basic idea of the smart adhesively bonded beam-
like joint systems is firstly illustrated and followed by respective theoretical analyses and
experimental validation. Based on the preliminary works on the smart beam-like joint
systems, the smart adhesively bonded composite pipe joint system is further developed. In
order to clarify the effect of the integrated piezoelectric layers on the smart pipe joint system,
the systematic theoretical model analyses and detailed solution procedure are presented.
l1 2l l2
ht
P
hb P
(a)
Possible bonding location of
piezoelectric patches/plates
P
(b)
Figure 1. (a) General adhesive bonding single-lap joints and (b) ideational view of the newly developed
smart adhesive bonding single-lap joints.
2. Smart Adhesively Bonded Beam-Like Joint

It is well-known that typical beam/plate-like adhesively bonded joints are composed of
adherends and adhesive, as shown in Fig. 1(a) for a conventional single-lap joint and Fig. 2(a)
for a conventional single-strap joint. As indicated above, the stress concentration existing in
the end regions of the adhesive layer is the main reason for joint failure. In order to reduce the
stress concentration in the joint system, piezoelectric materials have been used to bond with
the joint on the surface or integrated into the adherends to smartly create counter-balancing
forces or moments, thereby reduce the stresses. Previous studies have shown that the
piezoelectric patches can facilitate strain transferring by adaptively adjusting the applied
electric field. In the developed joint, piezoelectric patches were easily bonded fully or
partially on either the bottom or top surfaces of a joint or directly integrated into the
adherends, and then utilized their electro-mechanical coupling effect to create additional
forces and moments required to counter-balance the applied forces, as schematically shown in
Fig. 1(b) for a single-lap joint with surface bonded piezoelectric patches and Fig. 2(b-d) for a
single-strap joint with the surface /internal bonded/integrated piezoelectric patches or

piezoelectric reinforced composite layers. Obviously, it is expected that the size and location
of the piezoelectric patches/piezoelectric reinforced layers and applied electric fields will
have a significant effect on the resultant forces and moments in the various joint systems.
Thus, the following sections will be focused on discussing the effect of the integrated
piezoelectric patches/layers on the stress reorientation in the adhesive bondline for different
joint types: single-lap and single-strap joints through theoretical analyses and relevant
experimental studies. Furthermore, we here assume that the interface bonds among the
adherends and piezoelectric patches/layers are perfect for further studies. Since the main aim
of this chapter is to study the effect of the piezoelectric layer on the stress concentration
developed in the adhesive layer, the analysis of the interface between the adherend and
piezoelectric layer is not considered.
Adherends Adhesive layer
P P
(a) Common single-strap joint
Surface bonded piezoelectric patches
P P
(b) Smart single-strap joint with surface

bonded piezoelectric patches
Surface bonded piezoelectric composite layers
P P
(c) Smart single-strap joint with surface

bonded piezoelectric composite layer
Integrated piezoelectric composite layers
P P
(d) Smart single-strap composite joint integrated with

internal piezoelectric composite layer
Figure 2. Basic structures : (a)common and (b, c, d) smart adhesive bonded single-strap joint systems.
2.1. Smart Adhesively Bonded Single-Lap Joint
A conventional single-lap adhesively bonded joint always consists of two adherends and an
adhesive layer, as shown in Fig. 1(a). In the case of identical adherends, the single-lap joint is
an anti-symmetric joint system. Even if the adherends are non-identical in properties and
geometry, the single-lap joint can be approximately regarded as an anti-symmetric joint
system, hereafter referred to as a “quasi-anti-symmetric” joint. According to the investigation
by Roberts [5], the peel and shear stresses of a single-lap joint distributed symmetrically and
their peak in the joint edges can be reduced by varying the applied load. Therefore, our
intention is to integrate a single-lap joint with an electro-mechanical coupled piezoelectric

material, forming a novel smart single-lap joint system, as shown in Fig. 1(b). Undoubtedly,
the location and size of the patches would have a significant effect on the resulting stresses. In
terms of the anti-symmetrical structural characteristics of the single-lap joint, anti-symmetric
surface bonded piezoelectric patches are used to construct a new smart single-lap joint system
as shown in Fig. 3.
l1 l3 l4 l5 l6 l7 l2
x1 x5
P x3
x2 x4 x6 x7
P
z5
z1 z2 z3 z4 z6 z7
Figure 3. The schematic views of a smart single-lap joint with the anti-symmetric surface.
2.1.1. Forces and Bending Moments in the Smart Joint under Electro-mechanical
Loading
Considering the proposed smart single-lap joint subjected to an axial force, as shown in Fig.
3, the plane section in each adherend is assumed to remain plane to carry the applied force
and bending moment. Now, consider a representative segment model as shown in Fig. 4, the
1-D equilibrium equations for the different parts of the smart single-lap joint can be derived
per the classical plate theory as follows:
dx
x
z
P
Q+dQ
M Q dw
P+dP
M+dM
Figure 4. A representative segment model of a beam subjected to axial forces.
∂ 4 w1 ∂ 2 w1
D11 − P =0 0 < x1 < l1 (2-1a)
∂x14 ∂x12
∂ 4 w2 ∂ 2 w2
D12 −P 2 =0 0 < x 2 < l3 (2-1b)
∂x24 ∂x2
∂ 4 w3 ∂ M p 3 ( x3 ) ∂ 2 w3
2
D123 + − ( P + N 0
) =0 0 < x3 < l 4 (2-1c)
∂x34 ∂x32 ∂x32
P3
∂ 4 w4 ∂ 2 w4
D12 − P =0 0 < x 4 < l5 (2-1d)
∂x44 ∂x42
∂ 4 w5 ∂ M p 4 ( x5 ) ∂ 2 w5
2
D124 + − ( P + N 0
) =0 0 < x5 < l 6 (2-1e)
∂x54 ∂x5 ∂x52
2 p4
∂ 4 w6 ∂ 2 w6
D12 − P =0 0 < x6 < l7 (2-1f)
∂x64 ∂x62
∂ 4 w7 ∂ 2 w7
D22 − P =0 0 < x7 < l 2 (2-1g)
∂x74 ∂x72
where D11, D22, D123, D124, and D12 represent the flexural rigidities of the different segments
of the smart joint respectively, as shown in Fig. 3, and can be obtained as follows:
E1h13 3
D11 = ; D22 = E2 h2 ;
12(1 − μ1 )
2
12(1 − μ22 )
E2 [(h2 + d12 )3 − d123 ] E1[(h1 − d12 )3 + d123 ] ;

D12 = +
3(1 − μ22 ) 3(1 − μ12 )
E [(h + h + d )3 − (h + d )3 ] E [(h + d )3 − d123 ] E1[d123 + (h1 − d123)3 ]

3 3
D123 = 3 3 2 123 2 2 123 + 2 2 123 2 + ;
3(1 − μ3 ) 3(1 − μ2 ) 3(1 − μ12 )
E4 [(h4 + h1 − d124 ) 3 − (h1 − d124 ) 3 ] E1[d124

3
+ (h1 − d124 ) 3 ] E2 [(h2 − d124 ) 3 − d124
3
]
D124 = + + .
3(1 − μ3 )2
3(1 − μ1 )
2
3(1 − μ2 )
2
Moreover d12, d123, and d124 are the distances from the mid-plane to the neutral planes of
the different parts in the smart joint, respectively. And, Npi and Mpi (i=3, 4) denote the
resultant forces and moments induced by the piezo-effect of the ith surface bonded
piezoelectric patch and are represented by:
zi 1
N pi = − ∫ e 31
zk +1
*
k E 3 dz ; M pi = −∫ *
e 31 k E 3 zdz (2-2)
zi 0 zk
Vk
where E3 is the applied electric field and E 3 = − [ H ( x − x 0 ) − H ( x − x1 )] with the
hk
Heaviside step function H ( x − xa ) describing the distributed electrode of piezoelectric
patches/layers[43].
Further, the joint end boundary conditions can be represented by:
w1 = w1, xx = 0 at x1 = 0 ;
w7 = w7, xx = 0 at x7 = 0 ;
and the continuity conditions between the different parts must be satisfied as follows:
(1) At the boundary x1 = l1 and x2 = l3 :
w1 = w2 ; w1, x = −w2, x ; D11w1,xx = D12w2,xx + P(h 2 − d12 ) ;

1
D11w1,xxx − Pw1,x = −[D12w2,xxx − pw2,x ] .
(2) At the boundary x 2 = 0 and x3 = l 4 :
w2 = w3 ; w2, x = w3, x ; D12w2,xx = D123w3,xx + M p3 ( x) + P(d12 − d123) ;
∂M p3 (x)
D12w2,xxx − Pw2,x = −[D123w3,xxx + − (P + N p3 )w3,x ] .
∂x
(3) At the boundary x3 = 0 and x4 = l5 :
w3 = w4 ; w3,x = w4,x ; D123w2,xx + M p3 (x) + P(d12 − d123) = D12w4,xx ;
∂M p3 (x)
D123w3,xxx + − (P + N p3 )w3,x = −(D12w4,xxx − Pw4,x ) .
∂x
(4) At the boundary x 4 = 0 and x5 = l6 :
w4 = w5 ; w4,x = w5,x ; D12w4,xx + P(d124 − d12 ) = D124w5,xx + M p5 (x) ;
∂M p4 (x)
D12w4,xxx − Pw4,x = −[D124w5,xxx + − (P + N p4 )w5,x ] .
∂x
(5) At the boundary x5 = 0 and x6 = l7 :
w5 = w6 ; w5,x = w6,x ; D124w5,xx + M p4 (x) = D22w6,xx + P(d124 − d12 ) ;
∂M p4 (x)
D124w5,xxx + − (P + N p4 )w5,x = −(D22w6,xxx − Pw6,x ) .
∂x
(6) At the boundary x6 = 0 and x7 = l 2 :
w6 = w7 ; w6,x = w7,x ; D12w6,xx = D22w7,xx + P(h2 / 2 − d12 ) ;
D124w6,xxx − Pw6,x = −(D22w7,xxx − Pw7,x ) .
Obviously, for the governing fourth-order differential Equation (2-1), the general
analytical solution can be obtained in the following forms [5]:
For the elastic parts:
wi ( xi ) = Ai + Bi xi + Ci sinh[α i xi ] + Di cosh[α i xi ] (i=1, 2, 4, 6, 7) (2-3a)
For the electro-elastic parts:
wi ( xi ) = Ai + Bi xi + Ci sinh[α i xi ] + Di cosh[α i xi ] + wi ( xi )
*
(i=3, 5) (2-3b)
where Ai, Bi, Ci,, and Di are the unknown constant coefficients to be determined by the
boundary conditions. α i = P / Ei I i is as defined in Reference [5]. The variable wi * ( xi )
denotes the specified solutions due to the piezoelectric coupling effect and is selected based
on the relevant governing equations.
After substituting the general analytical solution, Equation (2-3), into the relevant
boundary conditions, the coefficients Ai, Bi, Ci, and Di can be calculated and then the applied
moments M 1 , M 2 at the joint-edge and the shear forces Q1 , Q2 in the joint can be obtained
by:
∂ 2 w1 ∂ 2 w7
M 1 = − D11 ; M 2 = D22 ; (2-4a)
∂x12 x1 =l1
∂x72 x7 = l2
Q1 = (D11w1,xxx − pw1,x ) x =l ; Q2 = (D22w7,xxx − pw7,x ) x =l . (2-4b)

1 1 7 2
2.1.2. Stress Analysis in the Adhesive Layer of the Smart Joint
In this section, in order to more accurately study the peel/shear stress distribution in the
adhesive bondline, the first-order shear theory (FOST) is used. Further considering that the
function of the piezoelectric patch is to provide the required additional force and moment
only, the thickness of the piezoelectric layer would be relatively thin in comparison to the
adherends. Therefore, the stiffness contribution by the piezoelectric patches is relatively
small, and may be neglected when analyzing the stress distribution in the adhesive layer.
Similarly, the stiffness of the adhesive layer between the piezoelectric layer and the adherends
can also be assumed to be negligible when analyzing the stress distribution in the adhesive
layer between the adherends.
Qt+dQt
Nt h1 Nt+dNt (a)
z x
Mt Qt Mt+dMt
τ1 σ1 τ1
(b)
ha
τ1 σ1 τ1
Qb+dQb
Nb x h2 Nb+dNb (c)
z
Mb Qb Mb+dMb
Figure 5. The infinitesimal substructures of a joint system: (a) the top adherend, (b) the adhesive layer,
(c) the bottom adherend.
The infinitesimal elements of the joint section are depicted in Fig.5. In terms of the static
equilibrium conditions for each layer, the 1-D fundamental equilibrium equations for any
segment of the smart single-lap joint having a unit width and a rectangular cross section can
be obtained as follows:
In the top adherend of the joint:
∂N t ∂M t h ∂Qt
+ τ1 = 0 ; − Qt + t τ 1 = 0 ; +σ1 = 0 ; (2-5a)
∂x ∂x 2 ∂x
In the bottom adherend of the joint:
∂N b ∂M b h ∂Qb
− τ1 = 0 ; − Qb + b τ 1 = 0 ; − σ1 = 0 . (2-5b)
∂x ∂x 2 ∂x
where the resultant forces N t , N b , Qt and Qb , and, moments M t and M b of the top and
bottom adherends can be obtained from the constitutive equations and relationships between
the strains and assumed mid–plane displacements (ut , wt ) and (ub , wb ) , and, rotations
φb and φt in terms of the first-order shear deformation theory by:
∂ut ∂φ ∂u ∂u
ht ht ht
Nt = ∫ 2
σ t dz = ∫ 2
ct*11ε t dz = ∫ 2
ct*11 ( + z t ) dz = ht ct*11 t = A11* t , (2-6a)
∂x ∂x ∂x ∂x
h h h
− t − t − t
2 2 2
ht ht
∂ut ∂φ h3c* ∂φ ∂φ
M t = ∫ σ t zdz = ∫
2 2 ct*11 ( + z t ) zdz = t t11 t = D11* t , (2-6b)
∂x ∂x 12 ∂x ∂x
h h
− t − t
2 2
5 2t * ∂wt 5ht ct*55 ∂wt ∂w

h h
5 2t
Qt = ∫
6 2−
ht σ xz dz = ∫
6 2−
c
ht t 55 (
∂x
+ φt ) dz =
6
(
∂x
+ φt ) = B11* ( t + φt ) ,
∂x
(2-6c)
∂ub ∂φ ∂u * ∂ub
hb hb hb
Nb = ∫ 2
σ b dz = ∫ 2
cb*11ε b dz = ∫ 2
cb*11 ( + z b )dz = hb cb*11 b = A22 , (2-6d)
∂x ∂x ∂x ∂x
h h h
− b − b − b
2 2 2
∂u b ∂φ h 3 c * ∂φ * ∂ φb
hb hb
Mb = ∫ 2
σ b zdz = ∫ 2
cb*11 ( + z b ) zdz = b b11 b = D22 , (2-6e)
∂x ∂x 12 ∂x ∂x
h h
− b − b
2 2
5 h2b 5 h2b * ∂wb 5h c* ∂w * ∂wb

Qb = ∫ hb σ bxzdz = ∫ hb cb55 ( + φb )dz = b b55 ( b + φb ) = B22 ( + φb ) (2-6f)
6 −2 6 −2 ∂x 6 ∂x ∂x
The stresses σ1 and τ1 , strains ε1 and γ 1 in the adhesive layers and rotations φt and
φb in the top and bottom adherends can also be derived from the mid-plane displacements
(ut , wt ), (ub , wb ) in the following forms:
E0 E 0 ( wb − wt )
σ1 = ε1 = (2-7a)
(1 − v0 ) (1 − v0 )
2 2
h0
G0 h h
τ 1 = G0γ 1 = [(ub − ut ) − ( b φ b + t φt )] (2-7b)
h0 2 2
where E0 and ν0 are the Young’s modulus and Poisson’s ratio of the adhesive, respectively.
The following twelve boundary conditions should be satisfied along the boundary edges
( x = ± l ) of the joint system, as shown in Fig. 1(a):
~ ~ ~
N t ( −l ) = N t ( −l ), M t ( −l ) = M t ( −l ), Qt ( − l ) = Qt (−l );
~ ~ ~
N t (l ) = N t (l ), M t (l ) = M t (l ), Qt (l ) = Qt (l );
~ ~ ~ (2-8)
N b ( −l ) = N b ( −l ), M b ( −l ) = M b ( −l ), Qb ( −l ) = Qb ( −l ),
~ ~ ~
N b (l ) = N b (l ), M b (l ) = M b (l ), Qb (l ) = Qb (l ).
where the superscript “~” denotes the prescribed boundary conditions as obtained by Eq.(2-4)
in Section 2.1.1.
After substituting Eq. (2-6) and (2-7) into the governing equation (Eq. (2-5)), the
displacement-based governing equations can be obtained by:
∂ 2 u t G0 h h
A11* + [(ub − ut ) − ( b φb + t φt )] = 0 (2-9a)
∂x 2
h0 2 2
∂ 2φt ∂w h G h h
D11* − B11* ( t + φt ) + t 0 [(ub − ut ) − ( b φb + t φt )] = 0 (2-9b)
∂x 2
∂x 2 h0 2 2
∂ 2 wt ∂φt E0 ( wb − wt )
B ( 2 +
*
)+ =0 (2-9c)
∂x ∂x (1 − v02 )
11
h0
∂ 2 u b G0 h h
*
A22 − [(ub − ut ) − ( b φb + t φ t )] = 0 (2-9d)
∂x 2
h0 2 2
∂ 2φb * ∂wb h G h h
*
D22 − B22 ( + φ b ) + b 0 [(ub − ut ) − ( b φb + t φt )] = 0 (2-9e)
∂x 2
∂x 2 h0 2 2
∂ 2 wb ∂φb E0 ( wb − wt )
*
B22 ( + )− =0 (2-9f)
∂x 2
∂x (1 − v02 ) h0
It is clearly seen that the above are a series of coupled constant coefficient second-order
differential equations. Here, we can utilize the state-space method to solve them analytically
[54]. In order to construct the state equations, some new unknown functions must first be
introduced, as follows:
∂ut ∂φ t ∂wt
Z1 = ut , Z 2 = Z1' = , Z 3 = φt , Z 4 = Z 3 = , Z 5 = wt , Z 6 = Z 5 =
' '
,
∂x ∂x ∂x
∂ub ∂φb ∂wb

Z 7 = ub , Z 8 = Z 7' = , Z 9 = φ b , Z 10 = Z 9 = , Z 11 = wb , Z 12 = Z 11 =
' '
.
∂x ∂x ∂x
Using the introduced unknown variables, the displacement-based governing Eq. (2-9) can
be represented by a first-order state equation system in the following matrix form:
{Z }' = [ A]{Z } (2-10)
In terms of Eq. (2-7), the peel and shear stresses in the adhesive layer can be rewritten by
the introduced state variables as follows:
− E0 E0
σ 1 = [0 0 0 0 0 0 0 0 0 0]{Z } (2-11a)
(1 − v0 )h0 (1 − v0 )h0
2 2
G0 G0 ht G0 G0 hb
τ 1 = [− 0 − 0 0 0 0 − 0 0 0]{Z } (2-11b)
h0 2h0 h0 2h0
where the matrix [A] has the following form:
⎡ 0 1 0 0 0 0 0 0 0 0 0 0⎤
⎢ G0 0 G0ht
0 0 0 −G0
0 G0 hb
0 0 0⎥
⎢ A11* h0 *
2 A11h0 *
A11h0 *
2 A11h0 ⎥
⎢ 0 0 0 1 0 0 0 0 0 0 0 0⎥
⎢ G0ht G0ht2 * *
−G0ht ⎥
⎢ 2 D11* h0 0 *
4 D11h0
+ B11
*
D11
0 0 B11
*
D11 *
2 D11h0
0 G0ht hb
*
4 D11h0
0 0 0⎥
⎢ 0 0 0 0 0 1 0 0 0 0 0 0⎥
⎢ E0 − E0 ⎥ (2-12)
⎢ 0 0 0 1 *
(1− v02 ) h0
0 0 0 0 0 *
(1− v02 ) h0
0⎥
[ A] = ⎢ B11 B11
0 0 0 0 0 0 0 1 0 0 0 0⎥
⎢ −G0 −G0ht G0 −G0hb ⎥
⎢ A22* h0 0 *
2 A22 h0
0 0 0 *
A22 h0
0 *
2 A22 h0
0 0 0⎥
⎢ 0 0 0 0 0 0 0 0 0 1 0 0⎥
⎢ G0hb * ⎥
−G0hb G0hb2 *
⎢ 2 D22* h0 0 G0ht hb
*
4 D22 h0
0 0 0 *
2 D22 h0
0 *
4 D22 h0
+ B22
*
D22
0 0 B22
* ⎥
D22
⎢ 0 0 0 0 0 0 0 0 0 0 0 1⎥
⎢ − E0
⎥
⎢⎣ 0 0 0 0 0 0 0 0 −1 E0
0⎥
*
B22 (1−v02 ) h0 *
B22 (1−v02 ) h0 ⎦
Without loss of generality, the general solution for the first-order state Eq. (2-10) can be
expressed by:
{Z } = e x[ A]{k} (2-13)
where {k} is a vector with twelve unknown coefficients determined by the boundary
conditions at x = ± l . Usually, the matrix [A] has an eigenvalue involving zero with
multiplicity of six.
Obviously, the matrix exponential can be derived directly by either the Cayley-Hamilton
theory or the simple Jordan method [54]. According to the state-space approach in
conjunction with the Jordan Canonical form, the general solution (i.e. Eq. (2-13)) can be
represented by:
{Z } = [ M ]e[ J ] x [ M ]−1{k} (2-14)
where the matrix [M] is the model matrix of [A], which contains the eigenvectors and
[ J ]x
generalized eigenvectors of matrix [A]. [J] is the Jordan matrix and e is a block diagonal
matrix deduced from the eigenvalues of matrix [A] and is presented as:
⎡1 x 1
2! x2 1
3! x3 1
4! x4 1
5! x5 0 L L 0 ⎤
⎢ 1 2 1 3 1 4 ⎥
⎢0 1 x 2! x 3! x 4! x 0 ⎥
⎢ 0 1 x 1
x2 1
x3 0 ⎥
⎢ ⎥
2! 3!
1 2
⎢ 0 1 x 2! x 0 ⎥
⎢ 0 1 x 0 ⎥
⎢ ⎥
M M ⎥ (2-15)
=⎢
0 1 0
e[ J ] x
⎢M O 0 e λ1 x
0 O M ⎥
⎢ λ2 x
⎥
⎢M O 0 e 0 O M ⎥
⎢ 0 e λ3 x
0 ⎥
⎢ ⎥
⎢ 0 e λ4 x 0 ⎥
⎢ 0 e λ5 x 0 ⎥
⎢ ⎥
⎣⎢0 L L L 0 e λ6 x ⎦⎥
The unknown constant coefficients {k} can be determined by using the twelve boundary
conditions (Eq. (2-8)), and, the relevant FOST based strain-stress and strain-displacement
relationships (Eq. (2-6)). Once the unknown coefficient {k} is determined by the boundary
conditions, the peel and shear stresses in the adhesive layer can be analytically calculated by
Eq. (2-11).
2.1.3. Numerical Examples and Analyses
In order to confirm the above theoretical model, some numerical examples are presented to
evaluate the effect of surface bonded piezoelectric patches on the stress redistribution in the
adhesive layer of a smart single-lap joint subjected to a combined mechanical and electrical
load. The following material properties and geometric parameters are used for the adherends,
adhesive, and piezoelectric ceramics:
Adherends: E1=E2=75 GPa, ν 12 =ν 21 =0.25;

Adhesive: Ea=7.5 GPa, ν a =0.33;
Piezoelectric: Ep =84 GPa, ν 3 =0.22, d31= - 310 pC/N;
Basic geometries: l1=500 mm; l2=500 mm; 2l=300 mm, ha=0.5 mm.
+V
Poling direction electrode
(a)
Ground
-V +V
Poling direction
Ground
(b)
Figure 6. The schematic shows for the piezoelectric layer covered with (a) single-polar electrode and
(b) bipolar electrode.
1400
1200
single polar
bipolar
Bending moments (N*m)
1000
800
600
400
200
-200
5 5 5 5 5 5
-6.0x10 -4.0x10 -2.0x10 0.0 2.0x10 4.0x10 6.0x10
Applied electric field (V/m)
(a)
1800
1600 single polar

bipolar
1400
1200
Shear forces (N)
1000
800
600
400
200
-200
5 5 5 5 5 5
-6.0x10 -4.0x10 -2.0x10 0.0 2.0x10 4.0x10 6.0x10
(b)
Figure 7. The influences of applied electric field in the anti-symmetrically surface bonding piezoelectric
layers on the joint-edge bending moments (a) and shear forces (b).
The effects of the size and location of the anti-symmetric surface bonded piezoelectric
patches and the applied electric field on the shear forces and bending moments (M1, M2, Q1
and Q2.) in the joint edges are first investigated. Here, two types of piezoelectric patches are
discussed: one is the common piezoelectric patch with a fully covered single-polar electrode,
and the other is bimorph piezoelectric patch with a partially covered bipolar electrode, as
schematically shown in Fig.6. For the convenience of numerical analysis, the thicknesses of
both adherends are set to be 40mm and the piezoelectric layer is taken as 1mm thick. Using
the analytical solution introduced in Section 2.1.1, the joint-edge bending moments and shear
forces are calculated and presented in Figs. 7-9. Figure 7 shows the influence of the applied
electric field on the joint-edge bending moments and shear forces. The results indicate that
adjusting the applied electric field in the piezoelectric layers can either increase or decrease
the joint-edge bending moments and shear forces. It is noted that the bimorph piezoelectric
layer can induce more drastic influences on the shear forces and bending moments than the
840
820
800
780 single polar
760 bipolar
740
720
700
680
660
640
620
600
580
560
540
520
500
2 4 6 8 10 12
Length of piezoelectric layer (cm)
(a)
1050
1000 single polar

bipolar
950
Shear forces (N)
900
850
800
750
700
650
2 4 6 8 10 12
Length of piezoelectric layer (cm)
(b)
Figure 8. The effect of the length of anti-symmetrically surface bonding piezoelectric layers on the
joint-edge bending moments (a) and shear forces (b) for a constant electric field.
commonly used single polar piezoelectric layer. Moreover, the size effect of the bonded
piezoelectric patches on the bending moments and shear forces are depicted in Fig. 8. It is
seen that the joint shear force and bending moment can be increased with an increase in the
piezoelectric length at a constant electric field and constant distance from joint edges. As for
the influence of the bonding location of the piezoelectric patches, Figure 9 shows that the
bonding location of the piezoelectric layer only has a minimal effect on the joint end-edge
shear forces and bending moments. According to the above analyses, it can be clearly seen
that the joint edge shear forces and bending moments can be reduced more significantly by
the bimorph piezoelectric layer than by the commonly used single polar piezoelectric layer.
680
660
640 single polar

bipolar
620
600
580
560
540
520
0 2 4 6 8 10 12
Distance l3 (cm)
(a)
860
840
820 single polar

bipolar
800
Shear forces (N)
780
760
740
720
700
680
660
0 2 4 6 8 10 12
Distance l3 (cm)
(b)
Figure 9. The influences of bonding location of the piezoelectric layers with constant electric field and
length on the joint-edge bending moments (a) and shear forces (b)
Having determined the joint edge bending moments and shear forces, we can apply the
relevant boundary conditions given in Eq. (2-8) and further obtain the solution presented in
Section 2.1.2 to determine the peel and shear stresses in the adhesive layer. Figures 10 and 11
display the effects of the applied electric field on the bimorph piezoelectric layers having a
constant length, and zero distance from the joint edge on the peel and shear stresses,
respectively. From Fig. 10, the maximum peel stress in the joint edges can be effectively
reduced by increasing the applied positive electric field, while the applied negative electric
field can conversely increase the maximum peel stress.
E3=-100KV/m
3
E3=0V/m
Peel stresses (MPa)
E3=100KV/m
2 FEM for -100KV/m
FEM for 0V/m
FEM for 100KV/m
1
-0.15 -0.1 -0.05 0 0.05 0.1 0.15

x(m)
Figure 10. The influences of applied electric field in the piezoelectric layers on the peel stresses.
E3=-100KV/m
2
E3=0V/m
Shear stresses (MPa)
E3=100KV/m
1.5
FEM for -100KV/m
FEM for 0V/m
FEM for 100KV/m
1
0.5
0
-0.15 -0.1 -0.05 0 0.05 0.1 0.15
x(m)
Figure 11. The effects of applied electric field in the piezoelectric layers on the shear stresses.
From Fig. 11, the maximum shear stresses in the joint edges can be decreased by
increasing the applied positive electric field in the piezoelectric patches, while the applied
negative electric field can increase the stress.
2.2. Experimental Validation
In order to validate the developed smart adhesively bonded joints, a detailed experimental
investigation and a numerical comparison are conducted. Here, the ASTM standard D5868-01
is used in the experimental investigation.
2.2.1. Specimen Fabrication
According to the ASTM Standard, the fiber-reinforced laminated plates with dimensions of
length×width×thickness = 250mm×210mm×2.5mm were prepared, using 20 layers of
unidirectional TENAX/R6378 carbon fiber/epoxy pre-preg (Hexcel Corp, CT, USA). The
R6376 is a high performance tough matrix formulated for the fabrication of primary aircraft
structures. Further, the graphite epoxy laminated plates were cured for 2 hours at 175°C and
700kN/m2 pressure with a heating rate of 2-5°C/min in an oven, as recommended by the
manufacturer. Each of the cured laminated plates was cut into two main parts with a
dimension of 100mm×177mm×2.5mm by means of a water-cooled diamond tip saw blade.
The remaining portion of the plate was used to prepare coupons for determining the basic
mechanical properties of the composite. Furthermore, surface preparation for bonding was
carried out according ASTM D2093. Sand paper (320 grit) was used to remove the glossy
finish of the laminate which produced a relatively rough surface for better mechanical
bonding. The surface was then wiped with acetone. The West System (MI, USA) room-cured
epoxy resin system 105 (with the 205 accelerator) was used as the adhesive. In order to
control the joint geometry, we used glass beads to control a 0.76mm adhesive bonding
thickness, ensuring a lap shear overlap area of 25.4mm×25.4mm. The joints were pressurized
by clamps, applying a consistent pressure when the adhesive was being cured at room
temperature per the guidelines.
Piezolayer
wire
specimen
Power supply
Figure 12. Experiment set-up.
Once the joints were cured for the recommended time period, the jointed plates were cut
into seven specimens with a width of 25.4mm. A diamond saw was also used to cut the 1mm
thick H4E piezoelectric plate obtained through PIEZO SYSTEMS Inc. (Cambridge, MA) into
25.4mm×10mm patches. Wires were then soldered to the patch. Prior to bonding the
piezoelectric patch to the graphite epoxy substrate surface, the bonding area was sanded and
cleaned to ensure a superior bond.
8000
7000
6000
5000
Load (N)
4000
3000
2000
1000
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Displacement (mm)
Figure 13. A typical load-displacement curve of the smart single-lap joint.
2.2.2. Test Procedure and Experimental Results
A servo-hydraulic universal testing machine with a digital data acquisition system (Model
8500+) was used to perform the tests. The test set up is schematically shown in Fig. 12. The
loading rate was set at 13mm/min per ASTM D5868-01 standard. In order to prevent
discharging, the exposed electrodes on the specimens were isolated by silicon grease. Four
series of tests (each having 5 single-lap specimens) were conducted, and categorized based on
the applied electric fields of 0V, 50V, 100V and 200V. The material properties are tabulated
in Table 1. A typical load-displacement curve is illustrated in Fig. 13. The experimental
observation indicates that all the tested joint systems fail in adhesive failure mode, as shown
in Fig. 14. Furthermore, the failure shear strength of the smart single-lap joint at various
levels of the applied electric field are obtained by dividing the failure load by the bonded area
and are summarized in Table 2.
Table 1. Materials properties of the Carbon/epoxy laminate and piezoelectric patch.
E11 E22 E33 G12 G13 -d31 d33

v12 v13
(GPa) (GPa) (GPa) (GPa) (GPa) (pC/N) (pC/N)
Composite 118 5.54 5.54 4.77 4.77 0.27 0.27
PZT 62 62 50 0.31 0.31 320 650
Table 2.The failure shear strength developed in the smart single-lap joint various
applied electric fields.
Applied electric field (kV/m) 0 50 100 200

Average failure strength (MPa) 10.64 10.99 11.58 12.87
Improved efficiency --- 3.29% 8.83% 20.9%
2.2.3. Numerical Comparison and Discussion
In order to further validate the integrity of the developed theoretical model, the numerical
comparisons between theory and experiment are conducted. These examples evaluate the
effect of the surface bonded piezoelectric patches on the stress redistribution in the adhesive
layer when the smart single-lap joint is subjected to a combined mechanical and electrical
load. The material and geometrical properties of the joint system, as given in Table 1, are
used to carry out the detailed theoretical analysis based on the theoretical model and solution
procedure in Section 2.1. The peel and shear stress distributions and their maximum values
could be determined by plugging in the experimental failure load into the analytical model
presented in the above sections. As mentioned in Section 2.1, the joint failure strength is
obtained by dividing the failure load by the bonded area. The comparison of the average
critical shear stress values could, therefore, demonstrate the strength improvement in the joint
and joint efficiency.
Figure 14. A typical failure mode of the testing specimen.
1.00
Stress ratio τPZT/τ0
0.95
0.90
0.85
Maximum shear stress
0.80
0 20000 40000 60000 80000 100000

(a)
Improved efficiency (*100%)
0.25
Exaperimental results (Table 2)
0.20 Theoretical analysis
0.15
0.10
0.05
0.00
0 20000 40000 60000 80000 100000
(b)
Figure 15. Numerical comparison of the improved efficiency between the theoretical analysis and
experimental investigation.
The comparison of the maximum shear stress as a function of the applied electric field is
shown in Fig. 15a. The results in the figure illustrate that both peel and shear strengths of the
joint could be improved by involving the piezoelectric patches. To appreciate the
improvement in the joint strength resulting from integration of the piezoelectric patches,
however, it would be adequate to compare the improvement in the joint shear strength. Figure
15b illustrates the percent improvement in the shear strength of the joint as a function of the
applied electric field. The plot also shows good agreement between the results obtained from
the analytical model and those from the experiment.
2.3. Smart Adhesively Bonded Single-Strap Joint
In this section, we investigate the behavior of an idealized smart single-strap joint system
integrated with piezoelectric reinforced laminates as shown in Fig. 2(c) and (d). For a
laminated joint system there is no doubt that the stacking sequence, along with the materials
properties, structures geometries and externally applied electro-mechanical loading etc, must
have a significant effect on the efficiency of such smart joints. Therefore, in order to more
accurately analyze the action of the integrated piezoelectric reinforced layers, a first-order
shear deformation theory (FOST) based theoretical model is established to obtain the peel and
shear stress distributions in the adhesive layer under the action of electro-mechanical loading.
2.3.1. Fundamental Equations for Smart Adhesively Bonded Single-Strap Joint
Now considering the proposed smart single strap joint subjected to an axial force, as shown in
Fig. 16, the displacement field assumption of the first-order shear deformation theory is
presented for the overlap joint part and bare adherends parts, in the following forms:
ui ( x, z ) = ui 0 ( x ) + ziφix ( x ) , (i=a, b, ab, bb) (2-16a)
wi ( x, z ) = wi 0 ( x ) ; (i=a, b, ab, bb) (2-16b)
where the subscripts ‘i=a’ and ‘i=b’ of the displacements denote the upper and bottom
adherends in the overlap joint part, and, ‘i=ab’ and ‘i=bb’ of the displacements denote the
upper and bottom bare adherend parts respectively. ui 0 and wi 0 are the mid-plane
displacements at z i = 0 in the different parts of the smart joint along x- and z-directions,
respectively, as illustrated in Fig. 16. φix are the rotations of the transverse normal about the
x-axis in the different joint parts, respectively.
In terms of the above first-order displacement field assumption, the strains can be
obtained as follows:
∂ui ∂ui 0 ∂φ
ε 11i = = + zi ix , (i=a, b, ab, bb) (2-17a)
∂x ∂x ∂x
∂wi ∂ui ∂wi 0

γ 13i = + = + φix . (i=a, b, ab, bb) (2-17b)
∂x ∂z ∂x
Overlap joint part Upper bare part

z1 z2 z3
Bottom bare part x3
P P
x1 x2 Qa, Ma
Mb,Qb
l1 l2 l3
Symmetric axis
Figure 16. The schematic view for the different parts of the smart single-strap joint.
Furthermore by considering the effect of piezoelectric reinforced composite layers, the

stresses for the upper and bottom adherends in the different parts as shown in Fig.16 can be
expressed as follows:
In the elastic bottom adherend:
∂ui 0 ∂φ
σ 11k i = E11k iε 11i = E11k i ( + zi ix ) (i= b, bb) (2-18a)
∂x ∂x
The upper adherend integrated with piezoelectric reinforced composite layers is shown in
Fig. 2(c-d). Considering the eccentric effect and electro-mechanical coupling performance of
the piezoelectric reinforced composite layers with the poling direction along the thickness z-
axis, we can present the electro-elastic relationships for the upper adherend as:
∂u i 0 ∂φ
σ 11k i = E11k i ε 11i − e31k E3k = E11k i ( + z i ix ) − e31
k
E 3k (i=a, ab) (2-18b)
∂x ∂x
D11k i = e31i ε 11i + κ 33 E 3

k k k
(i=a, ab) (2-18c)
where the superscript “k” means the kth layer of the laminated plate/beam. It is noted that the
piezoelectric constant e31 and dielectric constant κ33 should be equal to zero in the elastic
layers. And, Eq. (2-18c) can be defined as the sensing equation for the piezoelectric
composite layer to act as sensor.
Further, the resultant forces and moments can be obtained by integrating the stresses over
the cross-section area of the upper and bottom adherends of the smart joint, respectively, in
the following forms:
∂ua0 ∂φ
ha k
Na = ∫ 2ha σ11adz = ∑
zaei+1
∫ (E11k aε11a − e31E3 )dz = Aa11 + Ba11 ax − NPZT
k k
(2-19a)
−
2 i =1
zaei ∂x ∂x
ha k
∂ua0 ∂φ
Ma = ∫ 2ha σ11a zdz = ∑
zaei+1
∫ (E11k aε11a − e31E3k )zdz = Ba11 + Da11 ax − M PZT
k
(2-19b)
−
2 i =1
zaei ∂x ∂x
h
5 2a
h
5 2a ∂w 5h G ∂w ∂w
Qa = ∫ ha σ 13a dz = ∫ ha Ga ( a 0 + φ ax )dz = a a ( a 0 + φ ax ) = Aa 44 ( a 0 + φ ax ) , (2-19c)
−
6 2 −
6 2 ∂x 6 ∂x ∂x
hb hb hb
∂ub0 ∂φ ∂u ∂u
Nb = ∫ 2 σ 11b dz = ∫ 2 E11b ε 11b dz = ∫ 2 E11b ( + z bx )dz = hb E11b b0 = Ab11 b0 (2-19d)
∂x ∂x ∂x ∂x
h h h
− b − b − b
2 2 2
hb hb
∂u b 0 ∂φ h 3 E ∂φ bx ∂φ
Mb = ∫ 2
− b
h σ 11b zdz = ∫ 2
h
− b
E11b (
∂x
+ z bx ) zdz = b 11b
∂x 12 ∂x
= Db11 bx ,
∂x
(2-19e)
2 2
h
5 2b
h
5 2b ∂w 5h G ∂w ∂w
Qb = ∫ hb σ 13b dz = ∫ hb Gb ( b 0 + φbx )dz = b b ( b 0 + φbx ) = Ab 44 ( b 0 + φbx ) (2-19f)
−
6 2 −
6 2 ∂x 6 ∂x ∂x
with the definitions of piezoelectric-coupling induced resultant force NPZT and moment MPZT
due to the externally applied electric field in the following forms:
k
NPZT = ∑
zaei+1
∫
k k
e31E3 dz (2-20a)
zaei
i =1
k
MPZT = ∑
zaei+1
∫
k k
e31E3 zdz (2-20b)
zaei
i =1
k
where E3 is the electric field applied to the kth piezoelectric layer. For the distributed
electrode, it can also be described by the Heaviside step function H ( x − xa ) .
2.3.2. Equilibrium Equations and Boundary Conditions
Due to the symmetric and pseudo-symmetric characteristic of the single-strap joint system
with respect to z-axis, only half of such joint is theoretically considered and analyzed. As
shown in Fig.16, the half of such joint can be divided into three parts: overlap joint part,
upper bare beam part and bottom bare beam part. Here we would like to take the overlap joint
section as a detailed example to show the derivation of equilibrium equations. We consider an
infinitesimal element of the overlap joint section, similar to that presented in Fig. 5. In terms
of the static equilibrium conditions for each layer as shown in Fig. 5, we can further obtain
the fundamental equilibrium equations for any segment of the smart single-strap joint by
assuming a unit width of the whole beam (with a rectangular cross section) as follows:
In the top adherend of the overlap joint part:
∂N a ∂M a h ∂Qa
+ τ1 = 0 ; − Qa + a τ 1 = 0 ; + σ1 = 0 ; (2-21a)
∂x ∂x 2 ∂x
In the bottom adherend of the overlap joint part:
∂N b ∂M b h ∂Qb
− τ1 = 0 ; − Qb + b τ 1 = 0 ; − σ1 = 0 . (2-21b)
∂x ∂x 2 ∂x
where stresses σ1 and τ1 , and, strains ε1 and γ 1 are the stresses and strains of the adhesive
layers and can be derived from the mid-plane displacements (ua 0 , wa 0 ) and (ub 0 , wb 0 ) , and,
rotations φ ax and φ bx of the top and bottom adherents in the following forms:
E0 E 0 ( wb 0 − wa 0 )
σ1 = ε1 = (2-22a)
(1 − v0 ) (1 − v0 )
2 2
h0
G0 h h
τ 1 = G0γ 1 = [(ub 0 − ua 0 ) − ( b φ bx + a φ ax )] (2-22b)
h0 2 2
where E0 and ν0 are the Young’s modulus and Poisson’s ratio of the adhesive, respectively.
Similarly, the equilibrium equations for the upper and bottom bare adherend parts as
shown in Fig. 16 can be obtained by neglecting the adhesive layer stresses in Eq. (2-21) as
follows:
In the top bare adherend (beam):
∂N ab ∂M ab ∂Qab
= 0; − Qab = 0 ; = 0; (2-23a)
∂x ∂x ∂x
In the bottom bare adherend (beam):
∂N bb ∂M bb ∂Qbb
= 0; −Q bb = 0 ; = 0. (2-23b)
∂x ∂x ∂x
Here, the relevant boundary conditions of the adherend end and the continuity conditions
between the two parts can be expressed in-detail in the following forms:
At x1=0, i.e. in the end of the bottom bare beam under the external axial mechanical
loading, we have:
N bb (0) = P, wbb (0) = 0, φ bbx (0) = 0; (2-24a)
At x3=l3, i.e. in the symmetric axis, we obtain:

uab 0 = 0 , φ abx = 0 , wab 0 = 0 . (2-24b)
At x2=0, because the upper adherend of the overlap joint part is free, we have:
N a (0) = 0, M a (0) = 0, Qa (0) = 0; (2-24c)
At x2=l2, we also have the free boundary condition for the bottom adherend of the overlap
joint part as follows:
N b (l 2 ) = 0, M b (l2 ) = 0, Qb (l2 ) = 0; (2-24d)
At x1=l1 and x2=0, the continuity conditions can be obtained for the two bottom parts by:
N bb (l1 ) = N b (0), M bb (l1 ) = M b (0), Qbb (l1 ) = Qb (0) (2-24e)
ubb 0 (l1 ) = ub 0 (0), wbb 0 (l1 ) = wb 0 (0), φbbx (l1 ) = φbx (0) (2-24f)
At x2=l2 and x3=0, the continuity conditions can be obtained for the two upper parts by:
N ab (0) = N a (l2 ), M ab (0) = M a (l2 ), Qab (0) = Qa (l2 ) (2-24g)
uab 0 (0) = ua 0 (l2 ), wab 0 (0) = wa 0 (l2 ), φ abx (0) = φ ax (l2 ) (2-24h)
After substituting the relevant resultant forces and moments into the fundamental
equilibrium equations, i.e. Eq. (2-21) and (2-23), the displacement-based governing equations
for the four parts can be obtained as follows:
In the overlap joint segment:
∂ 2 ua 0 ∂ 2φax G0 h h
Aa11 + B + [(ub0 − ua 0 ) − ( b φbx + a φax )]
∂x ∂x
2 a11 2
h0 2 2 (2-25a)
= N PZT [δ ( x − l ) − δ ( x + l )]
∂2ua0 ∂2φax ∂w h G h h
Ba11 + D − Aa44 ( a0 + φax ) + a 0 [(ub0 − ua0 ) − ( b φbx + a φax )]
∂x ∂x ∂x (2-25b)
2 a11 2
2 h0 2 2
= MPZT[δ ( x − l ) − δ ( x + l)]
∂ 2 wa 0 ∂φ ax E0 ( wb 0 − wa 0 )
Aa 44 ( + )+ =0 (2-25c)
∂x 2
∂x (1 − v02 ) h0
∂ 2 u b 0 G0 h h
Ab11 − [(ub 0 − ua 0 ) − ( b φb 0 + a φ a 0 )] = 0 (2-25d)
∂x 2
h0 2 2
∂ 2φbx ∂w h G h h
Db11 − Ab 44 ( b0 + φbx ) + b 0 [(ub 0 − ua 0 ) − ( b φbx + a φ ax )] = 0 (2-25e)
∂x 2 ∂x 2 h0 2 2
∂ 2 wb 0 ∂φ bx E0 ( wb 0 − wa 0 )
Ab 44 ( + )− =0 (2-25f)
∂x 2
∂x (1 − v02 ) h0
In the upper and bottom bare adherend segments:
∂ 2 uab0 ∂ 2φabx
Aa11 + B =0 (2-26a)
∂x 2 ∂x 2
a11
∂2uab0 ∂2φabx ∂w
Ba11 + Da11 2 − Aa44 ( ab0 + φabx ) = 0 (2-26b)
∂x 2
∂x ∂x
∂ 2 wab 0 ∂φ abx
Aa 44 ( + )=0 (2-26c)
∂x 2 ∂x
∂ 2 ubb 0
Ab11 =0 (2-27a)
∂x 2
∂ 2φbbx ∂w
Db11 − Ab 44 ( bb 0 + φbbx ) = 0 (2-27b)
∂x 2
∂x
∂ 2 wbb 0 ∂φbbx
Ab 44 ( + )=0 (2-27c)
∂x 2 ∂x
∂H ( x − x0 )
where = δ ( x − x0 ) is used.
∂x
2.3.3. Solution Procedure
Similar to the single-lap joint, the state-space method can be utilized to solve the governing
equations analytically [54]. In order to construct the state equations, some new unknown
functions must firstly be introduced as follows:
∂ua 0 ∂φ ax ∂w a 0
Z1 = ua 0 , Z 2 = Z1' = , Z 3 = φ ax , Z 4 = Z 3 = , Z 5 = wa 0 , Z 6 = Z 5 =
' '
,
∂x ∂x ∂x
∂φ ∂w
Z 7 = ub 0 , Z 8 = Z 7' = ∂ub 0 , Z 9 = φbx , Z10 = Z 9' = bx , Z11 = wb 0 , Z12 = Z11' = b 0 .
∂x ∂x ∂x
∂φabx ∂wab0
X 1 = uab0 , X2 = X1' = ∂uab0 , X 3 = φ abx , X 4 = X 3' = , X 5 = wab 0 , X 6 = X 5 =
'
,
∂x ∂x ∂x
∂u bb 0 ∂φ ∂wbb0
Y1 = u bb 0 , Y2 = Y1' = , Y3 = φ bbx , Y4 = Y3 = bbx , Y5 = wbb 0 , Y6 = Y5 =
' '
.
∂x ∂x ∂x
Using the above introduced unknown variables, the displacement-based governing

equations for the different parts, i.e. Eq. (2-25) - (2-27), can be simply rewritten by the new
state equation systems as shown in the following matrix forms, respectively:
{Z }' = [Η ]{Z } + [Λ ] (2-28)
{X }' = [Δ ]{ X } (2-29)
{Y }' = [Ω]{Y } (2-30)
and furthermore, the peel and shear stresses in the adhesive layer given in Eq. (2-22) can be
rewritten by the introduced state variables as:
− E0 E0
σ 1 = [0 0 0 0 0 0 0 0 0 0]{Z } (2-31a)
(1 − v0 )h0 (1 − v0 )h0
2 2
G0 G0 ha G0 G0 hb
τ 1 = [− 0 − 0 0 0 0 − 0 0 0]{Z } (2-31b)
h0 2h0 h0 2h0
where [H] is a 12×12 matrix with the following non-zero elements:
H(1,2) = H(3,4) = H(5,6) = H(7,8) = H(9,10) = H(11,12) = 1 ;
(0.5ha Ba11 − Da11 ) G0

H (2,1) = − ;
Aa11 Da11 − Ba211 h0
(0.5ha Ba11 − Da11 ) ha G0 Aa 44 Ba11

H(2,3) = − − ;
Aa11 Da11 − Ba11 2h0
2
Aa11 Da11 − Ba211
Aa 44 Ba11 (0.5ha Ba11 − Da11 ) G0

H( 2,6) = − ; H ( 2,7) = ;
Aa11 Da11 − Ba11
2
Aa11 Da11 − Ba211 h0
(0.5ha Ba11 − Da11 ) hb G0

H( 2,9) = − ;
Aa11 Da11 − Ba211 2h0
G0 Ba11 − 0.5 Aa11 ha

H (4,1) = − ;
h0 Aa11 Da11 − Ba211
Aa 44 Aa11 G B − 0.5 Aa11ha ha

H( 4,3) = − 0 a11 ;
Aa11 Da11 − Ba11 h0 Aa11 Da11 − Ba211 2
2
Aa 44 Aa11 G B − 0.5 Aa11ha

H( 4,6) = ; H(4,7) = 0 a11 ;
Aa11 Da11 − Ba11
2
h0 Aa11 Da11 − Ba211
G0 Ba11 − 0.5 Aa11ha hb

H( 4,9) = − ;
h0 Aa11 Da11 − Ba211 2
1 E0
H(6,4) = −1 ; H (6,5) = ; H(6,11) = − H(6,5) ;
Aa11 (1 − v02 )h0
G0 G0 ha
H (8,1) = − ; H(8,3) = − ;
Ab11 h0 2 Ab11h0
G0 hb
H(8,7) = −H(8,1) ; H(8,9) = − ;
2 Ab11h0
G0 hb Ghh
H (10,1) = ; H(10,3) = 0 a b ; H(10,7) = − H(10,1) ;
2 Db11 h0 4 Db11h0
Ab 44 G0 hb2 A
H(10,9) = + ; H(10,12) = b 44 ;
Db11 4 Db11h0 Db11
1 E0
H (12,5) = − ; H(12,10) = −1 ; H(12,11) = −H(12,5) .
Ab 44 (1 − v 02 )h0
[Δ] and [Ω] are 6×6 matrices with the following no-zero elements:
Δ (1,2) = Δ(3,4) = Δ (5,6) = 1 ;
Aa 44 Ba11
Δ( 2,3) = − ;
Aa11 Da11 − Ba211
Aa 44 Ba11
Δ( 2,6) = − ;
Aa11 Da11 − Ba211
Aa 44 Aa11
Δ( 4,6) = ;
Aa11 Da11 − Ba211
Aa 44 Aa11
Δ ( 4,3) = ; Δ(6,4) = −1 .
Aa11 Da11 − Ba211
Ab 44
Ω(1,2) = Ω(3,4) = Ω(5,6) = 1 ; Ω( 4,3) = Ω( 4,6) = ; Ω(6,4) = −1 .
Db11
and, [Λ] is a 12×1 matrix and has the following non-zero elements:
'
Da11 N ab − Ba11 M ab
' '
Aa11M ab − Ba11 N ab'
Λ(2,1) = and Λ ( 4,1) =
Aa11 Da11 − Ba211 Aa11 Da11 − Ba211
with the following definitions
'
N ab = N PZT [δ ( x − l ) − δ ( x + l )]; Mab
'
= MPZT[δ (x − l) − δ (x + l)].
Usually the above state equations in Eq. (2-28)-(2-30) can be analytically solved by the
following solutions:
x
Z ( x ) = e x [ H ] {k1} + e x[ H ] ∫ e −ϑ [ H ] [ Λ ]dϑ (2-32)
X ( x ) = e x [ Δ ] {k 2 } (2-33)
Y ( x ) = e x[ Ω ] {k 3 } (2-34)
where {k1} is a vector with 12 unknown coefficients determined by the boundary and
continuity conditions at x = 0, l 2 , and, {k2} and {k3} are the vectors with 6 unknown
coefficients determined by the boundary and continuity conditions at x = 0, l1 and x = 0, l3 ,
as shown in Eq. (2-9), by using the stress-strain and strain-displacement relationships (Eq. (2-
17) and (2-18)). Once the unknown coefficients {ki} (i=1,2,3) are determined by the boundary
and continuity conditions, the peel and shear stresses in the adhesive layer can be analytically
obtained by Eq. (2-31).
2.3.4. Numerical Examples and Discussion
In this section, some numerical examples are presented by the above theoretical analysis to
evaluate the effect of the integrated piezoelectric composite layers on the stress redistribution
in the adhesive layer when the smart single-strap joint is subjected to combined electro-
mechanical loadings. Here, in order to improve the electro-mechanical coupling performance
of the piezoelectric reinforced composite, we can employ the piezoelectric polymer PVDF as
matrix to construct the piezoelectric reinforced composite [55,56]. The material properties
and geometric parameters of the adherends, adhesive, piezoelectric ceramics and matrix of
piezoelectric reinforced composite materials are listed as follows:
Adherends: E1=E2=75 GPa, ν 12 =ν 21 =0.25;
Adhesive: Ea=7.5 GPa, ν a =0.33;
Piezoelectric and polyvinylidene fluoride (PVDF) matrix properties:
Piezoelectric materials (PZT-5H):
E11=127 GPa, E12=80.2 GPa, E13=84.6 GPa, E33=117 GPa, E44=23.0 GPa,
E66=23.5 GPa, d31= -274 pC/N, d33=593 pC/N, d15=741 pC/N, κ11=3130κ0,
κ33=3400κ0, κ0=8.854×10-12 F/m .
PVDF materials properties:
E11= E22=2.0 GPa, v=0.29, G12=0.775 GPa,

d31=22 pC/N, κ=13κ0.
Geometric parameters: l1=0.8m; l2=0.3m; h0=0.5mm. ha= hb=40mm, hPZT=5mm.
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
e 31 (N*m/V)
-3.0
-3.5
Aspect ratio ρ
-4.0 ρ=1
-4.5 ρ=5
-5.0 ρ=10
-5.5 ρ=100
-6.0 ρ=10^5
-6.5
-7.0
-7.5
-8.0
0.0 0.1 0.2 0.3 0.5 0.6
Volume fraction V f
(*100%)
Figure 17. The effects of the aspect ratio ρ and volume fraction Vf of the reinforced piezoelectric
particle/fiber on the effective piezoelectric constant e31.
Applied electric field

6
E3=-300KV/m
E3=-100KV/m
Peel stress (MPa)

E3=-1KV/m
4 E3=0KV/m
E3=1KV/m
E3=100KV/m
E3=300KV/m
2
-2
-0.15 -0.1 -0.05 0 0.05 0.1 0.15
x2-0.15 (m)
Figure 18. The effects of applied electric field in the top surface bonded piezoelectric composite layer
(Vf=0.6) on the peel stress.
Applied electric field

Shear stress (MPa)
4
E3=-300KV/m
E3=-100KV/m
E3=-1KV/m
3 E3=0KV/m
E3=1KV/m
E3=100KV/m
2 E3=300KV/m
0
-0.15 -0.1 -0.05 0 0.05 0. 0.15
x2-0.15 (m)
Figure 19. The influences of applied electric field in the top surface bonded piezoelectric composite
layer (Vf=0.6) on the shear stress.
Firstly, based on the micromechanical Mori-Tanaka method and previous works [57-61],
the effective electroelastic properties of piezoelectric particles reinforced composite materials
can be theoretically predicted as a function of volume fraction and aspect ratio ρ of the
piezoelectric inclusions, as depicted in Fig. 17. From Fig.17, it is clearly seen that
piezoelectric constant e31 decreases with the increase in the volume fraction Vf and aspect
ratio ρ [57]. Here for the convenience of numerical simulation, we can take the piezoelectric
reinforced composite materials with smaller fiber aspect ratio (i.e. aspect ratio ρ=100) as the
calculation example. Further, the peel and shear stress distributions in the adhesive layer of a
smart single-strap joint integrated with the top surface bonded piezoelectric composite layer
(i.e. Ba11≠0), as shown in Fig. 2(c), are studied by using the following simulation parameters:
l3=0.005mm, volume fraction Vf =0.6 and mechanical loading P=37500N. The results are
presented in Fig. 18 for the peel stress distribution and Fig. 19 for the shear stress distribution.
Evidently the applied electric field in the top surface bonded piezoelectric composite layer
can remarkably change the peel/shear stresses distribution in the adhesive bondline. It is
found that the applied positive electric field can significantly reduce both the maximum peel
and shear stresses in the adhesive bondline; the applied negative electric field, however,
increases both the maximum peel and shear stresses, as presented in Fig. 20. Simultaneously,
the effects of the length l3 on the maximum peel and shear stresses are also analyzed as
depicted in Fig. 21. From Fig. 21, the effect of the length l3 on the peel and shear stress
distributions is minimal and can be neglected with comparison to the effect of the applied
electric fields.
8.0 7
7.5 Maximum peel stress
Maximum shear stress (MPa)

Maximum peel stress (MPa) Maximum shear stress 6
7.0
6.5
5
6.0
5.5
4
5.0
4.5 3
4.0
3.5 2
-400000 -200000 0 200000 400000
Figure 20. The influences of electric fields applied to the top surface bonded piezoelectric composite
layer on maximum peel stress and shear stress.
6.0 5.0
5.9 Peel stress 4.9

Maximum peel stress (MPa)

5.8 Shear stress 4.8
5.7 4.7
5.6 4.6
5.5 4.5
5.4 4.4
5.3 4.3
5.2 4.2
5.1 4.1
5.0 4.0
0.000 0.005 0.010 0.015 0.020
l3 (m)
Figure 21. The effects of the upper bare adherent part length l3 on the maximum peel and shear stresses.
Furthermore, the effect of the stacking sequence of the integrated piezoelectric composite
layers in the upper composite adherend on the peel and shear stress distributions in the
adhesive layer is also studied. Here, we assume that the upper composite adherend is
integrated with piezoelectric composite layers stacked symmetrically about the z-axis passing
through the centric surface of the upper adherend (i.e. Ba11=0); see Fig. 2 (c) and (d). Based
on the developed analytical model, the influences of the applied unidirectional electric fields
in the piezoelectric composite layers (i.e. NPZT≠0 and MPZT=0) on the peel and shear stress
distributions can be calculated and presented in Fig. 22 for the peel stress distribution and Fig.
23 for the shear stress distribution. Similarly, the electric fields can significantly re-orientate
the peel and shear stress distributions in the adhesive layer. The detailed redistribution
efficiency of the applied electric fields on the maximum peel and shear stresses in the
adhesive layer is shown in Fig. 24. Obviously, the applied positive electric fields can increase
both the maximum peel stress and maximum shear stress in the adhesive layer. Contrastively
in the case of the applied negative electric field, a low negative electric field can decrease
both the maximum peel stress and shear stress. However, when the applied negative electric
fields exceed a critical value, the maximum peel stress and shear stress will appear in the
opposite position and will increase, as shown in Figs. 22-24. On the other hand, when the
symmetrical integrated piezoelectric composite layers are subjected to the anti-symmetric
directional electric fields with the same voltage, i.e. NPZT=0 and MPZT≠0, the maximum peel
stress and shear stress in the adhesive layer can also be reduced by increasing the applied
positive electric fields. However, they will be increased while the applied negative electric
fields increse, as displayed in Fig. 25.
6
Applied electric field E3:
Peel stress (MPa)
E3=500KV/m
4 E3=100KV/m
E3=1KV/m
E3=0KV/m
E3=-1KV/m
2 E3=-100KV/m
E3=-500KV/m
-0.15 -0.1 -0.05 0 0.05 0.1 0.15

x2-0.15 (m)
Figure 22. The uni-direction electric fields applied to the two symmetrically integrated two
piezoelectric composite layers (Vf=0.6) in the upper adherent V.S. the peel stress distribution.
3.5
3
Shear stress (MPa)
2.5 Applied electric field E3:

E3=500KV/m
2 E3=100KV/m
E3=1KV/m
E3=0KV/m
1.5 E3=-1KV/m
E3=-100KV/m
1 E3=-500KV/m
0.5
-0.15 -0.1 -0.05 0 0.05 0.1 0.15

x2-0.15 (m)
Figure 23. The uni-direction electric fields applied to the symmetrically integrated two piezoelectric
composite layers (Vf=0.6) in the upper adherent V.S. the shear stress distribution.
7.5 4.
7.0

Maximum peel stress

6.5 3.
6.0
5.5 3.
x=0.15
5.0
4.5 2.
4.0
3.5 2.
-400000 -200000 0 200000 400000
Figure 24. The influences of the uni-direction electric fields applied to the symmetrically integrated two
piezoelectric composite layers on the maximum peel/shear stresses.
2.
8 Maximum peel stress
2.
7
2.

6 2.
5 2.
2.
4
2.
3
2.
2
-400000 -200000 0 200000 400000
Figure 25. The effects of the anti-direction electric fields applied to the symmetrically integrated two
piezoelectric composite layers on the maximum peel/shear stresses.
From the above analyses, it is confirmed that the peel and shear stress distributions in the
adhesive layer can be re-distributed and the maximum peel and shear stresses can be
controlled and reduced, leading to enhancement in the strength capacity of the single-strap
joint system. In order to compare the enhancement efficiency of the integrated piezoelectric
composite layers in the various studied cases, Figure 26 and Figure 27 summarize and present
the different efficiencies for the different stacking sequences of the integrated piezoelectric
composite layers. In the case of E3=0, it is clear that the maximum peel and shear stresses
with the top surface bonded piezoelectric composite layer are much larger than those in other
cases, which results from the asymmetric lamination induced extension-bending coupling
behavior of the upper adherend. From Fig. 26, the smart joint with the symmetrically
integrated piezoelectric composite layers subjected to the applied electric fields in the
opposite direction has the largest efficiency to reduce the maximum peel stress in the
adhesive layer among the studied examples. However, for the shear stress, it is numerically
shown from Fig. 27 that the smart single-strap joint with the symmetrically integrated
piezoelectric composite layers subjected to the unidirectional applied electric fields can more
efficiently reduce the maximum shear stress in the adhesive layer with comparison to the
other studied cases.
8.5
Surface bonded PZT composite layers
8.0
Symmetrically integrated PZT compoiste
7.5 layers with the uni-direction electric field
7.0
Maximum peel stress (MPa) layers with the anti-direction electric field
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
-400000 -200000 0 200000 400000
Figure 26. The efficiency comparisons of the maximum peel stress reduction among the different
integrated sequences of piezoelectric composite layers in the upper adherent.
6.0 Surface bonded PZT composite layers

5.5
layers with the uni-direction electric field
layers with the anti-direction electric field

5.0
4.5
4.0
3.5
3.0
2.5
2.0
-400000 -200000 0 200000 400000
Figure 27. The efficiency comparisons of the maximum shear stress reduction among the different
integrated sequences of piezoelectric composite layers in the upper adherent.
The integrated piezoelectric layers also have sensing function. It is easy to induce charges
in the piezoelectric layer due to the deformation of the joint system per Eq. (2-18c). This is
out of the scope of this chapter and will not be discussed in detail.
3. Smart Adhesively Bonded Composite Pipe Joint

Most of the adhesively bonded pipe joints used in engineering, such as adhesively bonded
socket joints, butt-weld and strap joints, heat activated coupling joints etc., can be basically
regarded as two pieces of composite pipes joined by a connection coupler via the bonding
adhesive, as shown in Fig. 28. As mentioned above, all of the experimental and theoretical
works have confirmed that the peel/shear stress concentration always exists in the adhesive
layer of such joints. Therefore, in order to reduce the stress concentration, the smart beam-
like joint concept is extended to develop a novel adhesively bonded smart composite pipe
pipe joint system by integrating the smart piezoelectric materials as actuators/sensors into the
connection coupler, as shown in Fig. 29.
Figure 28. Common schematic view of pipe joint system.
ith layer of composite

ith layer of composite
Coupler
kth integrated
Adhesive
piezoelectric layer
Pipe
Rci Rco
Rpo
Rpi
hp hc
ha
(a) Common pipe-joint system (b) Developed smart pipe-joint system
Figure 29. The basic structures of the common pipe-joint system (a) and present developed smart pipe
joint system integrated with the piezoelectric layer (b).
Similar to the single-lap or single-strap smart joint systems, adjusting the externally
applied electric fields can induce relevant deformation in the smart laminates, causing
additional counter-balancing force and moment at the joint edge so as to reduce the stress
concentration. Obviously, the piezoelectric layers can be freely integrated into any layer of
the composite coupler. There is no doubt that the stacking sequence and the dimension of the
piezoelectric layers should have a significant effect on the efficiency of such smart joint.
Therefore, in order to account for the function of the integrated piezoelectric layers and verify
the efficiency of the smart composite pipe joint system, a theoretical model is established to
conduct peel and shear stresses analysis in the adhesive layer under different electro-
mechanical loading cases by using the first-order shear deformation theory (FOST) in the
following sections.
3.1. Smart Composite Pipe Joint under Bending
3.1.1. Fundamental Equations for a Pipe Joint Subjected to End-Bending Moment
3.1.1.1. Displacements and Strains
According to the proposed smart composite pipe joint system as shown in Fig. 29 and Fig. 30,
the first-order shear deformation theory is employed to model and analyze the smart pipe joint
system and further obtain the relevant fundamental equations. Thus, based on the assumption
of the first-order shear deformation theory for a moderately thick shell, the displacement
fields can be assumed as functions of the mid-plane displacement (u0, v0, w0) and rotations (φ,
ϕ) in the following forms:
u i (ς , ξ , z ) = u 0i (ς , ξ ) + zφi (ς , ξ ) (3-1a)
vi (ς , ξ , z ) = v0i (ς , ξ ) + zϕ i (ς , ξ ) (3-1b)
wi (ς , ξ , z ) = w0i (ς , ξ ) (3-1c)
where (u0i, v0i, w0i) are the displacements of a point (ζ, ξ, 0) on the mid-plane of the shell,
and, (φi, ϕi) are the rotations of a normal to the reference surface in the ith relevant section of
the smart joint system as shown in Fig. 31. And, ‘i=c, p, b’ indicate the variables for the
connection coupler, coupling pipe and bare pipe sections respectively. This definition is also
used in the following expressions.
z, w Pipe hp
h
,u Adhesive ha
⌧
,v R
Coupler hc Rp
Ra Rc
(a) Common view (b) Cross-section view
Figure 30. The schematic geometric view of the pipe joint.

Symmetric axis
Connection coupler x1 x2
M M
Bare pipe Coupling pipe l1 l2
Figure 31. The schematic show for the different parts of composite pipe joint system.
In terms of the strain-displacement relationships in the general shell coordinate system as

shown in Fig. 30, the strain can be expressed as follows:
∂u ∂u 0 ∂φ
ε ς = ε1 = = +z ; (3-2a)
∂ς ∂ς ∂ς
w R ∂v w R ∂v ∂ϕ
εξ = ε 2 = + = + ( 0 + z ); (3-2b)
R + z R + z ∂ξ R + z R + z ∂ξ ∂ξ
∂w
ε z = ε3 = = 0; (3-2c)
∂z
R ∂w ∂v v R ∂w v R
ε ξz = ε 4 = γ 23 = + − = − 0 + ϕ; (3-2d)
R + z ∂ξ ∂z R + z R + z ∂ξ R + z R + z
∂u ∂w ∂w
εςz = ε5 = γ13 = + =φ + 0 ; (3-2e)
∂z ∂ς ∂ς
R ∂u ∂v R ∂u0 zR ∂φ ∂v0 ∂ϕ
εςξ = ε 6 = γ 12 = + = + + +z ; (3-2f)
R + z ∂ξ ∂ς R + z ∂ξ R + z ∂ξ ∂ς ∂ς
where R denotes the mid-plane radius for different parts of the joint, such as Rp and Rc are the
radius of the mid-plane for the pipe wall and connection coupler wall, respectively; see Fig.
30.
3.1.1.2. Laminate Constructive Equations
Considering the effect of piezoelectric layers with the poling direction along the z-axis, the
typical stress-strain relationships of the kth lamina can be represented in the tensor form as:
σ ijk = Cijkl
k
ε kl − eijkk Ek (3-3a)
Dik = eikl
k
ε kl + kijk E j (3-3b)
where the superscript “k” denotes the kth layer of the laminate panel. Cijkl, eijk and kij are the
elastic, piezoelectric and dielectric constants for the lamina respectively. It is noted that the
piezoelectric coefficients are equal to zero for the elastic composite layers. Moreover, when
the piezoelectric layer is subjected to the externally applied electric field as an actuator, the
additional forces/moments can be produced to increase/reduce the structure deformation.
When the piezoelectric layer acts as a sensor, Eq. (3-3b) can be used to theoretically derive
the sensing equation for monitoring the system deformation once the deformation of the pipe
joint system is determined [43, 49]. Some researchers have successfully used the embedded
piezoelectric sensor to experimentally measure the stress in the adhesive joint [62].
For the convenience of formulation, Eq. (3-3) can be expanded in the simple matrix form,
such as Eq. (3-3a) can be rewritten as:
k
⎧σ 1 ⎫ ⎧ε 1 ⎫ ⎧e31 ⎫
k k
⎡Q11 Q12 0 0 Q16 ⎤
⎪σ ⎪ ⎢ ⎥ ⎪ε ⎪ ⎪e ⎪
⎪⎪ 2 ⎪⎪ ⎢Q12 Q22 0 0 Q26 ⎥ ⎪⎪ 2 ⎪⎪ ⎪⎪ 32 ⎪⎪
⎨σ 4 ⎬ = ⎢ 0 0 Q44 Q45 0 ⎥ ⎨ε 4 ⎬ − ⎨ 0 ⎬ E3 (3-3a)
⎪σ ⎪ ⎢ ⎥ ⎪ε ⎪ ⎪ 0 ⎪
⎢ 0 0 Q54 Q55 0 ⎥
⎪ ⎪ 5
⎪ 5⎪ ⎪ ⎪
⎪⎩σ 6 ⎪⎭ ⎢Q
⎣ 16 Q16 0 0 Q66 ⎥⎦ ⎪⎩ε 6 ⎪⎭ ⎪⎩e36 ⎪⎭
where Qij are the transformed stiffnesses and can be obtained from the stacked lamina. eij
are the transformed piezoelectric coupling moduli of the kth lamina and E3 is the relevant
applied electric field in the actuating piezoelectric layer. Because most of the reinforcements
used in piping engineering are orthotropic, including chopped-strand mats, woven roving,
filament winding etc., the stress-train relationships of the pipe walls can be approximately
described in the following forms:
k
⎧σ 1 ⎫ ⎡Q11 0 ⎤ ⎧ε 1 ⎫ ⎧e31 ⎫
k k
Q12
⎪ ⎪ ⎢ ⎥ ⎪ ⎪ ⎪ ⎪
⎨σ 2 ⎬ = ⎢Q12 Q22 0 ⎥ ⎨ε 2 ⎬ − ⎨e32 ⎬ E3 (3-4a)
⎪σ ⎪ ⎢ 0 Q66 ⎥⎦ ⎪ε ⎪ ⎪ 0 ⎪
⎩ 6⎭ ⎣ 0 ⎩ 6⎭ ⎩ ⎭
⎧σ 4 ⎫ 0 ⎤ ⎧ε 4 ⎫
k k
⎡ KQ44
⎨ ⎬ =⎢ ⎥ ⎨ ⎬ (3-4b)
⎩σ 5 ⎭ ⎣ 0 KQ55 ⎦ ⎩ε 5 ⎭
For a general laminate, the forces and moments can be deduced from the stress resultant
by integration of the stresses along the thickness. Considering the effect of the integrated
piezoelectric layers on different parts of the smart composite pipe joint system, the forces and
moments can be obtained as follows:
hi
( Ri + z ) n z k +1 ( R + z )
N iς = N i11 = ∫ 2hi σ 1dz = ∑ ∫ i
(Q11k ε 1 + Q12k ε 2 − e31k E3 )dz
− Ri z Ri
2 k =1 k
(3-5a)
∂u ∂φ 1 ∂v ∂ϕ
= Ai11 i 0 + Bi11 i + Ai12 wi + Ai12 i 0 + Bi12 i − N iPZT
ς
∂ς ∂ς Ri ∂ξ i ∂ξ i
hi n
N iξ = N i 22 = ∫ σ 2 dz = ∑ ∫
z k +1
2
h (Q21k ε 1 + Q22k ε 2 − e32k E3 )dz
− i zk
2 k =1
(3-5b)
∂u ∂φ 1 ∂v ∂ϕ
= Ai 21 i 0 + Bi 21 i + Ai 22 wi + Ai 22 i 0 + Bi 22 i − N iPZT
ξ
( Ri + z) zk +1 ( R + z )
hi n
M iς = M i11 = ∫ 2hi σ 1 zdz = ∑ ∫ i
(Q11k ε1 + Q12k ε 2 − e31k E3 ) zdz
− Ri zk R
2 k =1 i
(3-5c)
∂u ∂φ 1 ∂v ∂ϕ
= Bi11 i 0 + Di11 i + Bi12 wi + Bi12 i 0 + Di12 i − M iPZT
ς
∂ς ∂ς Ri ∂ξi ∂ξ i
hi n
∑∫
z k +1
M iξ = M i 22 = ∫ 2
h
− i
2
σ 2 zdz =
k =1
zk
( Q 21k ε 1 + Q 22k ε 2 − e32k E 3 ) zdz
(3-5d)
∂ui 0 ∂φ 1 ∂v ∂ϕ i
= B i 21 + D i 21 i + B i 22 wi + B i 22 i 0 + D i 22 − M iPZT
ξ
hi
( Ri + z ) n zk +1 ( R + z )
M iςξ = M i12 = ∫ 2
h σ 6 zdz = ∑ ∫ i
Q66k ε 6 zdz
− i Ri z Ri
2 k =1 k
(3-5e)
∂u ∂φ 1 ∂v 1 ∂ϕ
= Bi 661 i 0 + Di 661 i + ( Bi 661 + Di 661 ) i 0 + ( Di 661 + Ei 661 ) i
∂ξ i ∂ξ i Ri ∂ς Ri ∂ς
hi n
M iξς = M i 21 = ∫ σ 6 zdz = ∑ ∫
z k +1
2
h Q66k ε 6 zdz
− i zk
2 k =1
(3-5f)
∂ui 0 ∂φ ∂v ∂ϕ
= Bi 662 + Di 662 i + Bi 661 i 0 + Di 661 i
∂ξ i ∂ξ i ∂ς ∂ς
hi
Ri + z n z
k +1 R + z
Qiςξ = Qi12 = ∫ 2
h σ6dz = ∑∫ i Q66k ε6dz
−i Ri z Ri
2 k=1 k
(3-5g)
∂u ∂φ 1 ∂v 1 ∂ϕ
= Ai661 i0 + Bi661 i + (Ai661 + Bi661) i0 + (Bi661 + Di661) i
∂ξi ∂ξi Ri ∂ς Ri ∂ς
hi n
Qiξς = Qi 21 = ∫ 2hi σ 6 dz = ∑ ∫
zk +1
Q66k ε 6 dz
− zk
2 k =1
(3-5h)
∂ui 0 ∂φ ∂v ∂ϕ
= Ai 662 + Bi 662 i + Ai 661 i 0 + Bi 661 i
∂ξ i ∂ξ i ∂ς ∂ς
( Ri + z ) zk +1 ( R + z )
hi n
Qiξz = Qizξ = Qi 23 = Qi 32 = ∫ 2
h σ 4 dz = ∑ ∫ i
ΚQ44k ε 4 dz
− i Ri z Ri
2 k =1 k
(3-5i)
∂wi 1
= Ai 44 − Ai 44 vi 0 + Ai 44ϕ i
∂ξ i Ri
hi n
Qizς = Qiςz = Qi 31 = Qi13 = ∫ 2hi σ 5 dz = ∑ ∫
z k +1
ΚQ55k ε 5 dz
− zk
2 k =1
(3-5j)
∂wi 0
= Ai 55φi + Ai 55
∂ς
where Aij, Bij, Dij, Eij and Fij are defined as the stiffness matrices for the convenience of future
equation derivation. These resultant forces and moments are general expressions for any part
of the pipe joint system. For instance, the above resultant forces and moments will represent
the resultant forces and moments of the pipe if the radius R in the general expressions is
replaced by Rp. In the same manner, the resultant forces and moments for the other parts can
be obtained. The extensive shell stiffnesses are re-defined and used in the above derivation.
PZT PZT
The additional resultant forces N ij and moments M ij (i, j=1, 2) caused by external
electric fields that are applied to the integrated piezoelectric layers are defined as:
n
( Rc + z ) k k
11 = ∑ ∫
zk +1
N cPZT
ς = N cPZT e31E3 dz (3-6a)
k =1
zk Rc
22 = ∑ ∫
z k +1
N cPZT
ξ = N cPZT e32k E3k dz (3-6b)
zk
k =1
n
( Rc + z) k k
11 = ∑ ∫
zk +1
M cPZT
ς = M cPZT e31E3 zdz (3-6c)
k =1
zk Rc
ξ M c 22 = ∑ ∫
zk +1
M cPZT PZT
ze32k E3k dz (3-6d)
zk
k =1
with the electric field that is applied to the distributed covered surface electrode represented
by the 2-D Heaviside step function as:
E3k (ς , ξ ) = E30 [ H (ς − ς 0 ) − H (ς − ς 1 )] × [ H (ξ − ξ 0 ) − H (ξ − ξ1 )] (3-7)
3.1.2. Representative Volume Model and Equilibrium Equations
For a conventional composite pipe joint, it can be approximated as a symmetric structure, as

shown in Fig. 28, thus only half of the joint is to be modeled as shown in Fig. 31. A
representative infinitesimal element of the joint section is depicted in Fig. 32. In terms of the
static equilibrium conditions for each layer as shown in Fig. 32, the fundamental equilibrium
equations for any segment of the whole smart pipe joint system (with a rectangular cross
section) can be obtained as follows:
For the bare part of the pipe without the adhesive stress distribution effect, the
equilibrium equations from the infinitesimal element can be derived, which are in the local
coordinate system, as follows:
∂N bς ∂Qbξς
+ =0 (3-8a)
∂ς ∂ξ p
∂N bξ Qbξz ∂Qbξς
+ + =0 (3-8b)
∂ξ b Rp ∂ς
∂Qbςz ∂Qbξz N bξ
+ − =0 (3-8c)
∂ς ∂ξ p Rp
∂M bς ∂M bξς
− Qbςz + =0 (3-8d)
∂ς ∂ξ p
∂M bξ ∂M bςξ
− Qbξz + =0 (3-8e)
∂ξ p ∂ς
Qiζz+dQiζz
Niζ+dNiζ
Miζξ+dMiζξ
Miζ+dMiζ
Qiξz+dQiξz
Qiζξ+dQiζξ
Miξζ+dMiξζ
Qiζξ+dQiζξ p
τζ
Niξ+dNiξ
τξ
Miξζ τζ
Miξ +dMiξ τξ
τξ
p Qiξζ Miξ
Niξ τζ
Qiζξ p
Miζξ Qiξz
Miζ
Qiζz
Niζ
(b) Adhesive
(a) adherend
Figure 32. The stresses and forces on the infinitesimal substructure elements of a joint system: (a)
adherend element (connection coupler: i=c or main pipe: i=p), (b) the adhesive layer.
For the pipe part covered by the connection coupler, the following equilibrium equations
in the local coordinate system can be obtained by considering the effect of the adhesive layer
stresses:
∂N pς ∂Q pξς R po
+ = τς (3-9a)
∂ς ∂ξ p Rp
∂N pξ Q pξz ∂Q pξς R po
+ + = τξ (3-9b)
∂ξ p Rp ∂ς Rp
∂Q pςz ∂Q pξz N pξ R po
+ − =− p (3-9c)
∂ς ∂ξ p Rp Rp
∂M pς ∂M pξς h p R po
− Q pςz + = τς (3-9d)
∂ς ∂ξ p 2 Rp
∂M pξ ∂M pςξ h p R po
− Q pξz + = τξ (3-9e)
∂ξ p ∂ς 2 Rp
And in the connection coupler, the equilibrium equations can be described in the local
coordinate system by:
∂N cς ∂Qcξς Rci
+ =− τς (3-10a)
∂ς ∂ξ c Rc
∂N cξ Qcξz ∂Qcξς Rci

+ + =− τξ (3-10b)
∂ξ c Rc ∂ς Rc
∂Qcςz ∂Qcξz N cξ Rci

+ − = p (3-10c)
∂ς ∂ξ c Rc Rc
∂M cς ∂M cξς hc Rci
− Qcςz + = τς (3-10d)
∂ς ∂ξ c 2 Rc
∂M cξ ∂M cςξ hc Rci
− Qcξz + = τξ (3-10e)
∂ξ c ∂ς 2 Rc
Rci + R po
where Ra is the radius of the adhesive layer and Ra = . Rci and R po are the inner
2
radius of the connection coupler and the outer radius of the main pipe, i.e. the top and bottom
surfaces of the adhesive layer as shown in Fig. 29, respectively. Here, τζ, τξ and p denote the
shear and normal stresses in the adhesive layer in the ζ-axis,ξ-axis and z-axis, respectively.
Evidently, the shear and normal stresses in the adhesive layer are caused by the discontinuity
of the relative displacements on the top and bottom surfaces of the adhesive layer. Assuming
that the adhesive shear stresses are uniform throughout the thickness of the adhesive layer, the
shear stresses τζ and τξ can be obtained from the above assumed displacement fields of the
∂wc ∂w p ∂wc ∂w p
pipe and coupler by using the average values of , , and in the
∂ς ∂ς ∂ξ c ∂ξ p
following forms:
⎛ u p − u c ⎞ Ga ⎛ ∂wc ∂w p ⎞
τ ς = Ga ⎜⎜ ⎟⎟ − ⎜⎜ + ⎟⎟ (3-11a)
⎝ ha ⎠ 2 ⎝ ∂ς ∂ς ⎠
⎛ v p − v c ⎞ Ga ⎛ ∂w p ∂wc ⎞ Ga ⎛ v p + vc ⎞
τ ξ = Ga ⎜⎜ ⎟⎟ − ⎜ + ⎟+ ⎜⎜ ⎟⎟ (3-11b)
⎜ ∂ξ ∂ξ ⎟ 2
⎝ ha ⎠ 2 ⎝ p c ⎠ ⎝ Ra ⎠
In the same manner, the normal stress p of the adhesive layer can be determined from the
relative radial displacements of the pipe and coupler:
Ea ⎡ ⎛ wc − wp ⎞ ⎛ε +ε ⎞ ⎛ ε + ε ⎞⎤
p= ⎢(1 −υa )⎜⎜ ⎟⎟ +υa ⎜⎜ pς cς ⎟⎟ +υa ⎜⎜ pξ cξ ⎟⎟⎥
(1 +υa )(1 − 2υa ) ⎣ ⎝ ha ⎠ ⎝ 2 ⎠ ⎝ 2 ⎠⎦
Ea ⎡ ⎛ wc − wp ⎞ υa ⎛ ∂u p0 hp ∂φp ∂uc0 hc ∂φc ⎞
= ⎢(1 −υa )⎜⎜ ⎟⎟ + ⎜⎜ + + − ⎟
∂ς 2 ∂ς ⎟⎠
(3-11c)
(1 +υa )(1 − 2υa ) ⎣ ⎝ ha ⎠ 2 ⎝ ∂ς 2 ∂ς
υa ⎛⎜ wp Rp ∂vp0 hp ∂ϕ p wc Rc ∂vc0 hc ∂ϕc ⎞⎤

+ + ( + )+ + ( − ) ⎟⎥
2 ⎜⎝ Rpo Rpo ∂ξ p 2 ∂ξ p Rci Rci ∂ξc 2 ∂ξc ⎟⎠⎥⎦
where Ga, Ea and υa are the shear modulus, Young’s modulus and Poisson’s ratio of the
adhesive, respectively. ha is the thickness of the adhesive layer.
Furthermore, considering the symmetric smart pipe joint system under the action of the
end force and bending moment, as shown in Fig. 31, the relevant boundary conditions and the
continuity conditions can be described in detail for different parts of the joint as follows:
At x2=l2, when the end of the pipe is subjected to an externally applied force or a bending
moment, the relevant boundary conditions can be represented by:
~ ~ ~ ~ ~
N bς = N bς , Qbςξ = Qbςξ , Qbςz = Qbςz , M bς = M bς , M bςξ = M bςξ ; (3-12a)
At x1=l1, since the end of the coupler is free, the boundary conditions can be expressed as:
N cς = 0 , Qcςξ = 0 , Qcςz = 0 , M cς = 0 , M cςξ = 0 ; (3-12b)

At x1=0, due to the free end and symmetry, the boundary conditions for the pipe and
coupler can be expressed as:
N pς = 0 , Q pςξ = 0 , Q pςz = 0 , M pς = 0 , M pςξ = 0 (3-12c)
∂v0cς ∂ϕ cς ∂wcς
u 0cς = 0 , φ cς = 0 , = 0, = 0, =0 (3-12d)
∂ς ∂ς ∂ς
Similarly, at the end of the coupling part of the pipe, i.e. x1=l1 and x2=0, the continuity
conditions between the coupling part and bare part of the pipe can be represented by:
N pς = N bς , Q pςξ = Qbςξ , Q pςz = Qbςz , M pς = M bς , M pςξ = M bςξ , (3-12e)
∂v0 pς ∂v0bς ∂ϕ pς ∂ϕ bς ∂w pς ∂wbς

u0 pς = u0bς , φ pς = φbς , = , = , = . (3-12f)
∂ς ∂ς ∂ς ∂ς ∂ς ∂ς
where the top bar “~” of the above variables denotes the prescribed external forces and
moments.
In order to obtain the displacement-based governing equations for the different parts of
the composite pipe joint system, the resultant forces and moments (Eq. (3-5)) and the strain-
displacement relationships are substituted into the above equilibrium equations. For example,
in the coupled pipe part, the displacement-based governing equations can be expressed in the
local coordinate system as:
∂2up0 ∂2φp 1 ∂wp ∂2vp0 ∂2ϕp

Ap11 + Bp11 + Ap12 + (Ap12 + Ap661) + (Bp12 + Bp661)
∂ς 2 ∂ς 2 Rp ∂ς ∂ξ p∂ς ∂ξp∂ς
(3-13a)
∂2up0 ∂2φp
Rpo ⎡ ⎛ up − uc ⎞ Ga ⎛ ∂wc ∂wp ⎞⎤
+ Ap662 + Bp662 2 = ⎢Ga ⎜ ⎟− ⎜ + ⎟⎥
∂ξp
2
∂ξp Rp ⎣ ⎜⎝ ha ⎟⎠ 2 ⎜⎝ ∂ς ∂ς ⎟⎠⎦
∂2u p0 ∂2φp 1 ∂w
( Ap21 + Ap662) + (Bp21 + Bp662) + ( Ap22 + Ap44 ) p
∂ς∂ξ p ∂ς∂ξ p Rp ∂ξ p
∂ 2v p 0 ∂2ϕ p 1 1 ∂ 2v p 0 ∂2ϕ p
+ Ap22 + Bp22 + (− Ap44vp0 + Ap44ϕ p ) + Ap661 2 + Bp661 2 (3-13b)
∂ξ p2 ∂ξ p2 Rp Rp ∂ς ∂ς
Rpo ⎡ ⎛ vp − vc ⎞ Ga ⎛ ∂wp ∂wc ⎞ Ga ⎛ vp + vc ⎞⎤
= ⎢Ga ⎜ ⎟− ⎜ + ⎟+ ⎜ ⎟⎥
Rp ⎢⎣ ⎜⎝ ha ⎟⎠ 2 ⎜⎝ ∂ξ p ∂ξc ⎟⎠ 2 ⎜⎝ Ra ⎟⎠⎥⎦
1 ∂φ p ∂ 2 wp ∂ 2 wp 1 ∂v p0
( Ap55 − Bp 21 ) + Ap55 + A − ( Ap 44 + Ap 22 )
∂ς ∂ς ∂ξ p Rp ∂ξ p
2 p 44 2
Rp
1 ∂ϕ p 1 ∂u p0 1
+ ( Ap 44 − Bp 22 ) − ( Ap 21 + Ap 22 wp )
Rp ∂ξ p Rp ∂ς Rp
(3-13c)
Rpo Ea wc − wp υa ∂u p0 hp ∂φ p ∂uc0
=− {(1 −υa ) + ( + +
Rp (1 +υa )(1 − 2υa ) ha 2 ∂ς 2 ∂ς ∂ς
hc ∂φc υa wp Rp ∂v p0 hp ∂ϕ p w R ∂v h ∂ϕ
− )+ [ + ( + ) + c + c ( c0 − c c )]}
2 ∂ς 2 Rpo Rpo ∂ξ p 2 ∂ξ p Rci Rci ∂ξc 2 ∂ξc
∂ 2u p 0 ∂ 2φ p 1 ∂wp ∂ 2v p 0
Bp11 + Dp11 + ( Bp12 − Ap 55 ) + ( Bp12 + B p 661 )
∂ς 2 ∂ς 2 Rp ∂ς ∂ξ p ∂ς
∂ 2ϕ p ∂ 2u p 0 ∂ 2φ p
+ ( Dp12 + Dp 661 ) − Ap 55φ p + Bp 662 + Dp 662 (3-13d)
∂ξ p ∂ς ∂ξ p2 ∂ξ p2
hp R po ⎡ ⎛ u p − uc ⎞ Ga ⎛ ∂wc ∂wp ⎞⎤
= ⎢Ga ⎜ ⎟− ⎜ + ⎟⎥
2 Rp ⎣ ⎜⎝ ha ⎟⎠ 2 ⎜⎝ ∂ς ∂ς ⎟⎠⎦
∂2u p0 ∂2φp 1 ∂w ∂ 2v
(Bp21 + Bp661) + (Dp21 + Dp661) +( Bp22 − Ap44 ) p + Bp22 p20
∂ς∂ξ p ∂ς∂ξ p Rp ∂ξ p ∂ξ p
∂ ϕp
2
1 1 ∂ 2v p 0
+ Dp22 − (− Ap44vp0 + Ap44ϕ p ) + (Bp661 + Dp661) 2 (3-13e)
∂ξ p2 Rp Rp ∂ς
1 ∂2ϕ p hp Rpo ⎡ ⎛ vp − vc ⎞ Ga ⎛ ∂wp ∂wc ⎞ Ga ⎛ vp + vc ⎞⎤

+ (Dp661 + Ep661) 2 = ⎢Ga ⎜ ⎟− ⎜ + ⎟+ ⎜ ⎟⎥
Rp ∂ς 2 Rp ⎢⎣ ⎜⎝ ha ⎟⎠ 2 ⎜⎝ ∂ξ p ∂ξc ⎟⎠ 2 ⎜⎝ Ra ⎟⎠⎥⎦
Similarly, the displacement-based governing equations for the bare pipe part and
connection coupler part can also be obtained in the respective local coordinate systems.
Evidently, based on the above analyses, there are a total of 15 second-order differential
equations with 30 boundary conditions as shown in Eq. (3-12), which will be used to
determine 15 unknown functions, i.e. up0, φp, vp0, ϕp and wp in the coupled pipe part, ub0, φb,
vb0, ϕb and wb in the bare pipe part, and uc0, φc, vc0, ϕc and wc in the connection coupler part.
Thus, the problem is closed. In order to obtain the analytical solutions for these differential
equations, a coordinate transform is introduced to transform the above differential equations
into a uniform coordinate system as follows:
ξ a Ra ξ R
= and a = a (3-14)
ξ p Rp ξ c Rc
Further, some coordinate transform relationships can be represented by:
∂ (•) Ra ∂ (•)
= , (3-15a)
∂ξ p R p ∂ξ a
2
∂ 2 (•) ⎛⎜ Ra ⎞ ∂ 2 (•)
⎟
= ; (3-15b)
∂ξ p2 ⎜R ⎟ ∂ξ 2
⎝ p ⎠ a
∂ (•) Ra ∂ (•)
= , (3-15c)
∂ξ c Rc ∂ξ a
2
∂ 2 (•) ⎛ Ra ⎞ ∂ 2 (•)
= ⎜⎜ ⎟⎟ . (3-15d)
∂ξ c2 ⎝ Rc ⎠ ∂ξ a
2
where the notation ‘•’ inside the bracket denotes the differential variables.
After applying the above coordinate transforms to the displacement-based governing
equations for the three parts in their respective local coordinate system, a new set of
governing equations with 15 unknown variables and 30 boundary and continuity conditions
are obtained in the uniform coordinate system.
3.1.3. Analytical Solution Procedure
Considering the symmetry, anti-symmetry and continuity of the circular geometry and applied
loading, the general solutions for the variables by the Fourier series in the ξa-axis can be
expressed in the following forms:
nξ a
u0 (ς , ξ ) = ∑ U (ς ) cos( ) (3-16a)
n Ra
nξ a
φ (ς , ξ ) = ∑ Φ(ς ) cos( ) (3-16b)
n Ra
nξ a
v0 (ς , ξ ) = ∑ V (ς ) sin( ) (3-16c)
n Ra
nξ a
ϕ (ς , ξ ) = ∑ Ψ (ς ) sin( ) (3-16d)
n Ra
nξ a
w(ς , ξ ) = ∑ W (ς ) cos( ) (3-16e)
n Ra
It is noted that the above basic solutions are general solutions and suitable for the three
different parts of the joint. So far, 15 new unknown variables, U p (ς ) , Φ p (ς ) , V p (ς ) ,
Ψ p (ς ) , W p (ς ) , U b (ς ) , Φ b (ς ) , Vb (ς ) , Ψb (ς ) , Wb (ς ) , U c (ς ) , Φ c (ς ) , Vc (ς ) , Ψc (ς )
and Wc (ς ) , have been introduced. In order to simplify the solution process, it is assumed that
the applied bending moment M at the joint end is produced by the normal stress resultant with
~ ~ ξa
a cosine distribution around the pipe wall, i.e. N (ς , ξ ) = N 0 (ς ) cos( ).
Ra
Therefore, the assumed Fourier series solution can be further simplified to contain only
one sine or cosine term for the basic solutions. Further, the boundary conditions (Eq. (3-12a))
can be represented by:
~
M ξ
N bς = − 2 cos( a ) , Qbςξ = 0 , Qbzς = 0 , M bς = 0 , M bςξ = 0 ; (3-12a)
πRb Ra
After substitution of the above relevant solutions into the governing equations in the
uniform coordinate system, the coefficients of sine and cosine are collected to obtain a new
set of 15 ordinary differential equations involving the above 15 new variables. Here, the
detailed new ordinary differential equations for the coupled pipe part are obtained after
collecting the coefficients of sine and cosine in the resultant Eq. (3-13) in the following
forms:
∂2Up0 ∂2Φp 1 ∂Wp n ∂Vp0 n ∂Ψp

Ap11 + Bp11 + Ap12 +(Ap12 + Ap661) +(Bp12 + Bp661)
∂ς 2 ∂ς 2 Rp ∂ς Rp ∂ς Rp ∂ς
(3-17a)
n n Rpo ⎡ ⎛Up −Uc hpΦp +hcΦc ⎞ Ga ⎛ ∂Wc ∂Wp ⎞⎤
− Ap662( )2Up −Bp662( )2Φp = ⎢Ga⎜⎜ + ⎟⎟ − ⎜⎜ + ⎟⎟⎥
Rp Rp Rp ⎣ ⎝ ha 2ha ⎠ 2 ⎝ ∂ς ∂ς ⎠⎦
n ∂Up n ∂Φp 1 n
− ( Ap21 + Ap662) − (Bp21 + Bp662) − ( Ap22 + Ap44) Wp
Rp ∂ς Rp ∂ς Rp Rp
n 2 n 1 1 ∂2Vp ∂2Ψp
− Ap22( ) Vp − Bp22( )2 Ψp + (− Ap44Vp + Ap44Ψp ) + Ap661 2 + Bp661 2 (3-17b)
Rp Rp Rp Rp ∂ς ∂ς
Rpo ⎡ ⎛Vp −Vc hpΨp + hcΨc ⎞ Ga ⎛ n n ⎞ G ⎛V +V h Ψ − h Ψ ⎞⎤
= ⎢Ga ⎜⎜ + ⎟⎟ + ⎜ Wp + Wc ⎟ + a ⎜⎜ p c + p p c c ⎟⎟⎥
Rp ⎢⎣ ⎝ ha ⎜ Rc ⎟⎠ 2 ⎝ Ra
2ha ⎠ 2 ⎝ Rp 2Ra ⎠⎥⎦
1 ∂Φ p ∂ 2Wp n 1
( Ap55 − Bp 21 ) + Ap55 − [ Ap 44 ( ) 2 + 2 Ap 22 ]Wp − ( Ap 44
Rp ∂ς ∂ς 2
Rp Rp
n n n 1 ∂U p Rpo Ea
+ Ap 22 ) V + ( A − B ) Ψ − A = −
∂ς R p (1 + υa )(1 − 2υa )
2 p p 44 p 22 2 p p 21
Rp Rp Rp Rp
(3-17c)
Wc − Wp υ ∂U p0 hp ∂Φ p ∂U c0 hc ∂Φ c
×{(1 −υa ) + a( + + − )
ha 2 ∂ς 2 ∂ς ∂ς 2 ∂ς
υ a Wp Rp n hp n W R n h n
+ [ + ( Vp + Ψp ) + c + c ( Vc − c Ψc )]}
2 R po R po Rp 2 Rp Rci Rci Rc 2 Rc
∂ 2U p ∂ 2Φ p 1 ∂W n ∂Vp
Bp11 + Dp11 +( Bp12 − Ap55 ) p + ( Bp12 + Bp661)
∂ς 2 ∂ς 2 Rp ∂ς Rp ∂ς
n ∂Ψp n n
+ ( Dp12 + Dp 661) − [ Ap55 + Dp662 ( )2 ]Φ p − Bp662 ( )2U p (3-17d)
Rp ∂ς Rp Rp
hp Rpo ⎡ ⎛ U p − U c hp Φ p + hc Φc ⎞ Ga ⎛ ∂Wc ∂Wp ⎞⎤
= ⎢Ga ⎜ + ⎟⎟ − ⎜⎜ + ⎟⎥
2 Rp ⎣ ⎜⎝ ha 2ha ⎠ 2 ⎝ ∂ς ∂ς ⎟⎠⎦
n ∂Up n ∂Φp 1 n n 1
−(Bp21 + Bp661) −(Dp21 + Dp661) −( Bp22 − Ap44) Wp −[Bp22( )2 − Ap44]Vp
Rp ∂ς Rp ∂ς Rp Rp Rp Rp
n 2 1 ∂2Vp 1 ∂2Ψp (3-17e)
−[Dp22( ) + Ap44]Ψp +(Bp661+ Dp661) 2 +(Dp661+ Ep661) 2
Ra Rp ∂ς Rp ∂ς
hp Rpo ⎡ ⎛Vp −Vc hpΨp +hcΨc ⎞ Ga ⎛ n n ⎞ G ⎛V +V h Ψ −h Ψ ⎞⎤
= ⎢Ga ⎜⎜ + ⎟⎟ + ⎜ Wp + Wc ⎟ + a ⎜⎜ p c + p p c c ⎟⎟⎥
2 Rp ⎣⎢ ⎝ ha ⎜ Rc ⎟⎠ 2 ⎝ Ra
2ha ⎠ 2 ⎝ Rp 2Ra ⎠⎦⎥
In the same manner, the new ordinary differential equations for the connection coupler
part and bare pipe part can be obtained.
In order to solve these 15-ordinary differential equations, the state-space method can be
employed to simplify these equations and further obtain a new set of first-order state
equations by introducing the following variables:
∂U p ∂Φ p
Z1 = U p , Z 2 = Z1' = , Z3 = Φ p , Z 4 = Z 3' = , Z5 = Vp ,
∂ς ∂ς
∂V p ∂Ψp ∂W p
Z 6 = Z 5' = , Z 7 = Ψp , Z8 = Z 7 =
'
, Z 9 = W p , Z10 = Z 9 =
, Z11 = U c ,
'
∂ς ∂ς ∂ς
∂U c ∂Φ c ∂Vc
Z12 = Z11' = , Z13 = Φ c , Z14 = Z13 =
'
, Z15 = Vc , Z16 = Z15 =
'
, Z17 = Ψc ,
∂ς ∂ς ∂ς
∂Ψc ∂Wc
Z18 = Z17' = , Z19 = Wc , Z 20 = Z19 =
'
;
∂ς ∂ς
∂U b ∂Φ b
X1 = Ub , X 2 = X 1' = , X 3 = Φb , X 4 = X 3' =
, X 5 = Vb ,
∂ς ∂ς
∂V ∂Ψb ∂Wb
X 6 = X 5' = b , X 7 = Ψb , X 8 = X 7' = , X 9 = Wb , X 10 = X 9 =
'
.
∂ς ∂ς ∂ς
Using the above introduced new variables, the relevant differential equations for the
connection coupler and coupled pipe in the overlap part, as shown in Eq. (3-17), are presented
in the matrix form as:
[Ξ ]{Z }' = [ A]{Z } + {E piezo } (3-18)
where {Epiezo} is a 20×1 matrix and related to the actuating piezoelectric layer induced forces
and moments. [Ξ ] and [A] are the relevant coefficient matrices obtained from Eq. (3-17) etc.,
which details can be referred to Reference [53].
Similarly, the displacement based governing equations for the bare pipe part can be
obtained by neglecting the right-hand terms of Eq. (3-17) and are further presented in the
matrix form as follows:
[ Π ]{ X }' = [Β]{ X } , (3-19)
where the [∏] is a 10×10 matrix, in which the elements are equal to the relevant elements of
the first 10 columns and the first 10 rows of matrix [Ξ]. The matrix [B] is also a 10×10
matrix, which are equal to the part of the first 10 rows × 10 columns of matrix [A], only by
neglecting the underlined terms in the relevant elements as seen in Reference [53].
Further, the relevant differential equations for the connection coupler and coupled pipe in
the overlap part and the bare pipe part can be expressed in a state equation form respectively
as:
{Z }' = [ H ]{Z } + [Λ] (3-20a)
{ X }' = [ M ]{ X } (3-20b)
−1
where the matrix [H] in Equation (3-20a) is obtained as [ H ] = [Ξ ] [ A] , and the matrix [M]
−1
can be obtained by [ M ] = [Π ] [Β] . The [Λ] is a 20×1 matrix and related to the actuating
piezoelectric layer induced forces and moments due to externally applied electric fields and
its non-zero elements can be represented by:
ς )'ς − Bc11 ( M cς )'ς

Dc11 ( N cPZT ς )'ς − Bc11 ( N cς )'ς
PZT
Ac11 ( M cPZT PZT
Λ(12,1) = , Λ(14,1) = ,
Ac11Dc11 − Bc211 Ac11Dc11 − Bc211
( Dc661 + Ec661 / Rc )( N cPZT

ξ )'ξ − Bc 661 ( M cξ )'ξ
PZT
Λ(16,1) =
Ac661( Dc661 + Ec661 / Rc ) − Bc661( Bc661 + Dc661 / Rc ) ,
ξ )'ξ −( Bc 661 + Dc 661 / Rc )( N cξ )'ξ

Ac661( M cPZT PZT
N cPZT
ξ
Λ(18,1) = , Λ ( 20,1) = −
Ac661( Dc661 + Ec661 / Rc ) − Bc661( Bc661 + Dc661 / Rc ) Ac 55 Rc
∂ (•) ∂H ( x − x0 )
with the following derivative definitions: (•)' x = , = δ ( x − x0 ) and
∂x ∂x
∂ 2 H ( x − x0 )
= δ ' ( x − x0 ) .
∂x 2
Meanwhile, the shear and peel stresses in the adhesive layer can be re-written by the
introduced state variables in the following matrix forms:
Ga h p Ga G G hG G
τς = [ ,0, ,0,0,0,0,0,0,− a ,− a ,0, c a ,0,0,0,0,0,0,− a ]{Z } (3-21a)
ha 2ha 2 ha 2ha 2
Ga Ga h p Ga h p Ga Ga n
τ ξ = [0,0,0,0, + ,0, + ,0, ,0,0,0,0,0,
ha 2 Ra 2ha 4 Ra 2 Rp (3-21b)
G G hG hG G n
− a + a ,0, c a − c a ,0, a ,0]{Z }
ha 2 Ra 2ha 4 Ra 2 Rc
Ea υ υ h p υ n υa n h p 1 − υa υ a
p= [0, a ,0, a , a ,0, ,0,− + ,0,
(1 + υa )(1 − 2υa ) 2 2 2 2 Rpo 2 Rpo 2 ha 2Rpo (3-21c)
υa υa hc υa n υa n hc
1 − υa υa
0, ,0,− , ,0,− ,0, + ,0]{Z}
2 2 2 2 Rci 2 Rci 2 ha 2Rci
Now integrating both sides of Eq. (3-20a) over dummy variable ϑ from ζ0 to ζ, the final
solution is derived in the following form:
ς
Z (ς ) = eς [ H ]{k1} + eς [ H ] ∫ e −ϑ [ H ] [Λ ]dϑ (3-22a)
and the general solution for Eq. (3-20b) is:
X (ς ) = eς [ M ] {k 2 } (3-22b)
where {k1 } is a vector with 20 unknown coefficients determined by the relevant boundary
and continuity conditions at ς = 0, l1 , and, {k 2 } is a vector with 10 unknown coefficients
calculated by the boundary and continuity conditions at ς = 0, l 2 , as shown in Eq. (3-12).
With the help of the strain-stress and strain-displacement relationships (Eq. (3-2) ∼ (3-5)), the
unknown coefficients {k i } (i=1, 2) are determined by the boundary and continuity conditions
via the programmed Mathematica software. The peel and shear stress distributions in the
adhesive layer can be analytically calculated by Eq. (3-21).
3.1.4. Numerical Example and Discussion
In order to validate the effectiveness and efficiency of the integrated piezoelectric layer on the
connection coupler, some detailed numerical analyses are conducted when the joint is
subjected to a bending moment at the end of the joint. The 54-dregree filament-wound E-
glass/Derakane 470 composite pipe has been taken as the calculation samples for the pipe and
the connection coupler. The material properties and geometric parameters of the composite
pipe and coupler, adhesive and piezoelectric ceramics used in the detailed simulations are
assumed as follows:
Composite layer: E1=25.2 GPa, E2=7.5 GPa, G12=2.4 GPa, v12=0.32;

Epoxy adhesive: Ea=0.96 GPa, Ga=0.34 GPa, ν a =0.412;
Piezoelectric materials: EPZT =84 GPa, ν 3 =0.22, d31=d32= -310pC/N;

Geometric parameters: l1=25.4mm; l2=25.4mm; ha=0.0254mm. hp=hc=2.54mm,
Rpi=50.8mm.
Assuming that the smart connection coupler consists of six plys with the following
stacking sequence [Comp/PZT1/Comp/Comp/PZT2/Comp] and lamina thickness
hc hc hc hc hc hc
[ / / / / / ] , where the layers PZT1 and PZT2 are subjected to electric
6 6 6 6 6 6
1 2
fields E 3 and E3 , respectively. In order to validate the developed electro-mechanical
coupled analytical model, numerical comparisons are firstly made between the analytical
solution and finite element modeling (FEM) results. A whole smart pipe joint is meshed and
simulated by ABAQUS using the eight-node 3-D elasticity element (C3D8) and adhesive
element (COH3D8). It is seen from Fig. 33 and 34 that, with an applied bending moment
113N•m at the end of this smart joint, the analytical results are close to the FEM results. This
suggests that the developed analytical model is reliable. The analytical model can be used to
conduct parametric analysis. Thereafter, we utilize the verified analytical model to further
consider the structural response of the smart joint under the action of coupled
electric/mechanical loadings.
-0.5
Shear stress τζ(MPa)
-1.0
-1.5
Analytical solution
FEM result
-2.0
-2.5
-0.01 -0.005 0 0.005 0.01
ζ(m)
Figure 33. Numerical comparison of shear stress τ ς distribution.

Peel stress p (MPa)

-2
-4
-6
-8 Analytical solution
FEM result
-10
-0.01 -0.005 0 0.005 0.01
ζ(m)
Figure 34. Numerical comparison of peel stress p distribution.
-0.5
Shear stress τζ(MPa)
-1
-1.5 E31=100KV/m
E31=10KV/m
-2 E31=1KV/m
E31=0V/m
-2.5 E31=-1KV/m
E31=-10KV/m
E31=-100KV/m
-3
-3.5
-0.01 -0.005 0 0.005 0.01
ζ(m)
Figure 35. The influences of the external applied electric fields E 31 on the shear stress τζ distribution
along ζ-axial at ξ=0 in Case 1.
E31=100KV/m
2
E31=10KV/m
E31=1KV/m
E31=0V/m
Shear stress τξ(MPa)
E31=-1KV/m
1 E31=-10KV/m
E31=-100KV/m
-1
-0.01 -0.005 0 0.005 0.01

ζ(m)
Figure 36. The influences of the external applied electric fields E 31 on the shear stress τξ distribution
E31=100KV/m
2
E31=10KV/m
Shear stress τξ(MPa)

E31=1KV/m
E31=0V/m
1 E31=-1KV/m
E31=-10KV/m
E31=-100KV/m
-1
-0.01 -0.005 0 0.005 0.01

ζ(m)
Figure 37. The influences of the external applied electric fields E 31 on the shear stress τξ distribution
Subjected to the combined electric/mechanical loading, the peel and shear stress
distributions are calculated and the results are shown in Figs. 35 and 36 for the shear stress
distribution and Fig. 37 for the peel stress distribution along the ζ axial direction at ξa=0,
1 2
where E 3 = E3 is used and taken as Study Case 1. All the numerical results in Fig. 35-37
indicate that the peel/shear stress concentrations always present in the end edge region of the
joint; however, they can be significantly and adaptively changed by adjusting the electric
fields applied to the integrated piezoelectric layers. Further, in order to evaluate the effect of
different electric fields applied to different piezoelectric layers on the shear/peel stress
distributions, numerical simulations are conducted and the results of the maximum stress
values are presented in Fig. 38 for four study cases: Case 1, i.e. E 3 = E 3 which can induce
1 2
N iPZT ≠ 0 and M iPZT ≈ 0 ; Case 2, i.e. E32 = − E31 which can yield N iPZT ≈ 0
and M i
PZT
≠ 0 ; Case 3, i.e. E31 ≠ 0 and E32 = 0 which means N iPZT ≠ 0 and M iPZT ≠ 0 ;
and Case 4, i.e. E 3 = 0 and E 3 ≠ 0 which indicates N i ≠ 0 and M iPZT ≠ 0 . From the
1 2 PZT
1
numerical results in Fig. 38, it is seen that the applied negative electric fields E 3 can
drastically reduce the maximum values of all the shear stresses τζ, τξ and peel stress p in Case
1. Specifically, the shear stress τζ is reduced from -3.23MPa to -1.77MPa, the shear stress τξ
is changed from 2.25MPa to –1.76MPa including zero, and the peel stress is changed from
77.4MPa (tension) to -97.7MPa (compression) including zero. This means that the stress
concentrations in the adhesive layer can be successfully controlled and even eliminated by
applying appropriate electric fields through the integrated piezoelectric layers. To the
1
opposite, a positive electric field E 3 increases the maximum values of peel stress p and shear
stresses τζ and τξ in Case 1. Case 4 experiences the same effect as the Case 1. Compared to
Case 1, the applied negative and positive electric fields in Case 2 can induce completely
reversed effects, i.e. the applied negative electric fields E31 can significantly
-1.6 3
-1.8 Case 1 Case 1

Case 2 Case 2
2
-2.0 Case 3 Case 3
Case 4 Case 4
Maximum stress (MPa)

-2.2
1
-2.4
-2.6 0
-2.8
-1
-3.0
-3.2 -2
-3.4
-100000 -50000 0 50000 100000 -100000 -50000 0 50000 100000
Applied electric field (V/m) Applied electric field (V/m)
(a) Shear stress τζ (b) Shear stress τξ

100
80 Case 1
Case 2
60 Case 3
40 Case 4
Maximum stress(MPa)
20
-20
-40
-60
-80
-100
-120
-100000 -50000 0 50000 100000

(c) Peel stress p
Figure 38. The effect comparison of the applied electric fields E31 on the maximum shear stresses τζ,τξ
and maximum peel stress p in Cases 1-4.
increase the maximum values of all the peel and shear stresses in Case 2 as depicted in Fig.
38. However, the applied negative and positive electric fields only have very limited effects
on the maximum peel and shear stresses in Case 3. These results indicate that the smart
composite pipe joint is designable and can be optimized by controlling the electric fields
applied to different piezoelectric layers.
-1.0 3
-1.2
Case 1 Case 1
-1.4
Case 2 Case 2
-1.6 2
Case 5 Case 5
-1.8 Case 6
Maximun stress (MPa)

Case 6
-2.0
-2.2 1
-2.4
-2.6
0
-2.8
-3.0
-3.2
-1
-3.4
-3.6
-3.8
-2
-4.0
-100000 -50000 0 50000 100000
-100000 -50000 0 50000 100000
Applied electric field (V/m) Applied electric field (V/m)
(a) Shear stress τζ (b) Shear stress τξ
160
140
120 Case 1
100 Case 2
80 Case 5
60 case 6
40
20
0
-20
-40
-60
-80
-100
-120
-140
-160
-180
-100000 -50000 0 50000 100000
(c) Peel stress p
Figure 39. The influences of the piezoelectric layers’ stacking sequence and thickness on the maximum
shear stresses τ ς , τ ξ and peel stress p in Cases 1, 2, 5, 6.
The thickness effect of the integrated piezoelectric layers in the connection coupler is
also investigated. Here, it is assumed that the composite connection coupler has the same
hc hc hc hc hc hc
stacking sequence with different lamina thicknesses [ / / / / / ] . Similarly,
6 4 12 12 4 6
four cases for this geometric parameter are examined, including Case 5, E 3 = E 3 , Case 6,
1 2
E32 = − E31 , Case 7, E31 ≠ 0 and E32 = 0 , and Case 8, E31 = 0 and E32 ≠ 0 . Figure 39
illustrates the detailed numerical results for the thickness effect of the integrated piezoelectric
layers on the joint strength enhancement. From Fig. 39, it is evident that the thicker integrated
piezoelectric layers can achieve higher efficiency on changing the maximum peel and shear
stresses than the thinner piezoelectric layers.
-1.0
-1.2 Case 1 Case 2
-1.4
Case 3 Case 4
Case 5 Case 6
-1.6
Case 7 Case 8
-1.8

-2.0
-2.2
-2.4
-2.6
-2.8
-3.0
-3.2
-3.4
-3.6
-3.8
-4.0
-100000 -50000 0 50000 100000
Figure 40. The detailed efficiency comparisons of the integrated piezoelectric layers on the maximum
shear stress τζ in all the study cases.
3
Case 1 Case 2
Case 3 Case 4
2 Case 5 Case 6
Case 7 Case 8
-1
-2
-100000 -50000 0 50000 100000
shear stress τξ in all the study cases
In order to compare and summarize the efficiency of the integrated piezoelectric layers in
different study cases, some more detailed comparisons of the maximum peel/shear stresses
for all the study cases are presented in Fig. 40-42. From the numerical comparisons, it is
again confirmed that the thickness of the integrated piezoelectric layers has a significant
effect on the maximum peel and shear stresses, and the thicker integrated piezoelectric layers
can speed up the enhancement/reduction of the maximum peel/shear stress under the relevant
applied electric fields. Due to the overall material properties change of the coupler caused by
thickening the integrated piezoelectric layers, the initial maximum peel/shear stresses (i.e. the
maximum peel/shear stresses at E3 = E3 = 0 ) have a little increase, as shown in Fig. 40-42.
1 2
Through the comparison, it is found that the smart pipe joint structure in Case 6 can achieve a
better ability and higher efficiency in reducing the maximum peel and shear stresses.
160
140 Case 1 Case 2
120 Case 3 Case 4
100 Case 5 Case 6
80 Case 7 Case 8

60
40
20
0
-20
-40
-60
-80
-100
-120
-140
-160
-180
-100000 -50000 0 50000 100000
peel stress p in all the study cases.
From the above detailed numerical analysis, it is evident that the integrated piezoelectric
layers can significantly reduce the maximum peel/shear stresses in the adhesive layer with
suitable stacking sequence, lamina thickness and applied electric fields. The strength of the
smart joint can be adaptively enhanced through proper design.
3.2. Smart Composite Pipe Joint under Axial Extension
3.2.1. Fundamental Equations for Smart Composite Pipe Joint under Axial Tension
3.2.1.1. Displacements and Strains
Now consider the proposed smart composite pipe joint that is subjected to an axial tensile
~
force N , as shown in Fig. 43. Due to the axial-symmetric characteristic of the composite
pipe joint system under the axial tensile loading, the overall pipe joint system can be regarded
as a two-dimensional problem. Therefore in terms of the first-order shear deformation plate
theory, the displacements u, v and w in the different sections of the joint can be simplified
from the Eq. (3-1) and presented respectively as follows:
ui ( x, z ) = u0i ( x ) + zφi ( x ) ; vi ( x, z ) = 0 ; wi ( x, z ) = w( x ) . (3-23)
where the ‘i=c, p, b’ denote the variables for the connection coupler, overlapping pipe and
bare pipe sections respectively. The u0i and wi are the mid-plane displacement and φi is the
rotation of the different sections of the joint.
Symmetric axis
Coupler x1 x2
N N
Bare pipe Coupling pipe l1 l2
Figure 43. A schematic view for the different parts of composite pipe joint system.
Similarly, the strains of the pipe and coupler in this case can be rewritten in the following
simple forms as:
∂ui ∂u0i ∂φ wi ∂wi

ε 1i = ε xi = = + z i ; ε 2i = ε si = ; ε zi = = 0;
∂x ∂x ∂x Ri + z ∂z
∂u i ∂wi ∂w
ε xsi = ε szi = 0 ; ε xzi = + = φi + i . (3-24)
∂z ∂x ∂x
where R also denotes the radius of the mid-plane for the different sections, as shown in Fig.
30.
3.2.1.2. Laminate Constitutive Relationship
Considering the strain expression in Eq. (3-24) and fiber orientation angle of the kth layer, the
stress-strain relationships for the adhesively bonded smart composite pipe joint system
subjected to axial tension can be further simplified from Eq. (3-4) as follows:
⎧σ 1 ⎫ ⎡Q11 Q12 ⎤ ⎧ε 1 ⎫ ⎡ e31 ⎤

k k k
⎨ ⎬ =⎢ ⎨ ⎬ − ⎢ ⎥ {E3 }
k
⎥ (3-25a)
⎩σ 2 ⎭ ⎣Q21 Q22 ⎦ ⎩ε 2 ⎭ ⎣e32 ⎦
{σ 5 }k [
= KQ55 ] {ε }
k
5 (3-25b)
where Qij are the transformed stiffness and can be obtained from the relevant lamina as
defined above.
Further the relevant resultant forces and moments can be obtained by integration of the
stresses as shown in Eq. (3-5) in the following simple forms:
h
Ri + z ∂u ∂φ
N xi = ∫ 2 σ 1i dz = Ai11 0i + Bi11 i + Ei12 wi − N xcPZT (3-26a)
∂x ∂x
h
− Ri
2
h
Ri + z ∂u ∂φ
M xi = ∫ 2h zσ 1i dz =Bi11 0i + Di11 i + Fi12 wi − M xcPZT (3-26b)
−
2
Ri ∂x ∂x
h
Ri + z ∂u ∂φ
N si = ∫ 2h σ 2i dz =Ai 21 0i + Bi 21 i + E 22i wi − N scPZT (3-26c)
−
2
Ri ∂x ∂x
h
∂wi
Q xi = ∫ σ 5 dz =Ai 55φi + Ai 55
2 (3-26d)
∂x
h
−
2
where Aij, Bij, Dij, Eij and Fij are defined as the stiffness matrices for the convenience of
further formulation. Here, the resultant forces and moments induced by the piezoelectric layer
as actuators can be presented in the following forms:
n
Ri + z k k
N xcPZT = ∑ ∫
hk +1
e31 E3 dz ;
k =1
hk Ri
n
Ri + z k k n hk +1 R + z
M xcPZT = ∑ ∫ ze31 E3 dz ; N scPZT = ∑ ∫
hk +1
i
e32k E3k dz (3-27a)
k =1
hk Ri h
k =1 k Ri
It is evident that the electric field–induced additional forces and moments can be
controlled through adjusting the lamina thickness and applied electric field in the different
piezoelectric layers. Further, in order to consider the effect of the surface covered electrode
region [x0, x1] in the piezoelectric layers, we can apply the Heaviside step function to describe
the applied electric field in the following form
Vk
E3k = − [ H ( x − x0 ) − H ( x − x1 )] (3-27b)
hk
with H ( x − xa ) being the Heaviside step function.
3.2.2. Equilibrium Equations and Boundary Conditions
Now considering the smart pipe joint subjected to an axial tension, the infinitesimal elements
of the joint section and the static equilibrium conditions for each layer can be described as
shown in Fig. 44. From Fig. 44, the fundamental equilibrium equations for any segment of the
joint can be obtained as follows:
Qxi+dQxi Nxi+dNxi
Mxi+dMxi
q
τ
Nsi τ
q
Nsi+dNsi τ
q
Mxi
Qxi
Nxi
(a) Adherends (b) Adhesive
Figure 44. The infinitesimal elements of a joint system: (a) adherends (connection coupler or main
pipe), (b) adhesive layer.
In the connection coupler, we have:
∂N xc R ∂M xc h R ∂Q xc N sc Rci
= − ci τ ; − Q xc = c ci τ ; − = q (3-28)
∂x Rc ∂x 2 Rc ∂x Rc Rc
and in the overlapping pipe section as shown in Fig. 43 and 44, we can obtain the equilibrium
equations as:
∂N xp R po ∂M xp h p R po ∂Q xp N sp R po
= τ; − Q xp = τ; − =− q (3-29)
∂x Rp ∂x 2 Rp ∂x Rp Rp
where Rc and Rp are the central radius of the coupler and pipe respectively. Rpo is the outer
radius of the pipe and Rci the inner radius of the coupler as defined in Fig. 30.
Since the pipe joint system is only subjected to an axial tension loading, the shear stress τ
and peel stress q in the adhesive layer are caused only by the inhomogeneity of the
longitudinal, tangential and radial deformations in the pipe and coupler. Thus, the shear stress
τ in the adhesive layer can be expressed by the longitudinal displacement change from the
inner surface of the coupler to the outer surface of pipe and the relative first-order axial
derivative of their radial deflections in the following form:
Ga h h G ∂w ∂w
τ= [(u0 p − u0 c ) + ( p φ p + c φ c )] − a ( p + c ) (3-30)
ha 2 2 2 ∂x ∂x
And, the peel stress p is mainly caused by the radial displacements difference between
the coupler and pipe and written as:
Ea
q= ( wc − w p ) (3-31)
ha
where Ga and Ea are the shear and Young’s modulus of the adhesive layer with the thickness
ha .
Similarly, the conditions of force equilibrium for the bear pipe section, as shown in Fig.
43, can be obtained by neglecting the shear and peel effects from Eq. (3-29) as follows:
∂N xp ∂M xp ∂Q xp N sp
= 0; − Q xp = 0 ; − =0 (3-32)
∂x ∂x ∂x Rp
Furthermore, the relevant boundary conditions and continuity conditions between the
different sections of the smart composite pipe joint system can be presented in the following
details when the axial-symmetric tension loading is applied to the pipe end as shown in
Fig. 43:
At x1=0, due to the free overlapping pipe and the symmetric characteristics of the joint
system for the coupler, we have the relevant boundary conditions for the overlapping pipe and
coupler respectively as:
N xp (0) = 0 , M sp (0) = 0 , Q xp (0) = 0 ; (3-33a)
dwc
u 0 c ( 0) = 0 , (0) = 0 , Q xc (0) = 0 ; (3-33b)
dx
Similarly, at x1=l1 due to the free edge of the smart coupler end, we have:
N xc (l1 ) = 0 , M sc (l1 ) = 0 , Q xc (l1 ) = 0 ; (3-33c)
While at x1=l1 and x2=0, the coupling pipe section and the bare pipe section is continuous,
we can present the continuity conditions for the pipe as:
u0 p (l1 ) = u0b (0) , φ p (l1 ) = φb (0) , w p (l1 ) = wb (0) ,
du0 p du0b dφ p dφ dw p dw
(l1 ) = (0) , (l1 ) = b (0) , (l1 ) = b (0) ; (3-33d)
dx dx dx dx dx dx
Finally, at x2=l2, i.e. the end of the pipe joint, it is subjected to a tensile loading, which
can yield:
~
N xb (l2 ) = N x 0 , M sb (l2 ) = 0 , Q xb (l 2 ) = 0 . (3-33e)
Now, substituting the relevant resultant forces and moments into the above force
equilibrium equations in Eq. (3-28), (3-29) and (3-32), we can obtain the displacement-based
governing differential equations for the smart composite pipe joint system as follows:
In the coupler, we have
∂ 2 u0 c ∂ 2φc ∂w
Ac11 + B + Ec12 c
∂x ∂x ∂x
2 c11 2
(3-34a)
R G h h G ∂w ∂w ∂N xcPZT
= − ci { a [(u p 0 − uc 0 ) + ( p φ p + c φc )] − a ( p + c )} +
Rc ha 2 2 2 ∂x ∂x ∂x
∂ 2 u 0c ∂ 2φc ∂w ∂w
Bc11 + D + Fc12 c − ( Ac55φc + Ac55 c )
∂x ∂x ∂x ∂x
2 c11 2
(3-34b)
hc Rci Ga hp hc Ga ∂w p ∂wc ∂M scPZT
= { [(u p 0 − u c 0 ) + ( φ p + φc )] − ( + )} +
2 Rc ha 2 2 2 ∂x ∂x ∂x
∂φc ∂ 2 wc 1 ∂u ∂φ
A55 + A55 − ( Ac 21 0 c + Bc 21 c + Ec 22 wc )
∂x ∂x 2
Rc ∂x ∂x
(3-34c)
R E N PZT
= ci a ( wc − wp ) − sc
Rc ha Rc
and the new displacement based expression for the overlapping pipe section can be rewritten
as:
∂ 2 u0 p ∂ 2φ p ∂w p
Ap11 + B p11 + E p12
∂x 2
∂x 2
∂x
(3-35a)
R G h h G ∂w ∂w
= po { a [(u p 0 − uc 0 ) + ( p φ p + c φ c )] − a ( p + c )}
R p ha 2 2 2 ∂x ∂x
∂ 2 u0 p ∂ 2φ p ∂w p ∂w p
B p11 + D p11 + Fp12 − ( Ap 55φ p + Ap 55
)
∂x 2 ∂x 2 ∂x ∂x
(3-35b)
h R G h h G ∂w ∂w
= p po { a [(u p 0 − uc 0 ) + ( p φ p + c φ c )] − a ( p + c )}
2 R p ha 2 2 2 ∂x ∂x
∂φ p ∂ 2 wp 1 ∂u0 p ∂φ p Rpo Ea
Ap55 + Ap55 − ( Ap21 + Bp21 + E p22wp ) = − (wc − wp ) (3-35c)
∂x ∂x 2
Rp ∂x ∂x Rp ha
Similarly, we can present the displacement-based governing equations for the bare pipe
section as:
∂ 2 u0 p ∂ 2φ p ∂w p
Ap11 + B p11 + E p12 =0 (3-36a)
∂x 2
∂x 2
∂x
∂ 2 u0 p ∂ 2φ p ∂w p ∂w p
B p11 + D p11 + Fp12 − ( Ap 55φ p + Ap 55 )=0 (3-36b)
∂x 2
∂x 2
∂x ∂x
∂φ p ∂2wp 1 ∂u ∂φ
Ap 55 + Ap 55 − ( Ap 21 0 p + B p 21 p + E p 22 w p ) = 0 (3-36c)
∂x ∂x 2
Rp ∂x ∂x
3.2.3. Solution Procedure
Similarly to Section 3.1, we can also apply the state-space method to conveniently solve the
above differential equations. However, we only need to introduce a smaller number of
unknown variables to simplify the above equations:
∂u0 c ∂φ c ∂wc
Z1 = u0 c , Z 2 = Z1' = , Z 3 = φc , Z 4 = Z 3 = , Z 5 = wc , Z 6 = Z 5 =
' '
,
∂x ∂x ∂x
∂u0 p ∂φ p ∂wp
Z 7 = u0 p , Z 8 = Z 7' = , Z 9 = φ p , Z 10 = Z 9 = , Z 11 = w p , Z12 = Z11 =
' '
;
∂x ∂x ∂x
∂u 0 b ∂φb ∂w
X1 = u0b , X 2 = X 1' = , X 3 = φb , X 4 = X 3 = , X 5 = wb , X 6 = X 5 = b .
' '
∂x ∂x ∂x
Using the above unknown variables, the displacement-based governing equations (i.e. Eq.
(3-34)-(3-36)) can be represented by the first-order state equation systems respectively in the
following matrix forms:
{Z }' = [ A]{Z } + [Λ ] (3-37)
{X }' = [ B ]{ X } (3-38)
where [Λ] is a 12×1 matrix related to the piezoelectric-induced forces and bending moments
and has the following non-zero elements:
Dc11 N xcP ' − Bc11 M xcP ' Ac11 M xcP ' − Bc11 N xcP ' N scPZT
Λ(2,1) = , Λ ( 4,1) = and Λ (6,1) = −
Ac11 Dc11 − Bc211 Ac11 Dc11 − Bc211 Ac55 Rc
with the following definitions N xcP ' = N xcPZT [δ ( x − l ) − δ ( x + l )]; MxcP' = MxcPZT[δ (x − l) −δ (x + l)].
And the detailed non-zero elements of coefficient matrices [A] and [B] can be referred to
Reference [51].
Clearly in terms of Equations (3-30) and (3-31), the peel and shear stresses in the
adhesive layer can be obtained by:
Ea Ea
q = [0 0 0 0 0 0 0 0 0 − 0]{Z } (3-39a)
ha ha
Ga Ga hc Ga Ga Ga h p
τ = [− 0 0 0 − 0 0 0 0]{Z } (3-39b)
ha 2ha 2 ha 2ha
The common exponent analytical solutions for the above two state equations (i.e. Eq. (3-
37) and (3-38)) can be generally expressed in the following forms:
x
Z ( x ) = e x [ H ] {k1} + e x[ H ] ∫ e −ϑ [ H ] [ Λ ]dϑ (3-40)
X ( x ) = e x [ Δ ] {k 2 } (3-41)
where {k1 } is a vector with 12 unknown coefficients determined by the relevant boundary
and continuity conditions at x = 0, l1 and {k 2 } is a vector with 6 unknown coefficients
calculated by the boundary and continuity conditions at x = 0, l2 , as given in Eq. (3-33),
with the help of strain-stress and strain-displacement relationships (Eq. (3-24) and (3-25)).
Once the unknown coefficients {k i } (i=1, 2) are determined by the boundary and continuity
conditions, the peel and shear stress distributions in the adhesive layer can be analytically
calculated by Eq. (3-39).
3.2.4. Numerical Analysis and Discussion
Using the same materials properties used in Section 3.1.4, we calculate some detailed
numerical examples to validate the efficiency of the developed smart pipe joint system with
the following geometric parameters: l1=25.4mm; l2=127mm; ha=0.0127mm. hp=hc=2.54mm,
Rpi=50.8mm, which is subjected to a 25kN axial tensile loading.
25
20 Electric field:
Peel stress (MPa)
E3=5MV/m
15 E3=10kV/m
E3=0V/m
10 E3=-10kV/m
E3=-5MV/m
5
-5
-0.01 -0.005 0 0.005 0.01

x1-l1/2 (m)
Figure 45. The influence of applied electric fields in the integrated piezoelectric layers on the peel stress
distribution for Case 1.
25
Shear stress (MPa)

Electric field:
20 E3=5MV/m
E3=10kV/m
15 E3=0V/m
E3=-10kV/m
10 E3=-5MV/m
-0.01 -0.005 0 0.005 0.01

x1-l1/2 (m)
Figure 46. The effect of applied electric fields in the integrated piezoelectric layers on the shear stress
distribution for Case 1.
Firstly, we assume that the developed smart coupler is laminated by the following
stacking sequence [Comp/PZT1/Comp/Comp/PZT2/Comp] with the ply thicknesses
hc hc hc hc hc hc
[ / / / / / ] , where the piezoelectric layers PZT1 and PZT2 are subjected to
6 6 6 6 6 6
1 2
the electric fields E 3 and E3 respectively. Then, some detailed calculations of the peel and
shear stress distributions for such stacking sequence and lamina geometries of the joint under
1 2
the combined mechanical axial loading and applied electric fields E 3 = E3 , which is set as
study Case 1, are firstly carried out. The results for Case 1 are shown in Fig. 45 for the peel
stress distribution and Fig. 46 for the shear stress distribution. The numerical results in Fig.
45 and 46 both indicate that the peel/shear stress concentrations always present in the end
edge region of the joint and can be significantly and adaptively controlled by the electric
fields applied to the integrated piezoelectric layers. Further, Figure 47 shows the detailed
influences of the different applied electric fields on the maximum peel/shear stresses for Case
1, i.e. E 3 = E 3 , which result in N i ≠ 0 and M iPZT ≈ 0 , and, Case 2, i.e. E32 = − E31
1 2 PZT
which can lead to N i

PZT
≈ 0 and M iPZT ≠ 0 . From Fig. 47, it is seen that the applied
1
negative electric field E 3 can dominantly reduce both the maximum peel and shear stresses
1
but the positive electric field E 3 increases the maximum peel and shear stresses in Case 1. In
Case 2, the enhancement effect of the integrated piezoelectric layers becomes more
1
complicated, namely, the applied negative electric field E 3 can decrease the maximum shear
stress but remarkably increase the maximum peel stress; contrastively, the positive applied
electric field can achieve the opposite effect. Furthermore, two other study cases for such
composite pipe joint, including the study Case 3: E 3 ≠ 0 and E3 = 0 , and study Case 4:
1 2
E31 = 0 and E32 ≠ 0 , both of which result in N iPZT ≠ 0 and M iPZT ≠ 0 , are modeled and
studied as depicted in Fig. 48. In case 3, it is obvious that the applied negative electric field
E31 can notably reduce the maximum shear stress. However, the positive electric fields
increase the maximum shear stress. The effects of applied electric fields on the maximum
peel stress are to the opposite of the maximum shear stress. With comparison to the results of
Case 3, the applied electric fields in Case 4 only have little influence on the maximum shear
stress in the adhesive layer. However, the negative electric fields can considerably reduce the
maximum peel stress, as presented in Fig. 48.
45
Maximum shear stress in Case 1
40 Maximum peel stress in Case 1
35 Maximum peel stress in Case 2
30
25
20
15
10
0
-4.0 -2.0 0.0 2.0 4.0
Figure 47. The influence of applied electric fields on the maximum peel and shear stress for Case 1 and
Case 2.
35 Maximum shear stress in Case 3

Maximum peel stress in Case 3
Maximum peel stress in Case 4

30
25
20
15
10
-4.0 -2.0 0.0 2.0 4.0
Applied electric field (MV/m)
Figure 48. The effect of applied electric fields on the maximum peel and shear stress for Case 3 and
Case 4.
Further, the thickness effect of the integrated piezoelectric layers on the

increase/reduction of the maximum peel and shear stresses is considered. Here, the smart
hc hc hc hc hc hc
coupler with the lamina thickness parameters [ / / / / / ] is utilized to
6 4 12 12 4 6
compute and analyze the detailed size effect. Under the same axial tensile loading, we
consider the following study cases: Case 5: E 3 = E 3 , Case 6: E 3 = − E 3 , Case 7:
1 2 2 1
E31 ≠ 0 and E32 = 0 and Case 8: E31 = 0 and E32 ≠ 0 . Figure 49 displays the numerical
comparison of the maximum peel/shear stresses between the study Case 1 and Case 5, which
indicates that the thickness of laminated piezoelectric layers can change the maximum stress.
32 Maximum shear stress at case 1

Maximum peel stress at case1
30 Maximum shear stress at case 5
Maximum peel stress at case 5

28
26
24
22
20
18
16
-4.0 -2.0 0.0 2.0 4.0
Figure 49. The influences of the integrated piezoelectric layer thickness on the maximum peel/shear
stress.
32
Case 7
30 Case 8
Case 3
28 Case 4
26
24
22
20
18
16
-4.0 -2.0 0.0 2.0 4.0
Figure 50. The effect of applied electric field on the maximum shear stress for Cases 3, 4, 7 and 8.
Some more detailed comparisons for the size effect of the maximum peel/shear stresses
among the different study cases are further presented in Fig. 50-52, which also reveal and
confirm the influence of the integrated piezoelectric layers thickness on the maximum
peel/shear stresses. It is found that thicker integrated piezoelectric layers can speed up the
enhancement/reduction of the maximum peel/shear stress under the relevant applied electric
fields. However, due to the change of the overall material properties of the coupler caused by
thickening the integrated piezoelectric layers, the initial maximum peel/shear stresses (i.e. the
maximum peel/shear stresses at E3 = E3 = 0 ) also have a slight increase, as shown in Figs.
1 2
50-52, which further clarifies the integrity of the developed strength improvement method
and designability of the composite pipe joint.
40
Case 7
35 Case 8
Case 3
Case 4
30
25
20
15
10
-4.0 -2.0 0. 2.0 4.0

Figure 51. The effect of applied electric field on the maximum peel stress for Cases 3, 4, 7 and 8.
32
Case 1
30
Case 2
Case 5
28
Case 6
26
24
22
20
18
16
-4.0 -2.0 0.0 2.0 4.0
Figure 52. The effect of applied electric field on the maximum shear stress for Cases 1, 2, 5 and 6.
From the above detailed numerical analyses, it is validated that the integrated
piezoelectric layers can significantly reduce the maximum peel/shear stress in the adhesive
layer with the suitable stacking sequence, lamina thickness and applied electric fields. Of
course, the integrated piezoelectric layers can also be used as sensors to monitor the joint
structural deformation. The sensing results can be obtained from sensing equation as shown in
Eq. (3-3b) after the structural deformation is determined. Here, we neglect the detailed
theoretical work on the sensing functions of the integrated piezoelectric layers.
4. Conclusion
In order to adaptively enhance the failure strength of the adhesively bonded joint system, a
smart adhesively bonded joint concept is introduced by bonding/integrating the
electromechanical coupling piezoelectric materials into the joint adherends. Through piezo-
effect of the surface bonded or embedded piezoelectric patches/piezoelectric composite
layers, the externally applied electric fields can adaptively induce additional forces and
moments which would act oppositely to those developed internally, thereby alleviating the
stress concentration in the joint edges and smartly improve the joint strength. In order to
verify the various smart adhesively bonded joint systems, theoretical modeling, numerical
analyses and relevant experiment studies are conducted. From both the detailed numerical and
experimental results, it is concluded that the developed smart adhesively bonded joint systems
can adaptively achieve a significant improvement in joint strength.
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Chapter 3
THERMOSETTING LAMINATES QUALITY: FROM

FIBER WAVINESS TO FEM CURE MODELING
Ch. Jochum1* and J. C. Grandidier2

1
Laboratoire de Mécanique des Structures Navales, Ensieta, 2 rue François Verny, F-
29806 Brest cedex 9, France
2
Laboratoire de Mécanique et de Physique des Matériaux, UMR CNRS 6617, Ensma, BP
40109, F-86961 Futuroscope Chasseneuil Cedex, France
Abstract
This paper focuses on the problem of material quality and internal stress encountered
during the curing of structural thermosetting laminates. The first part presents the relevant
problem of internal stresses generated by the curing for both thin and thick structural
thermosetting laminates. Needs for accurate description of laminates properties and internal
stress state presented at the end of the curing is a strategic problem for high performance
application. Despite of numerous studies performed for internal stress description and fiber
waviness measurement, the way of cure modeling appears inevitable for three dimensional
composites structures analysis. The foundations of a thermal, chemical and mechanical
coupling model are developed in the second part of the chapter, within a thermodynamically
and viscoelastic framework and takes into account any coupling, namely species diffusion.
Then, on the basis of parametric studies provided by the coupling model, a predictive internal
stress coupling model is presented in the third part of the chapter and is validated for three
dimensional internal temperature prediction, -hence, exothermic effects, and elastic internal
stress level during the hot stage of the curing. Accuracy of thermosetting matrix history
description provided by the model was then successfully tested in the last part of the chapter
for the fiber waviness phenomenon.
Keywords: FEM, epoxy curing, viscoelasticity, couplings, internal stress, fiber

microbuckling.
*
E-mail address: jch@ensieta.fr
150 Ch. Jochum and J. C. Grandidier
Introduction
It is well known today that the use of composites for structural applications has become
increasingly important. In particular, thermosetting laminates are more and more used for
transportation applications to improve payload and reduce energy costs. Their low densities in
association with their high strengthening are more and more attractive for the designers.
Moreover, these trends have recently emerged in naval and offshore construction since the
optimization of the structures became inevitable. Simultaneously to the economical interest of
this kind of high performance composites, numeric tools were developed for design
efficiency. Of course, low cost access to computational mechanics computers made it easier
for the designers, but at the same time several works were done by the scientific community
to improve composite material constitutive law description and modeling.
Consequently, several fields were explored. Starting several years ago from the
elastostatic behavior of a laminate, with a special mention for laminate compressive
strengthening, research focuses now on its dynamic and aging behavior. Indeed, continuous
improvement of fiber mechanical properties and strengthening opens more and more
structural applications. Hence, the question of the manufactured laminate’s quality is
becoming a new strategic question. In behalf of design improvement and costs optimization
for thermosetting laminates applications, a highly accurate knowledge of material properties
and of the internal state obtained at the end of the manufacturing process is required.
This topic started in the eighties with the residual stress problem. Many works were done,
demonstrating therefore the importance and the complexity of this question for thermosetting
composites designs.
Therefore this chapter draws the reader’s attention to the problem of material quality and
internal stress encountered during the curing of structural thermosetting laminates. Fiber
waviness observed at the end of the curing clearly demonstrates the existence of internal
stress mechanism that was simultaneously developed. However, reinforcement misalignment
knowledge (undulation, waviness) is one of the most important key points for failure criteria
modeling.
To face the question of laminate quality and residual stress determination, the strategy of
a three-dimensional finite element modeling (FEM) approach of the cure is presented by
taking into account the couplings between the chemistry, the thermal and the mechanics of
the thermosetting material during the curing.
More precisely, needs for such strategic information about laminate quality is detailed in
the first part of this chapter that presents the relevant problem of internal stresses generated
by the curing for structural thermosetting laminates. The internal stress problem already exists
in thin laminates and is illustrated by the question of compressive strength limitation that is
exposed in a comprehensively and detailed way with a state of the art survey. However, the
chemical shrinkage associated to the thermosetting reaction is able to destabilize the fiber
reinforcement alignment. The proof of internal stresses occurring during the curing is clearly
demonstrated by real time video records of fiber waviness mechanism. The case of thick
laminates is then also analyzed. Thick laminates are more and more developed, namely for
naval and offshore applications and are also subjected to internal stress development and fiber
waviness. Moreover, thermal gradients are generated because of the thermo activated and
exothermic behavior of thermosetting resins leading to several imperfections (bubbles, cracks
Thermosetting Laminates Quality: From Fiber Waviness to Fem Cure Modeling 151
etc, …) therefore decreasing the quality of the composite. The main factor is the thermal
history applied during the curing within the matter. As the thickness increases (more than 3-4
mm), the coupling effect between the thermo activated and exothermic behavior of
thermosetting systems cannot be neglected. The quality of the laminate obtained is therefore
quite different from the theoretical considerations that designers used to apply. This is
especially critical for thick laminates and must be taken into account for the design. Of course
even if post mortem tests can be done, they are usually expensive and time consuming. On the
other hand several models exist to take into account laminate quality by either fiber waviness
parameters and/or matrix heterogeneity description in order to improve as much as possible
structural design usually done by computational mechanics. But they all require input data of
the laminate assumed quality.
Simultaneously, several works exist in the literature about internal stress. Most of them
are focusing on thermal stresses generated by the cool down step (coefficient of thermal
expansion, warpage analysis,…), but more and more authors agree with the fact that internal
stresses are not only thermal stresses but also chemical shrinkage stresses. This point has to
be considered and its relevancy is detailed with the example of thick matrices. Strong thermal
gradients appear during the curing, inducing the degree of cure gradients. The matrix in
progress is more and more heterogeneous and gradients of mechanical properties are
generated. Gradients of matrix properties (degree of cure, cure shrinkage, viscoelasticity) are
clearly established for an epoxy matrix and their dependency to the cure is presented. The
trend of a coupling modeling approach between the chemistry, the thermal and the mechanic
appears. However, it seems that no work exists at the time about a complete coupling
modeling approach between the thermal, the chemistry and the mechanics applicable for the
curing of real three-dimensional (3D) structures. The understanding of matrix’s history can be
considered as a powerful and strategic way to face the question of internal stress
development, hence, fiber waviness, residual stress and gradients of properties.
A new challenging work thus appears: to be able to carry out material properties growth
and gradients during the process of cure for real 3D laminate structures.
To face this challenge, foundations of a thermal, chemical and mechanical coupling
model for cure simulation are presented by the authors in the second part of the chapter within
a thermodynamically framework, based on finite element simulation. The finite element
simulation was considered as a possible and helpful way to understand material quality
gradients and internal stress mechanism appearing during the curing. Results are compared
with experimental data and demonstrate the applicability of a finite element modeling
approach to provide local information during the curing.
Consequently, in the third part of the chapter, an extension towards a predictive internal
stress model is presented. Validation of internal stress and matrix quality estimation is
provided by fiber microbuckling simulation compared with experimental data of fiber
waviness and is exposed in the last part of the chapter.
The Internal Stress Problem

High performance applications and structures optimization are not only strongly dependent on
laminate accurate property description, but also on the existing internal stress state. This was
clearly observed for thin and thick laminates and is detailed hereafter.
The Case of Thin Laminates
Thin laminates are subjected to internal stresses in a significant way and to illustrate this
statement, the compressive strength limitation in fiber direction is a convincing example. A
weakness of laminates strengthening was observed in the early sixties for fiber direction
compressive load in comparison with tensile load. This limitation cannot be neglected since
compressive parts exists and must be verified for structural designs. Moreover, it was also
observed that fiber strengthening and properties improvement did not increase the
compressive behavior of the laminate in the same way as they did for tensile behavior.
Many studies about laminate compressive behavior were done, and were strongly
intensified from the eighties, since the first one developed by Rosen (1964, [1]). These works
have clearly established today that a buckle instability mechanism at fiber scale (fiber
microbuckling) is at the origin of the compressive failure. This instability triggers failure by
kinking band generation. Several authors, (Budiansky 1993 [2], Fleck 1995 [3]) have shown
that matrix non linearity on one hand and especially fibers misalignments (undulations,
waviness) on the other hand significantly decrease microbuckling critical load. Unfortunately,
it has been shown in practice that fiber undulation or waviness has a negative influence on the
stiffness and strength of fiber-reinforced composites [4-11]. Of course, compressive strength
is also influenced by the stacking sequence (Wisnom 1991, [12]; Drapier et al. 1997, [13]).
Several modeling approaches were used in order to determine this loss of strength.
Existing models only solve the macroscopic strengthening of a composite, either by means of
a parametric study of the description of fiber defects (Drapier et al. 2001, [14]), kink band
approaches (Fleck et al.1995, [3]), or the spectral density of waviness (Liu et al. 2004, [15]).
Figure 1. T300/914 ply failure strain dependency to wavelength defect and angular defect.
However, it appears that the compressive strength limitation of long fibers laminates is
mainly driven by their internal state, more precisely by the plastic behavior of the matrix and
especially by the reinforcement misalignment. In fact, fiber misalignment description that can
be given by corresponding wavelength and amplitude is strategic information for compressive
failure prediction as illustrated in Figure 1 by Drapier et al. (2001, [14]), one of the most
convenient and accurate prediction for failure strain. In this figure, failure strain can be three
times less in comparison with a defect free ply.
Anyway, quality of the predictions also depends on the initial value of the wavelength
and amplitude of the fiber, observed at the end of the cure process.
Figure 2. Three-dimensional view of T300 carbon fibers progress in an 914 epoxy matrix (Paluch [19]).
Some authors tried to measure fibers undulations. Yugartis (1987, [16]) observed the
fiber section shape after laminate transverse section cuts. Main axis of elliptic shapes of fibers
section cuts was used to estimate fibers undulation, assuming a perfect circular fiber section.
Frost (1992, [17]) proposed an estimation of fibers curvature by the comparison of
experimental failure tests with theoretical results. This interesting method depends on the
failure model employed. Other optical method were developed like the one of Clarke (1995,
[18]) using laser beams diffractions, but this requests good optical transparency of the
laminate and this is usually not the case for high performance systems like carbon epoxies.
The most realistic way for fiber undulation characterization is certainly the one developed by
Paluch (1994, [19]) which has rebuilt the three-dimensional progress of carbon fibers inside
of a ply using several fibers cross section cuttings and an appropriate statistical analysis of the
position of fibers section centers. Figure 2 shows the result obtained for T300 carbon fibers
inside of an epoxy 914 matrix.
For example carbon fiber wavelength was observed by Paluch inside of an epoxy matrix
to be around 1200 to 2400 microns with amplitude between 0.5 and 6 microns. Unfortunately,
these works are time consuming and expensive since they must be performed on the real
manufactured structure to be reliable in regard to cure conditions.
It is obvious to understand that fibers undulations are a visible manifestation of internal
stresses developed during the curing since they were initially straight. Some authors were
convinced that the main mechanism of fiber waviness and hence corresponding internal stress
development was generated by the cooling step of the curing. However, based on a simple
single fiber model, Drapier et al. (2000, [20]) demonstrate that the hypothesis of fiber
waviness induced during the cooling stage fails. A new approach was proposed by Jochum
and Grandidier (2004, [21]) for the question of fiber microbuckling mechanism. They
demonstrated that chemical shrinkage associated to the curing is the power unit for fiber
alignment destabilization. Fiber can be considered as a beam surrounded by a matrix acting as
a foundation that interacts. Polarised light pictures of microbuckling on single fiber
specimens clearly establish the existence of a matrix area affected by fiber undulation as
shown in Figure 3. Moreover, it was observed that the fiber instability phenomenon is
repetitious and that the waviness is periodic.
Figure 3. Carbon fiber microbuckling and description of the matrix area affected by the T300 carbon
fiber microbuckling within an LY556 epoxy matrix (Jochum and Grandidier 2004, [21]).
In an elastic framework, Jochum and Grandidier (2004, [21]) have shown that fiber
microbuckling instability mechanism can be described by following equation of balance:
d4v Gm d²v Em
Ef If dx4 + [ π (R²+r²) r (R-r) – N] dx² + 2π r R v = 0 (1)
R denotes the interacting matrix radius surrounding the fiber whose radius is noted r. Ef
denotes fiber longitudinal Young modulus and If quadratic moment of the fiber section. Gm
and Em are respectively the shear modulus and Young modulus of the matrix and N is the
normal force applied to fiber section. The transverse displacement field solution of equation
(1) is searched under a classical sinusoidal form like : v(x)=A sin(αx) where α denotes the
wave number and A the amplitude. The authors showed that this lead to the critical buckle
instability load P(α) as a function of wave number as follows:
Gm 2 π r Em
P(α) = -π (R²+r²) r (R-r) + Ef If α2 + (2)
α2 R
FEM computation of elastic applied load, consequently to chemical shrinkage during the
curing on a T300 carbon fiber in an LY556 epoxy resin and by taking into account matrix’s
Young modulus evolutions during cure, have demonstrated that fiber instability is detected as
being possible during all the thermosetting stage of the resin. Indeed, the applied load by
chemical shrinkage is quite 30 to 100 times higher than the loading necessary to trigger the
instability. This gap is very important, but the elastic calculation of the compressive loading
certainly overestimates the real load that is probably subjected to relaxation as the matrix is
forming because of the viscoelasticity of the material.
Nevertheless in 2007, Jochum et al. (2007, [22]) published a detailed real time video
record of fiber microbuckling instability that was clearly observed during the chemical
reaction stage of the curing. The instability happens quickly in around 10 seconds, is a
reproducible and systematic phenomenon and was observed in an epoxy and in a polyester
matrix with the same T300 carbon fiber. Representative video frames are presented in Figure
4 for fiber waviness development.
This experimental observation confirms that fiber waviness is an excellent internal stress
indicator and the video confirms that internal stresses are generated during the hot stage of the
curing.
From a modeling point of view, the case of a fiber surrounded by an infinite matrix
medium was also studied by Jochum and Grandidier (2000, [23]) based on stability equations
developed by Minahen and Knauss (1989, [24]). Jochum and Grandidier demonstrate that the
elastic approach for a single fiber stability shows real microbuckling possibilities and they
proposed an extend for the case long fiber laminates. Fiber critical wavelength was found to
be between 1000 and 3000 microns depending on matrix chemical shrinkage. These values fit
well with data provided by Paluch (1994, [19]). Moreover, the taken into account of the
viscoelasticity of the matrix in formation was studied (Jochum 1999, [25], Drapier et al. 2000,
[20]), on the single fiber model surrounded by an infinite matrix. Matrix viscoelasticity
evolution during the curing was described by a Zener model based on DMA-TMA
(Dynamical Mechanical Analysis-Thermal Mechanical Analysis) Cole-Cole plots.
Viscoelastic critical wavelength approach for the T300 carbon fiber microbuckling was found
to tend to 170 microns before cooling for the LY556 epoxy system. This result correlates well
with the wavelength observed experimentally by video records on single fiber specimen that
stays around 150 to 210 microns, depending on curing conditions.
Fiber still straight
Figure 4. Continued on next page.

First undulations
Undulations growth
Fiber undulations stabilized
Figure 4. Video sequences of the appearance of T300 fibre undulations in an LY556 epoxy matrix with
a fibre diameter of 7 microns (Jochum et al. 2007, [22]).
Of course, thermal stress developed by the cooling will increase the compressive load
applied on the fibers due to the well known thermal mismatch of the fiber and matrix system.
Definitely, thermal coefficient of expansion of a carbon fiber is 200 times smaller than for an
epoxy matrix and owns an opposite sign (-0.74 E-6 °C-1 for carbon fiber in axial direction, 150
E-6 °C-1 for epoxy matrix). Hence, thermal stress produced by the cooling generates a
compressive stress state in the fiber, since the matrix shrinks during cooldown. Anyway, the
fiber was previously pre-stressed by the chemical shrinkage of the resin. Thus, during the
cooling down, the compressive stress state of the fiber is enhanced by matrix thermal
shrinkage. Moreover at the same time, the fiber tries to dilate thermally, thus increasing its
compressive stress level developed by the matrix interaction. The equilibrium of the fiber
matrix system leads to a tensile stress state in the matrix that embeds the fiber that tries to
dilate.
However, fiber undulation wavelengths observed by video records have indicated a slight
wavelength increase of around 10% during the cooling for return at room temperature. This is
explained by the viscoelastic behavior of the matrix during the cooling (especially during the
glass transition (Tg) crossing) that enables matrix tensile stress relaxation, leading therefore
to a decrease of fiber compressive stress and as a consequence an increase of its undulation
wavelength. On the basis of these experimental facts on one hand and on the other hand on
corresponding matrix state during the curing, a proposal for a long-fiber microbuckling
scenario during the cure of a thermosetting matrix was proposed by Jochum et al. (2007,
[26]). The main information is that fiber instability appears during the rubbery stage of the
curing, and relaxes slightly after the return at room temperature. It appears that fiber
wavelength recording provides useful information on internal stress development during the
complete process of curing. Furthermore, the single fiber specimen can be considered as a
technological specimen to qualify and validate any further model of internal stress
development.
Thermal stress is definitely not the only one mechanism of internal stress. Internal stress
appears during the chemical reaction of the thermosetting reaction, during the hot stage of the
process as demonstrated by fiber microbuckling development.
Consequently, process improvement cannot only focus on the cooling stage since internal
stresses are not only thermal stresses. This fact was also stated by L.G. Zhao et al. (2006,
[27]) who conclude that the determination of residual stress in polymer–matrix composites
should include contributions from both the chemical shrinkage of the resin and the thermal
cooling contraction of the fiber and the resin. Analyses considering the thermal cooling stress
only may underestimate the overall residual stress during cure.
The case of Thick Laminates
The internal stress problem presented for the case of thin laminates cannot be avoided for
thick laminates because same mechanisms still exist. Moreover, an additional difficulty
appears as the thickness increases, in regard to matrix quality.
Quality Defects
The thermal and chemical coupling during the curing is more and more important as the
thickness increases and quality defects appear. The formation of internal stress can be high
enough to initiate material damage before loading such as interface debonding and matrix
microcracking as shown in Figure 5. This observation is especially critical for thick

laminates; usually more than 5 mm. Figure 5 illustrates an example of defects observed inside
of a carbon epoxy raiser for deep water petrol extraction.
Figure 5. Defects across thickness in an 80 mm thick carbon epoxy raiser tube (by courtesy of Ifremer:
French Research Institute for Sea Exploitation).
Matrix cracking and delamination are observed during the processing of thick carbon
epoxy tubes. As also mentioned by Ruiz and Trochu (2005, [28]), this kind of defects
commonly appear in thick thermosetting composites processed at high mold temperature.
Consequently, bubbles, cracks and porosity are clearly observed decreasing therefore the
mechanical performance of the composite. In addition to the fiber waviness problem
encountered for thin laminates, these defects demonstrate clearly the existence of internal
stresses effects. They are resulting from the complex process of curing that mixes thermal,
chemical and mechanical phenomenon. Indeed, as the thickness increases, the coupling
between the thermal and the chemistry is enhanced because of the thermo activated and
exothermic behavior of the thermosetting reaction. This aspect is detailed in next section
which presents exothermal facts observed.
Exothermic Facts
An easy illustration of exothermic level of the thermosetting reaction was obtained by the
curing of a 30 mm thick cylindrical sample of epoxy matrix as presented in Figure 6. In this
figure a strong matrix color change was observed in the center of the sample as the duration
of the curing increases. In comparison with the 120°C isothermal oven temperature setting as
displayed in Figure 7, the internal temperature measured in the center of the matrix raises
more than two times the scheduled process temperature.
20 min at 120°C
Thermocouple
Figure 6. Exothermic effect by matrix color change.
300 Heart temperature

250
Temperature (°C)
200
150
100
Oven temperature
50
0
0 500 1000 1500 2000
time (s)
Figure 7. Exothermic effect by local temperature rise.
The thermosetting reaction is therefore affected by the cure cycle and the mass effect.
The heterogeneity of the temperature field generates degree of cure gradients and therefore
gradients of chemical shrinkage. This is important information that must be taken into
account to understand the development of internal stress within the matrix.
Discussion
The internal stress problem appears to be a delicate and complicated one. As exposed in this
section visible signs of internal stress are observed for both thin and thick laminates. Fiber
undulation is the first proof of internal stress for thin laminates. Its effect on compressive
strength was demonstrated and modeled. Fiber waviness mechanism was analyzed and
quantitative data about waviness exist. Internal stresses are developed during the curing and
are increased during the cooling due to the thermal mismatch of the fiber and matrix system.
Thus, complementary to the fiber waviness question, several works were done to quantify
internal stress level present at the end of cure.
These works are mainly experimental or semi-experimental approaches, based for
example on warp analysis or slitting techniques for cylinder thin tubes (Seif et al., 2007 [29])
or thick walled composites cylinder (Casari et al., 2006 [30]; J.W. Kim et al., 2006 [31]).
Recently, more and more optical fiber Bragg grating (FBG) sensors are used as tools for non
destructive internal strain measurements in composite materials. However these techniques
provide local information since they either depend on the slitting area or on the FBG sensors
position. Moreover, for FBG techniques, M. Mulle et al. (2007, [32]) observed that the
information delivered by FBGs, in terms of longitudinal residual strains measurement, is
highly dependent of the transverse effects that should imperatively be taken into account
when using FBGs to achieve thermal and process-induced strains evaluations.
Nevertheless, Colpo et al. (2007, [33]) develop an interesting FEM coupling method to
obtain the radial dependence of the residual strains in the matrix, but it works only for a single
fiber composite. On the other hand, the classical hole drilling technique for residual stress
measurement seems now to be completely studied and well analyzed, even for thick walled
composites (M.G. Bateman, 2005 [34] and for orthotropic materials (Baldi, 2007 [35]), but it
provides only local information and is destructive. Of course strain gage techniques are still
existing, and they can ideally be improved by being combined with optical technique via
Moiré Interferometry developed by W.A. Schulz et al. (2005, [36]). Thus, numerous methods
exist to determine residual stresses in polymer-matrix composites but they are often expensive
and time consuming. Experimental methods, either destructive or not can only provide local
information and are inappropriate for a complete composite structure inspection. Concerning
analytical methods, residual stresses in composites were generally studied on the macro and
meso-micro levels. On the macro level, Classical Lamination Theory (CLT) is generally used
and gives predictions at the ply level (Olivier and Cottu 1998, [37]; Gopal et al. 2000, [38]),
but it did neither account for properties gradients, nor chemical shrinkage. Nevertheless,
W.A. Schulz (2005, [36]) proposed a modified CLT taking into account chemical shrinkage
of a material system and its expansion properties as a function of temperature. On the meso-
micro level, the representative volume element (RVE) approach based on the periodic
structure of the laminate is usually adopted. The analysis is often performed using a
numerical procedure such as the finite element method (Sweeting and Thomson, 2004 [39];
Zhang et al., 2004 [40]) and leads to residual stress and strain fields prediction at the fiber
matrix level. Unfortunately, these approaches did not account for mass effects and thermal
and chemical coupling.
Although analyses of residual stress have been extensively studied in polymer-matrix
composites, a generalization of these experimental techniques for a continuous internal stress
description seems difficult and expensive, namely for 3D structures. Though they provide a
wide range of data, an improvement of internal stress measurement requires inevitably the
taken into account and the understanding of chemical, thermal and mechanical phenomena
involved during the curing of the thermosetting matrix. The coupling of these phenomena
must be considered, even for thin laminates. This statement is confirmed by P.A. Olivier
(2006, [41]) who studied in a detailed way the development of process-induced stresses
during the curing of thin carbon epoxy laminates, by thermomechanical analysis. It was
observed that even for thin laminates (4 plies) chemical shrinkage quite accounts for 8% of
the final deformation. Thick laminates are moreover subjected to quality defects induced by
the coupling between the thermal and the chemistry and an heterogeneous, stressed laminate
is obtained.
An illustration of coupling effects on matrix heterogeneity was presented by Jochum and
Grandidier (2007, [42]) for gradients of curing, of chemical shrinkage and of mechanical
properties. The use of cure kinetics simulation was applied for heart and edge temperature
profiles corresponding to the resin curing presented in Figures 7. For epoxies, the most
accurate and widely used autocatalytic model developed by Kamal and Sourour [43] was
taken for degree of cure simulation and results are displayed in Figure 8.
1
0.9
Heart
0.8 degree of
Degree of cure 0.7 cure
Edge degree
0.6 of cure
0.5
0.4
0.3
0.2
0.1
0
0 500 1000 1500 2000 2500
time (s)
Figure 8. Degree of cure gradient observed in a 30 mm thick epoxy sample.
time (s)
0%
0 500 1000 1500 2000 2500
-1%
Heart shrinkage
-2%
Cure shrinkage
-3%
-4%
-5%
-6% Edge shrinkage
-7%
Figure 9. Cure shrinkage evolutions at heart and edge positions during the curing (LY556 epoxy resin).
Figure 8 clearly demonstrates that temperature gradients, induced by mass effect as

shown in Figure 6, strongly influence the history of the cure. Even if the remaining difference
in degree of cure levels observed at the end of cure between heart and edge positions is
around 5%, the cure profile obtained at heart position corresponds to a fast curing whereas the
profile obtained at edge position denotes a significant slower curing. Degree of cure profile
obtained within the matrix sample is completely different between the heart and the edge
areas of the matrix. The curing is heterogeneous throughout the matrix and consequently
gradients of volume variation will appear since the curing of a resin corresponds to a phase
change from a liquid state to a solid state. This phase change owns like most of phase changes
a volume variation and, in the case of resins, the associated volume variation corresponds to
shrinkage. Li et al. (2004, [44]) established a bilinear relationship for cure shrinkage as a
function of degree of cure, with a break point at gelation. They observed that neither the
degree of conversion rate nor the isothermal level of the curing did affect the bilinear
evolution of chemical shrinkage. Thus, it is assumed that this can be relevant to non
isothermal curing. Consequently, local degree of cure history observed for the resin curing
presented in Figure 7 leads to the corresponding local chemical shrinkage history as presented
in Figure 9.
Shrinkage gradients are observed during the curing throughout the thickness. However,
even if at the end of the cure the total shrinkage tends to be the same, the history of its
evolution is significantly different within the matrix sample. This difference in cure shrinkage
evolution is one of the basic mechanisms that must be taken into account for internal stress
development and especially for thick matrices.
Moreover, the existence of gradients of curing throughout the thickness means that the
associated crosslinking reaction is not done in an homogeneous way and consequently the
molecular branching will differ throughout the thickness. Thus, even if the final degree of
cure is the same, the corresponding mechanical property will differ because of differences in
the thermal history of the curing. This was clearly observed by DMA-TMA analysis of the
curing as shown in Figure 10. In this figure, the elastic shear modulus evolution versus time
differs significantly between two matrices cured with a continuous 1°C/min oven heating and
a 120°C isothermal oven heating. DMA-TMA tests were performed on thin samples of resin
poured into shear plates in order to control as best as possible the local temperature applied on
the blend for the curing. The matrix is cured inside of the DMA oven before the start of the
cooling analysis. The continuous 1°C/min ramp was performed up to 180°C whereas the
120°C isothermal cure never exceeds 140°C for the matrix temperature.
1200
Elastic shear modulus G'(MPa.)
1000
1°C/min ramp
800
cured matrix
600
120°C isothermal
400 cured matrix
200
0
220 180 140 100 60 20
Temperature (°C)
Figure 10. Cure conditions effect on matrix elastic shear modulus growth during the final cooling down
to room temperature for an LY556 epoxy resin, 1Hz. DMA analysis.
Elastic modulus differences observed are around 8% at the end of the final cooling step
and return to room temperature. The importance of the thermal history of the curing is
highlighted. Thus, this does not lead to the same material at the end of cure since the elastic
modulus growth during the cooling and the final value reached are not equal. This result is to
be related to thick matrix cure where strong thermal gradients exist and demonstrates the
heterogeneous aspect of matrix mechanical properties throughout its thickness.
A challenging work appears thus naturally: the taken into account of the couplings
between the thermal, the chemistry and the mechanics, devoted to real composite structures.
This approach enables prediction of matrix properties growth during the curing and hence
accounts for internal and residual stress prediction.
This trend appears recently. Ruiz and Trochu (2005, [28]) proposed a numerical analysis
of cure temperature and internal stresses in thin and thick RTM parts taking into account the
couplings between the thermal and the chemistry for glass polyester composites. Mechanical
properties were described as a function of degree of cure and glass transition. Internal stresses
were calculated in an elastic framework with thermal and chemical strains. It is an interesting
contribution for implementation in fast looping for curing optimization as further exposed by
Ruiz and Trochu (2006, [45]). However, the model proposed by Ruiz and Trochu is a one-
dimensional through thickness curing model and the assumption was made that in-plane heat
flows are much smaller than through-thickness flows and can be neglected. As pointed out by
the authors, this may not be the case for ribbed thick parts and an extension of this model for
three-dimensional parts by selecting test points requires the determination of the
corresponding appropriate thermal boundary conditions. This point is delicate since it cannot
be computed by the one-dimensional approach.
On the other hand, a three-dimensional anisotropic thermo-viscoelastic formulation based
on finite element model was proposed by Clifford et al. (2006, [46]) to predict the residual
stress state and dimensional stability of large complex shaped composite parts. However, the
authors assumed that the part was stress-free at the start of cool-down, from 160°C and thus
only studied the cool down stage. This point is critical since Olivier (2006, [41]) and W.A.
Schulz (2005, [36]) observed that chemical strain accounts for 8 to 15% of the thermal
stresses. Moreover, the study only concerns thin parts without chemical, thermal or
mechanical gradients. Nevertheless it is interesting to note that Clifford et al. used the ‘user
material’ (UMAT) facility of a commercial finite element package, e.g. Abaqus® TM to
describe the material model in Fortran 90. With this facility, the Abaqus® program sends
time, temperature and strain data to the UMAT subroutine for every integration point and the
UMAT subroutine returns the updated values for the stresses and material stiffness, in the
local element coordinate system. This technique enables three-dimensional user material
behavior description and is certainly very promising.
Finally, one of the most advanced study for a thermal, chemical and mechanical, three-
dimensional, coupling model seems to have been developed by Zhao et al. (2007, [47]) who
analyzed the process-induced residual stress in fiber epoxy unidirectional laminate by using a
thermo-viscoelastic micromechanical model and the finite element method. The technique of
a three-dimensional unit cell representing the periodic microstructure was considered. Cure
residual stress of fiber composites induced by chemical shrinkage of the epoxy resin and
thermal cooling contraction of the whole fiber and resin system was computed. However, due
to the RVE approach, heat of the thermosetting reaction was not taken into account, hence no
thermal and chemical coupling was considered. Anyway, the approach is interesting since the
viscoelasticity of the matrix during the curing was taken into account as a function of the
temperature and the degree of cure and it confirms that stress relaxation effect must be
considered since it leads to a reduction in residual stress in comparison with the elastic
solution. Unfortunately, the viscoelasticity of the matrix during the curing was described by a
linear function of the degree of cure. This modeling fails for the non linear evolution of the
mechanical behavior especially at gelation and on the other hand, material properties changes
at Tg crossing were not considered.
Thus, as a conclusion of the internal stress problem, the most promising way seems to be
the way of a coupling model for the curing. The modeling approach must be representative of
a complete thermal, chemical and mechanical, three-dimensional, coupling model taking into
account the heat produced by the reaction for the thermal balance. It appears to be the best
strategy for thermosetting laminates quality description since it accounts for material history
description. The question of fiber waviness development related to internal stress
development, on one hand and, on the other hand, the question of gradients and residual stress
state should therefore be faced thanks to the history of the matrix during the curing. Hence, a
complete coupling strategy for the curing is presented in this chapter. First of all, in order to
stay coherent with the physics, the problem of cure modeling is presented in a
thermodynamically framework to provide the foundations of a thermal, chemical and
mechanical coupling model. A parametric study is performed to evaluate results sensitivity
and limitation of the model. Thus, an extension towards a predictive internal stress model is
presented in the third part of this chapter and its validity is compared with experimental
results.
Foundations of a Thermal, Chemical and Mechanical Coupling

Model
Internal stresses and quality defects (cracks, bubbles, fiber waviness…) developed during the
cure of a composite matrix result from a complex process mixing thermal, physicochemical,
viscosity and mechanical phenomena. This complexity is increased by the thermo activated
and exothermic behaviors of the thermosetting chemical reaction of the resin and during the
cure, mechanical characteristics are evolving with temperature and degree of conversion of
the chemical reaction. Therefore construction of simulation tools for curing modeling requires
the development of coupling models between the mechanics, the thermal, the diffusion and
the chemistry. From a theoretical point of view, these four aspects of the problem were
generally approached separately. Models of coupling between the thermal and the chemical
kinetics exist (Chachad 1996, [48]; Roux et al. 1998, [49]; Ruiz and Trochu 2005, [28]).
Tools using advanced finite elements made their appearance (Sunil et al. 2001, [50]) and
tends to be generalized as seen before, but all the couplings are not completely taken into
account. Moreover the chemical reaction is generally approached as a scalar relation covering
the degree of conversion only. But works on chemical reactions showed that due to the initial
heterogeneities of the fractions of the components (non stoichiometric fractions) the chemical
reaction kinetics vary and diffusion of the different elements is developed. These phenomena
strongly influence the characteristics of the matter during the cure, as well as at the end of it.
The modeling of these phenomena coupled with the temperature and with the mechanics
seems to have never been approached before.
The general aim of this section is therefore to give a formulation as simple as possible of
some fundamental couplings for the curing of a thermosetting matrix. It will lead to discuss
the possibility of linking thermal, diffusion and mechanical phenomena together and to
evaluate rapidly the effects of such couplings. The set of local balance equations and resulting
constitutive laws in a viscoelastic framework is detailed hereafter. The framework of
generalized standard mediums was chosen in order to simplify future numerical developments
devoted to industrial software. Material parameters were first considered as being constants in
order to simplify the equations for first ideas about the heaviness of the coupling model.
Modeling Approach
Description of the System
The system to cure is supposed to be a traditional continuous medium, made up with a blend
of resin, hardener and accelerator (Bowen 1976, [51]). The macroscopic representative
volume element is considered homogeneous, open and characterized by averaged physical
units defining the blend. Thus, only the averaged behavior of the RVE is involved here. It is
an acceptable assumption, since experiments of mechanical characterization exhibit only the
macroscopic behavior. The diffusion of each “species” is assumed to be described by a
molecular diffusion phenomenon following a Fick law. It is controlled by the gradients of
concentration or mass ratio of the various species. In this RVE the various species react
amongst themselves in order to create the matrix. This evolution of the blend, governed by
the equations of the diffusion and the equations of the chemistry, is taken into account in the
equations of the thermal and of the mechanics.
Mass Balance
By noting ρ the density of the blend, Yi the mass fraction of each species (where the subscript
i = p denotes the resin; i = a denotes the accelerator, i = d denotes the hardener and i = m
m
denotes the obtained matrix), Mi the current molar mass of species i and J i the associated
relative mass flow, υir the stoichiometric coefficient of the component part i for the reaction r,
wr the reaction rate for the reaction r, the mass balance of the component part i which leads to
the equation of distribution of the corresponding species can then be written as follows
(Bowen 1976, [51]):
ρẎi = ∑ υir Mi wr - div (J i )

m
(3)
r
where ‘˙’ denotes the time derivative function and div the divergence operator. In order to
simplify the modeling approach, an unique reaction is only taken into consideration (r = 1),
despite of the fact that many reactions are evolving during the thermosetting reaction of an
epoxy resin. Moreover the accelerator mass ratio, which is very low in comparison with other
current species, can be neglected for equation (3). On the other hand, its effect is reintroduced
through the kinetics law of the chemical reaction rate. These assumptions did not reduce the
generality of model.
The total mass conservation in the RVE leads to a relation between the mass ratio of the
resin, of the hardener and of the obtained matrix such as Ym + Yp + Yd = 1. Hence, variation
of matrix mass fraction can be expressed as a function of hardener and resin under following
form:
o o o o o
Ym -Ym = (1 –Yd –Yp) - (1 -Yd -Yp ) = - [(Yd –Yd ) + (Yp -Yp )]. (4)
This relation was used in the formalism to simplify the expressions.
Mechanical Balance
In regular points of the non-polar body, the mechanical balance leads to the classical equation
of motion (5) where σ denotes the Cauchy stress tensor applied to the blend and f denotes the
mass density of forces applied to the RVE. Accelerations have been neglected because the
cure is supposed to be quite a slow process.
div σ + ρf = 0 (5)
Thermodynamic Balance, State Laws
The total energy conservation of the system, as described by the first principle of
thermodynamics, is expressed locally in the following traditional form:
ρ u̇ = σ : ε̇ - div Jq + r (6)
where ‘u’ is the specific internal energy of the blend, ε the infinitesimal strain tensor
associated with the blend, Jq the heat flux and r the external heat supply per unit volume. Note
that ‘:’ denotes the dyadic product.
The thermodynamic system is supposed to be close to its equilibrium. The classical
assumption of a local accompanying state allows us to describe at any time the state of a
given material (defined by the RVE) by a set of state variables. One admits first the existence
of one homogeneous absolute temperature T valid for the blend and for all its constituents.
As polymers exhibit a viscous behaviour for small loadings and deformations,
viscoelasticity must be taken into account. It is based on a simple representation, namely
Kelvin–Voigt’s model defined by the arrangement of springs with a dashpot (Figure 11).
In the classical framework of linear viscoelasticity, total strain is usually separated into
e an
elastic and anelastic (non reversible) components, denoted ‗ ε and ‗ ε respectively, and is
ε =‗
e an
written as ‗ ε +‗ε .
The partition of strain suggested here consists in introducing an elastic (or instantaneous)
e an in
ε and an anelastic (or delayed) one. The latter is here denoted ‗
strain ‗ ε (instead of ‗ ε ) and
is regarded as an internal variable. This mechanical model assumes also a partition of the
an vr an
σ into an anelastic part ‗
stress tensor ‗ σ and a viscous reversible part σ ‗ , such as σ ‗=σ ‗ +
vr an an
σ , so that the thermodynamic affinity associated with ‗
‗ ε is expressed in terms of σ
‗ . Note
that second order tensor notation (‗) will be suppressed in next equations to lighten the
reading.
σ σ
vr
‗ ‗
∞ ∞
λ ,μ
λ ,μ
o o
λ ,μ
v v
σ
an
‗
ε ε
e an
‗ ‗
ε
‗
Figure 11. Kelvin - Voigt rheological model.
Of course, it is a first level model to represent a viscoelastic behavior for a polymer and it
is certainly poor to predict exactly the complete evolution of the mechanical behavior of the
blend during the curing. However the aim of this work is to present a modeling approach, and
the Kelvin-Voigt model could be effective by taking into account the effect of temperature
and degree of cure on mechanical characteristics. On the other hand its implementation work
in FEM software is simple.
Thus, assumptions presented before allow the material state to be defined by following
variables: temperature T, elastic and viscous strains, εe, εv, resin and hardener mass ratios Yp
and Yd. The specific free energy potential ψ is a function of all these variables like ψ = ψ (T,
εe, εv, Yp , Yd). Laws can then be established under the assumption of a normal parameter
setting (Germain 1983, [52]). By considering the framework of small perturbations, i.e.
infinitesimal strains and few thermal and mass variations, the second order development of
the potential ψ allows the construction of coupling linear behavior laws as follows:
o o o
σ = σo + λ ( tr εe) I + 2μ εe - 3K [α t ΔT - αdm ΔYd - αpm ΔYp] I
o o o
o o ∞ ∞
s = so + C ΔT + 3K α t ( tr εe ) + 3K α t ( tr εv ) + Dt m ΔYd + Dt p ΔYp
To ρ ρ
o o ∞ ∞
μm = μm – Dmd ΔYd – Dmp ΔYp - 3K αm trεe - 3K αm trεv - Dm t ΔT
o
ρ ρ ρ
o o ∞ ∞ (7)
+ Ddm ΔYd + (Ddm - Ddp) ΔYp - 3K αd trεe - 3K α d trεv - Dd t ΔT
o
μd = μd
ρ ρ ρ
o o ∞ ∞
μp = μp + (Dpm- Dpd) ΔYd + Dpm ΔYp - 3K αp trεe - 3K α p trεv - Dp t ΔT
o
ρ ρ ρ
∞ ∞ ∞
σvr = σ o + λ∞( tr εv ) I + 2μ∞εv - 3K∞ [α t ΔT - αdm ΔYd - αpm ΔYp] I
vr
o
3K = 3λ + 2μ ; 3K∞ = 3λ∞ + 2μ∞ ; ΔT = T-To ; ΔYd = Yd-Yd ;
o o o
o ∞ ∞ ∞ o o o
ΔYp = Yp-Yp ; α ij = α i -α j ; αij = α i -α j
o
s and μi denote respectively specific entropy and chemical potential of species i. To, Y i , σo, so
o
and μ i correspond respectively to initial values for temperature, mass ratio of species i, stress
tensor, specific entropy and chemical potential of each species. The parameters λ , μ , λ∞ ,
o o
∞
μ denotes respectively instantaneous and long term Lame’s coefficients. The scalar C is the
o ∞
specific heat at constant strain and mass ratios, Dij, Di T, α i , α i are coefficients denoting
coupling effects between thermodynamical forces and state variables associated with different
phenomena (diffusion between species, thermal diffusion of species, mechanic). The trace
operator of a tensor is noted ‘tr’.
In these linear laws, the chemical potentials depend on the hydrostatic pressure (products
of bulk modulus with volume strain), which is the consequence of the mechanical loading
combined with the boundary conditions applied to the structure. Moreover the Kelvin-Voigt
model allows us to consider instantaneous and long time coupling effects. Although the
framework is linear, the possibilities of the models are interesting. In a more traditional way,
the stress tensors are directly influenced by the change of density, which depend on diffusion
and degree of cure. Consequently this coupling interacts directly in the equations of diffusion
as detailed in next paragraph.
In order to improve the model, intrinsic dependences must be integrated into the different
characteristic parameters. However the protocol of parameter identification of the matrix
thermo-mechanical behavior during its formation should take into account these various
couplings.
Entropy Description – Second Principle
Evolution of open systems is considered. The mass entropy s, associated to any representative
element of mass of the blend, is defined as an homogeneous first degree function of the
extensive parameters which are the internal specific energy u of the blend, the elastic strain
tensor εe, the mass ratio of the Yi components. Within the general framework of open
systems, the total differential of the mass entropy checks the fundamental Gibbs generalized
equation, where local variation of entropy is expressed as follows:
T ṡ = u̇ - 1 σ : ε̇ e - μm Y
˙ - μ Y
m
˙ ˙
p p - μd Yd (8)
ρ
According to the first principle of the thermodynamics, the fundamental relation of Gibbs
and equations of diffusion, the local variation of entropy (s˙e ) due to the external exchanges
and entropy variation related to internal evolutions (˙si ) are formulated as follows:
se = - div Js + r ;
ρ˙
T
μ (9)
ρ ˙si = 1 σ : ε̇ v + Jq .∇( 1 ) - ∑ J i . ∇( i ) + 1 ∑ [ ∑ μi υir M i wr]
m
T T i=m,d,p T T r i=m,d,p
Volume dissipation ϕ established from the internal entropy production can be split up into
four contributions and must check therefore the fundamental inequality of the second
principle as expressed by equation (10):
Js =
1 q
J - ∑ μi ;
T T
i=m,d,p
(10)
ϕ = ρ T ˙si = σ : ε̇ v - Js . ∇T - ∑ Jmi ∇μi + ∑ [ ∑ μi υir Mi wr] ≥ 0
i=m,d,p r i=m,d,p
The first part of ϕ corresponds to the dissipation generated by the viscous phenomena of
the blend, and the two following parts are the quantities respectively associated to the
gradient of temperature (heat transfer) and to the gradient of chemical potential (mass
transport). The last part corresponds to the chemical reaction.
Potential of Dissipation - Complementary Constitutive Equations
A second potential is introduced in order to define the evolution laws, namely the pseudo-
potential of dissipation, more exactly its dual form d* that can be written as a function of (σan,
- ∇T , - ∇μi , αr) obtained by a Legendre-Fenchel transformation. If dissipation phenomena
are supposed being governed by linear laws (small perturbations close to the thermodynamic
balance) and by the assumption of the validity of the Curie principle, the dual potential d* can
be expressed under a quadratic form and hence evolution laws are:
v v
ε̇ v = 1 +vν σ an - ν v tr (σan ) I + crs αr I ;
E E
m µ µµ µt
J d = - kd ∇(μd-μm) - cpm . ∇( μp-μm ) - c d ∇T ; (11)
m µ µµ µt
Jp =- kp ∇(μp-μm ) - cdm . ∇( μd-μm ) - cp ∇T ;
tµ tµ
J = - kT ∇T -
s
cdm ∇(μd-μm) - cpm ∇(μp-μm) wr = kr αr + crs tr σ an
µ µ ij
Tensors kT, kd and kp denote the ‘Fourier’ and ‘Fick’ tensors repectively. Tensors cuv and
coupling scalar crs, are not classical. crs stands for inelastic hydrostatic pressure effect
coefficient on cure kinetics. What can especially be pointed out is the effect of anelastic
hydrostatic pressure stress (subscript s) on resin (subscript r) thermosetting reaction in the
cure kinetics equation and in the viscoplastic strain evolution. However, Rambert et al., 2005
[53] have showed that the effect of a coupling between the thermal and the diffusion on the
response of a polymer structure can be neglected. The innovation here comes from the taking
into account of the direct couplings, which are interacting on the rate of degree of conversion
of the reaction since it is influenced by the inelastic hydrostatic pressure (crs tr σ an). The
thermosetting reaction depends on the chemical potentials of the various species, which are
connected by the state laws to the mass fraction of the species, the temperature and the state
of the volume strain within the matter. These couplings induce non-traditional effects of
acceleration or deceleration of the chemical reaction. The viscous flow is also modulated by
the reaction and this induces an indirect effect on the material behavior. These effects are
perhaps second order effects, but they have to be considered in order to identify the viscous
behavior throughout the curing.
Extension to non Linear Chemistry
Complementary constitutive equations (11) have lead to a linear law for the expression of the
rate of degree of conversion (or degree of cure) wr of the reaction as a function of the degree
of conversion (coefficient kr). This is not correct since, for the case of epoxies, many works
established a non linear expression governing the rate of degree of conversion. It is usually a
power law whose coefficients are modulated by the temperature and for epoxies the Kamal
and Souror model [43] is widely used as follows:
dα/dt = (K1 + K2 αm)(1-α)n (12)
with K1=a1exp (-e1/T) and K2=a2exp (-e2/T).

Nevertheless, by choosing another potential of dissipation and another expression of the
free energy, coherent with the non linear dependency to the mass ratio of the chemical
potential instead of linear function as obtained in equation (7), the non linearity of the
chemistry can be obtained. Indeed the chemical potential is well known as being under
following expression (Prigogine and Kondepui 1999, [54]):
µi (p, T, xi) = µ i (p, T) +RT log(γiYi)Γi

o
(13)
where γi denotes the coefficient of activity for species i and Γi a coefficient for cure kinetics
velocity modulation. Correct chemical potential expression for species m,d and p of the epoxy
blend is then given by equations (8):
o o o
o o (3λ + 2μ ) αp
•μm = μm - 1Dmd (Yd -Yd ) - 1Dmp(Yp -Yp ) - -
o
tr ‗εe -
ρ ρ ρ
∞ ∞ ∞
(3λ + 2μ ) α p v
tr ‗ε
ρ (14)
- Dm t (T-T0) + RT log (γm (1-Yd-Yp)) Γm ,
ρ
o
•μd = μd + 1D dm (Yd -Yd) + 1(Ddm - Ddp)(Yp -Yp ) -
o o
ρ ρ
o o o ∞ ∞ ∞
(3λ + 2μ ) αp (3λ + 2μ ) α p v
- tr ‗εe - tr ‗ε
ρ ρ
- Dd t (T-T0) + RT log (γdYd) Γd ,

ρ
o o
•μp = μp + 1 (Dpm- Dpd) (Yd -Yd ) +1D pm (Yp -Yp ) -
o
ρ ρ
o o o ∞ ∞ ∞
(3λ + 2μ ) αp (3λ + 2μ ) α p v
- tr ‗εe - tr ‗ε
ρ ρ
- Dp t (T-T0) + RT log (γpYp) Γp ,

ρ
Discussion about the Couplings in the Equation of Heat and the Equation of
Diffusion
By denoting Jq the heat flow and r the external sources of heat (radiation), equations of heat
and of diffusion containing all the couplings in the framework of linear viscoelasticity can
then be written under following expression:
Equation of heat transfer:
ρCT˙ = - div Jq + r + σan : ε̇ v - T {3Ko αo I : ε̇ e + 3K∞ α∞ I : ε̇ v}

t t
D D o o
+ ρ{T ( mt
- pt
)- (μp - μm + (Dpm- Dpd + Dmd)ΔYd + (Dpm + Dmp)ΔYp -
ρ ρ
o o o ∞ ∞ ∞
3K (αp - αm) trεe - 3K (α p - αm) trεv - Dp t - Dmt ΔT)} Y
˙ . +ρ{T (Dm t - Dd t)- (μo - (15)
p
ρ ρ ρ ρ ρ
d
o o o ∞ ∞ ∞
μm + (Ddm + Dmd)ΔYd + (Ddm - Ddp + Dmp)ΔYp - 3K (αd - αm) trεe - 3K (α d - αm)
o
ρ ρ
trεv - Dd t - Dmt ΔT)} Y
˙
d
ρ
Equation of diffusion for a species with linear chemistry:
(16)
ρẎi = ∑ υir Mi kr αr+ crs tr σ an - div (- kd ∇(μd-μm) - cpm . ∇( μp-μm ) - c d ∇T)
µ µµ µt
It is pointed out the fact that Jq is a function of the quantities ∇T, ∇μd, ∇μm, ∇μp, μd, μm,
μp and that the potentials depend on following parameters: Yd, Yp, tr εe, tr εv, T. The
association of linear complementary laws with coupling state laws enables the determination
of non linear local equation of diffusion and non linear equation of heat. In the equation of
heat, the quantities for conduction and radiation are logically present, and also the quantities
relating to the traditional mechanical aspect in thermo-viscous-elasticity. The last two
quantities are new and correspond to the evolution of the blend during the chemical reaction.
Since chemical potentials are functions of the mass ratio and of the change of elastic and
viscous volume, this dependency appears in the differential equation governing the
temperature.
Concerning the equation of diffusion, for the same reason as previously, the modification
of the blend, mainly governed by the chemical reaction, is also influenced by the state of
deformation of the blend. If a compacting or contracting loading is considered, the diffusion
of the species is more or less accelerated. It is also perhaps a second order effect but, if the
prediction of the precise evolution of the state of the matter throughout the curing is searched,
it must be considered.
The evolution of the species is influenced by the gradient of temperature, but also by the
temperature itself through the state laws concerning the chemical potentials as indicated in
equation (7).
Parametric Study on a Simple and Basic Version of the Coupling Model
Foundations of a complete thermal, chemical, mechanical and including diffusion, coupling

model have been presented in previous section in a viscoelastic framework. Nevertheless, this
modeling must be tested in an easy way to check its possibilities. This section presents then a
simplified version of the complete coupling model. Only the elasticity of the matrix was taken
into account with non linear chemistry. Gradients effects and hydrostatic pressure effects of
species diffusion in equation (16) were not considered. Hence equations of diffusion for pre
polymer and hardener with only non linear chemistry are given by:
Simplified equation of diffusion:
dYd υd Md
= (K + K2 (1-Yd - Yp )m )(Yd + Yp)n
dt υm Mm 1
(17)
and
dYp υp Mp
= (K + K2 (1-Yd - Yp )m )(Yd + Yp)n
dt υm Mm 1
In the same way, thermal effects on species diffusion (coupling coefficients Di T) and
diffusion between species (coupling coefficients Dij) were considered as second order effects
in comparison with other contributions of the equation of heat transfer (15) which simplified
expression is then as follows:
Simplified equation of heat transfer:
T ]} + r
ρ Cp dT = - div{λ T [-grad (18)
dt
e
‗ε
- T { (3λ + 2μ) αT }tr ˙
- ρ{( μd - μm) - 1 (3λ+2μ)(αd –αm)( tr‗

εe )} dYd
o o
ρ dt
- ρ{( μp - μm ) - 1 (3λ+2μ)(αp –αm)( tr‗
εe )} dYp
o o
ρ dt
where Cp stands for specific heat, λΤ stands for thermal conductivity, λ and μ are the
Lamé coefficients and αT is the coefficient of thermal expansion of the matrix in formation. r
stands for the heat radiation imposed by the oven.
Mechanical balance equation remains unchanged and is as following without gravity
effects:

εe ) ‗I + 2 μ ‗
div {λ (tr ‗ εe - (3λ + 2μ) [αT (T - To) +
(19)
o o
+ αdm (Yd -Yd ) + αpm (Yp -Yp ) ] ‗I } = 0
The solving of this basic and simplified coupling model is presented in this section for
the simulation of the curing of a thick epoxy sample.
Finite Element Modeling
The very low mass of accelerator, as it concern only 1% of the pre-polymer mass, was
neglected for the simulation of pre-polymer and hardener mass ratios evolutions. However,
effects of the accelerator were taken into account by cure kinetics coefficients of the Kamal
and Sourour equation and obtained from the real resin blend. Thus, aims of the simulation
will be the numerical determination of temperature field, displacement field, degree of
conversion of the reaction, strain field and stress field during the thermosetting reaction of the
LY556 epoxy resin. Precise details for numerical implementations are provided by Rambert
(2005, [53]). Validity of numerical implementation was first tested with Abaqus® 6.3 FEM
thermoelastic solutions. According to long time of computation induced by viscoelastic
calculations exceeding a week on a Silicon Graphics Station (SGI origin 300, Processor R
1400 Mips, 600 Mhz, Irix system), only elastic simulations without species diffusion could be
performed. User element library (UEL) developed contains therefore four degrees of freedom
(three axis displacement and temperature). Fortran 77 programming language was used for
UEL implementation into the finite element calculation software Abaqus® 6.3. A 20 nodes
isoparametric three-dimensional element with quadratic interpolation functions was necessary
to solve the coupling model. Note that the use of axi-symetric elements has considerably
reduced, around ten times less, the calculation time for this problem, but the model was
developed in 3D to be useful for real composites structures.
Material Parameters Input

o o
According to the mass quantities employed, initial mass ratio are Yp =0.527, Yd =0.473. Data
were extracted from Jochum, (1999, [25]) and Smaali, (2005, [55]) on the basis of a 75%
cured epoxy matrix that correspond to the highest degree of cure reachable for the cure
schedule to simulate.
Two kinds of simulation were performed. The first one considers all material properties
constant during the curing in order to check the possibilities of the model. The second one
assumes specific heat and coefficient of thermal expansion (CTE) to be a linear function of
degree of conversion (α) during the curing. Thus, the framework of linear thermal, diffusion
and elastic behavior with non linear chemistry was considered and representative data of the
curing are given in Table 1. This choice is a first and certainly far approach of the real
behavior of the epoxy blend, since real behavior is a non linear viscoelastic one. Nevertheless,
it is first of all a necessary way to check the model exposed in this chapter, and secondly
viscoelastic computations were excessively too long as mentioned earlier.
Table 1. Representative data for the cure dependent elastic model.
Initial conditions Chemical

o o
Yp =0.527 , Yd =0.473 υp Mp υd Md
o o υm Mm = -0.527, υm Mm = -0.473
μd–μm=185.103 J.kg-1
o o
μp–μm= 185.103 J.kg-1 e1=6000 K , e2=7855 K
a1=1.35.103 s-1, a2=1.77.106 s-1
σo=0 Pa, so=0 J K-1.kg-1
m=0.75 , n=1.75
To=291.05 K
Mechanic Thermal Diffusion

αT =1.6.10-4 K-1
E=19 MPa. αT linear = (1-α).3.9.10-4 + α 1.6.10-4
αd –αm =0.04755
ν=0.38 Cp = 1325 J K-1.kg-1
αp –αm =0.04268
ρ=1200 kg.m-3 Cp linear = (1-α).1000 + α.1380
λT=0.2 W.m-1.K-1
An initial difference of 185.103 J.kg-1 was introduced between the chemical potential of
the pre-polymer, the hardener and the matrix. It is an arbitrary value, but it takes into
consideration the contribution of the latent heat in the equation of heat transfer (15). By the
same way, according to experimental results observed for volume shrinkage, an average value
of 4.5% was chosen for mass expansion coefficients difference αd –αm and αp –αm.
Experimental Device
The modeling approach proposed in this work was tested for to the curing of an LY556 Ciba-
Geigy epoxy resin. 30g of resin was cured and mass quantities employed were as follows:
15.789g of LY556 pre-polymer, 14.211g of HY917 hardener according to mass
stoichiometric ratio of 100% for pre polymer and 90% for hardener.
Figure 12 shows the experimental device used by Smaali (2005, [55]) and modelled by
3D nodes meshing by Jugla (2005, [56]) for the curing of the LY556 epoxy resin. Liquid
resin is poured into a metallic cylinder up to the half of its capacity. The assembly is airtight
and plunged into a sand mould to assume an homogeneous heating of the cylinder by an
electric plate. Internal air pressure and temperature are monitored throughout the cure done
with a 0.6°C/min ramp followed by a plateau around 85°C. A special protocol taking into
account gas emission during cure and based on perfect gas rules allows the calculation of
volume variations induced by the chemical reaction during the cure cycle.
Experimental data provided are chemical shrinkage during cure, air temperature elevation
T2(t) produced by exothermic effects of the thermosetting reaction of the epoxy resin and
temperature boundary conditions T1(t) applied by the heating.
32.0
Resin
Air
Steel
36.5
f1(T)
T2(t)
136
Thermocouple
68.1 136
(T)
1
T
T1(t) 10.0
z 45.0
O
x
Figure 12. Experimental device for epoxy cure data and 3D 20 nodes meshing of the resin block.
Only a quarter of the resin block was meshed due to the symmetry of problem. Outputs
were selected on element 136 located close to the center point of the resin block where a
thermocouple probe was plunged for internal temperature measurement.
Results
Local Temperature Evolution
Results for local temperature evolution of internal element 136 of the block of matrix are
presented in figure 13.
It is interesting to note that whatever choice of specific heat, the simulated temperature
evolution remains the same. Moreover, an exothermic peak is obtained and demonstrates
therefore that the coupling between the thermal and the chemistry was taken into account.
The magnitude of the exothermic peak is low in comparison with the experiment for a value
of Cp= 1325 J.kg-1.J-1. The level of the peak can be increased by decreasing Cp, since less and
less heat will be necessary to increase the temperature. On the other hand it appears obvious
that the linear dependency of Cp to the degree of cure underestimates the reality. In a same
manner, CTE dependency to degree of conversion did not affect the level of the exothermic
peak, only a small time shift was observed. Exothermic peak is much more sensible to
specific heat determination and this point must therefore be improved. Additionally to this
point, a significant difference in characteristic time for exothermic peak appearance is
observed. According to the equation of heat, this difference denotes the sensibility of the
model to initial data for chemical potential and mass expansion difference. The accuracy of
the model requires thus a better description of these properties. Nevertheless, despite of
material parameters that must be improved, the temperature results demonstrate that internal
temperature evolution during the curing is possible with this kind of model. The weakness of
the model stays in the fact that it requires high precision for material parameters such as
specific heat, chemical potential or mass expansion that may be not obvious to obtain.
430
410
390
Temperature (°K)
370
350
Cp=1325 [J.K-1.Kg-1]
330 Cp linear
CTE linear + Cp=1325
310 Experimental
290
0 3000 6000 9000 12000 15000
time (s)
Figure 13. Local temperature simulation results for element 136.
0.8
Mass fraction of matrix
0.6 Cp1325
Cp linear
0.4
CTE linear +
Cp=1325
Experimental
0.2
0
0 5000 10000 15000
time (s)
Figure 14. Local matrix mass ratio (degree of cure) simulation results for element 136.
Mass Ratio Evolution
In a similar way, results for matrix mass ratio evolution (i.e. degree of cure) are exposed in
Figure . Experimental degree of cure evolution was computed from experimental internal
temperature, measured in the center of the resin block, applied to the cure kinetics equation of
the Kamal and Sourour model.
The same comments as for temperature evolution can be considered here. Simulation
results for matrix mass ratio evolve earlier than the experiment since simulated temperature
grows faster as indicated in Figure 13.
Shrinkage Strain Evolution
Shrinkage result is defined as being the difference between total axial strain (z axis strain) and
thermal strain. Assuming small perturbation context, axial strain was obtained from axial
displacement Uz divided by initial axial length. Thermal strain was calculated, in a usual way,
from coefficient of thermal expansion and temperature variation. Simulated shrinkage strain
evolution defined by elastic strain in addition with mass diffusion strain was compared with
experimental macroscopic shrinkage strain of the resin block obtained from internal air
temperature and pressure records, after deduction of thermal expansion. The attention of the
reader is taken to the fact that local information for shrinkage strain is compared with
macroscopic data of shrinkage. Normally, local shrinkage information should have been
integrated throughout the block of resin before comparison with the experiment.
Nevertheless, the final local shrinkage level should tend to be in the same order as for the
macroscopic one with the assumption of no strong gradients of degree of cure throughout the
matrix block at the end of the curing. This assumption is critical, but seems acceptable since it
was observed in Figure 8 that the final level of degree of cure tends to the same level for other
curing conditions. Results for shrinkage strain evolution are displayed in Figure 15.
1% Longitudinal strain (z axis)
time (s)
0%
0 3000 6000 9000 12000 15000
-1%
-2%
-3%
-4% Cp=1325 [J.K-1.Kg-1]

Cp linear
CTE linear + Cp=1325
-5% Experimental
Figure 15. Local shrinkage strain simulation results for element 136.
Apart from characteristic time of simulated shrinkage start, that appears logically early
according to temperature (Figure 13) and matrix mass start (Figure ) results, the final level
obtained by the simulation are encouraging but slightly overestimates the experiment. One
cannot state on this difference since experimental data have of course some margin of error.
On the other hand equation of motion (5) shows sensitivity to the mass expansion parameters
for the pre-polymer and the hardener which are not obvious to determine as stated previously.
Internal Stress Evolution
Assuming a simple linear elastic behavior for matrix evolution during the curing, where the
coefficients of Lamé are modulated by the degree of conversion as indicated in Table 1,
results for internal elastic stress evolution are presented in Figure 16.
4.E+07 Longitudinal stress (z axis)
Cp=1325
3.E+07 [J.K-1.Kg-1]
Cp linear
2.E+07 CTE linear +

CP=1325
1.E+07
0.E+00
0 3000 6000 9000 12000 15000
-1.E+07
time (s)
Figure 16. Internal elastic stress simulation results for element 136.
It is interesting to note that internal stress evolves quickly during the curing. This
evolution is simultaneously induced by thermal gradients and chemical shrinkage. At the
beginning, internal stress is positive (tensile stress) and is exclusively produced by thermal
expansion gradients. Then, at gelation start (around 6000 sec. i.e. 55% degree of cure for the
LY 556 epoxy blend) a compressive stress is observed. In this area, a strong shrinkage is
developed as indicated in Figure 15 and coincides with the exothermic peak. The highest
level of internal stress is observed in this area and results from the shrinkage strain and
thermal expansion strain gradients that are maximal. Thermal expansion strain decreases
logically after the exothermic peak is done and leads to a decrease of internal stress. Special
attention is taken to the fact that internal stress tends to an horizontal asymptote that is around
0.8MPa. This demonstrates the existence of internal stresses still existing at the end of the
curing and produced by gradients of thermal expansion and shrinkage. Of course, elastic
internal stress should tend to zero in case of a perfect matrix without any gradient and the end
of the heating stage.
Discussion
Numerical results exposed here were obtained in the framework of linear thermal, diffusion
and elastic behavior with non linear chemistry. Even if this assumption for material
description is quite simple in comparison with the real non linear viscoelastic behavior of the
resin, simulation results obtained are coherent and not so far from the experiment. It was
observed that the thermosetting reaction produces an exothermic peak in the center of the
matrix block that generates thermal gradients throughout the thickness. Consequently
gradients of shrinkage are developed by the heterogeneous matrix in creation. The
competition between thermal and shrinkage gradients is the power unit of internal strain and
hence internal stress. A first order of internal stress magnitude developed during the curing is
proposed by the elastic approach and was found to be around one MPa., before the cooling
stage. This is in the right order of magnitude with the literature for elastic approach (Ruiz and
Trochu 2005, [28]), but internal stress estimation at the end of the curing needs a better
description of material behavior. The viscoelasticity must be considered on one hand, and
material properties change at glass transition crossing has to be added on the other hand.
However, the modeling approach proposed here is a powerful technique that allows the
taken into account of any phenomenon like species diffusion for example. From a theoretical
point of view a quite complete coupling between the thermal, the chemistry, the diffusion of
species and the mechanics was developed within the framework of the standard generalized
mediums in the context of linear viscoelasticity for non reversible out of balance
thermodynamic processes. The foundation for a multi physics coupling approach is
established. Moreover, this technique for material history description enables post cure
description.
Nevertheless this kind of approach requires high accuracy for unusual material
parameters like chemical potential and mass expansion coefficient. These parameters strongly
influence characteristic time of exothermic peak and gelation start. Simulation results have
indicated that species diffusion contribution, as it was not computed, seems to have a small or
second order contribution to local temperature evolution since temperature result was quite
satisfying. This statement must still be verified by a specific parametric study devoted to
species diffusion. Anyway, temperature is one of the main governing parameter of the
problem, and its simulation result appears to be perceptible to specific heat for its magnitude
and to chemical potential for its characteristic time. Thus, even if the foundation of the
coupling problem has been established, the model exposed here appears to be heavy for
unusual material parameter definition and the UEL technique is still time consuming in
elasticity and is not reasonable with viscoelasticity. Extension of this way of cure modeling
must therefore be improved for industrial, built in, finite element resolution.
Towards a Predictive Internal Stress Coupling Model

Foundations of a complete coupling model have been established. If this is satisfying from a
theoretical point of view, it appears obvious that all the couplings could not be taken into
account for industrial simulation according to the heaviness of parameters definition. Unusual
coupling coefficients are requested on one hand and material parameters dependency to the
curing must be considered on the other hand. The couplings that are considered must be
revised to make the model more accessible.
Thus following assumptions are done:
- Only the elastic behavior of the curing is considered

- Gradients effects and hydrostatic pressure effects (coupling coefficient crs) are
ignored for species equation of diffusion.
- Coefficients of diffusion expansion αij between species i and j are not considered for
their stress contribution in equation (7).
Equation of species diffusion is then only controlled by the chemistry and in our case
with a non linear chemistry as given by the cure kinetics model of Kamal and Sourour
(equations 12 and 17).
Hence mechanical balance equation (19) is simplified as follows:

div {λ (tr ‗ εe - (3λ + 2μ) [αT (T - To)] ‗I } = 0
εe ) ‗I + 2 μ ‗ (20)
Furthermore, it is interesting to remark that the two last quantities of the equation of heat
(15), that are in product with mass ratio evolution for resin (subscript p) and hardener
(subscript d) species, can be related to the heat flow produced by the chemical reaction as
defined by differential scanning calorimeter (DSC) analysis. Hence, their expression can be
rewritten in a more convenient way like ρ ΔHr dα/dt, where ΔHr stands for the enthalpy of the
reaction. Therefore, if we consider only the elastic approach, expression of heat transfer is
expressed in a more convenient and usual way as follows:
Elastic equation of heat transfer rewritten with usual expressions:
T ]} + r + ρ ΔHr dα/dt - T {(3λ + 2μ) α }tr ˙εe

ρ CpdT = - div{λ T [-grad (21)
dt
T ‗
Nevertheless, the coupling with the mechanics in the equation of heat transfer can be
supposed a second order contribution if temperature level obtained by the only chemical and
thermal coupling is satisfactory. According to Ruiz and Trochu results (Ruiz and Trochu,
2005 [28]), this assumption seems to be acceptable as they obtained exothermic peak easily
with only a thermal and chemical coupling.
Finally, a new, much more accessible, formulation of the coupling model is described by
governing equations (20) and (21). If material parameters appear to be more usual, their
evolution laws are requested since the matrix is a different material at each time of the curing
and this point cannot be neglected. In the same way, elastic strain evolution must be defined
during the curing. Evolution laws for material parameters, curing characteristics and strain
formulation that were highlighted by bold letters in governing equations (20) and (21) are
presented in next subsections. Moreover, because of the impossibility to perform material
parameters identification tests for any degree of cure, models must be developed for material
parameters and strain evolutions dependency to the degree of cure. The validity of this
modeling approach is then compared with the experiment (Rabearison 2007, [57]).
Curing Parameters and Strains Modeling
Elastic Strain Modeling
The curing of thermosetting systems owns thermal strain and chemical strain (shrinkage). In
the framework of small perturbation that is assumed here, the total strain increment can be
expressed as:
dεij (t) = dεije(t) + dεch thermal ij(t) + dεijth (t) (22)
where dεije(t) stands for elastic strain increment, dεijch (t) stands for chemical shrinkage strain
increment, as defined in Figure (17), and dεijch (t) stands for thermal strain increment.
Chemical Strain Model
The Li et al. (2004, [44]) model that defines chemical shrinkage as a bilinear function of
degree of cure was adopted here. The fit of the Li et al. model with experimental data
provided by the LY556 epoxy resin manufacturer for a 120°C isothermal curing is presented
in Figure 17.
The total cure shrinkage of -6% at 100% of degree of cure was extrapolated from the
bilinear relationship. The experimental data was provided by the resin manufacturer by help
of the Archimedes technique.
Degree of cure
0%
0% 20% 40% 60% 80% 100%
-1%
-2% dy/dx=-0.099
Cure shrinkage
-3% Li et al. model

Experiment
-4%
-5% dy/dx=-0.013
Gelation at 55%, -5.4%
-6%
Total cure shrinkage: -6%
-7%
Figure 17. Cure shrinkage evolution versus degree of cure (LY556 epoxy resin).
Matrix Thermal Strain Estimation during the Curing
Matrix temperature is variable and non uniform during the curing. This heterogeneous
temperature field generates expansion or shrinkage. An additional difficulty is linked to the
fact the curing of the resin is related to a different and changing material at each time. At each
time, thermal volume strain evolution for a temperature increment ΔT can be expressed by
following linear relation where αT stands for the CTE of the blend.
dεVol thermal ij(t) = αT (t) ΔT. δij (23)
One way to solve the determination of the changing CTE is to consider the chemical
blend as a mixture of resin and matrix weighted by the degree of cure.
In this context, coefficient αT (t) is defined by
αT (t) = [1- α (t)] αT uncured epoxy + α (t) αT fully cured epoxy (t) (24)
which is a mixture rule relation weighted by the degree of cure, between the uncured liquid
state (resin) and the fully cured solid state (matrix). αT uncured epoxy denotes the thermal
expansion coefficient per unit volume for the epoxy resin in its liquid state before gelation
and αT fully cured epoxy denotes the thermal expansion coefficient per unit volume for the fully
cured epoxy matrix. However, for amorphous polymers, like epoxies, αT fully cured epoxy is
temperature dependant and glass transition dependent. Identification of coefficients of
thermal expansion for the LY556 epoxy system was performed by DMA-TMA analysis.
Thus, for the LY epoxy system, αT liquid epoxy = 5E-4 °C-1 and α T fully cured epoxy = 450E-
6°C-1 for a vitrified matrix (below Tg) and α T fully cured epoxy = 450E-6 + 4.1E-6 (T-Tg) for a
rubbery matrix (above Tg).
This modelling requires Tg determination at each time of the curing. Tg was calculated
by the usual Pascault and Williams (1990, [58]) relation (also called Di-Benedetto equation)
as follows:
(Tg - Tg0)/(Tg infinity - Tg0) = λα/[1 - (1 - λ)α] (25)
where λ is an adjustable, structure-dependent parameter, which ranged between 0.46 and 0.58
for several amine epoxy systems. Tg0 (Tg at α = 0) is the lower limit temperature for the start
of the thermosetting reaction of the epoxy blend that stays below Tg0 in a glassy state. Tg
infinity must be viewed as an estimated value for an idealized fully cured network, physically
unachievable.
Several Tg determinations were performed by DSC analysis on LY556 epoxy matrices
samples initially cured at different isothermal plateaux. The glass transition appears as an
endothermic shift in the heat flow over a temperature interval. Tg is measured as the midpoint
of the step transition. By the way, the residual heat of reaction of the remaining reactants
(DHr) appears as an exothermic peak in the temperature region of the rubbery state of the
material. This technique allows the determination of the corresponding degree of cure of the
studied sample of matrix. It is then possible to plot a curve of Tg versus degree of cure α. Tg0,
Tg infinity and λ are estimated from these experimental data by a fitting technique. Accuracy of
the parameters is presented in Figure 18.
170 Tg points by DSC

Tg model (Pascault and Williams)
150
Tg0=35°C; Tginfinity=155°C; λ=0.46
130
Tg (°C)
110
90
70
50
50% 60% 70% 80% 90% 100%
Degree of cure
Figure 18. Tg evolution with degree of cure.
Cure Kinetics Model
Because the chemical reaction associated to the curing of a resin occurs over time, its
corresponding degree of conversion evolution will be controlled by the temperature history.
Thus cure kinetics of a thermosetting resin will lead to the determination of the degree of cure
dependency on temperature history. For the case of epoxy resins, like the LY556 presented in
this chapter, the autocatalytic model developed by Kamal and Sourour (1976, [43]) seems to
be the most accurate and widely used to describe cure kinetics. It fits very well with cure
kinetics characterized by DSC scans. The way of cure simulation was adopted here to carry
out local information for degree of cure history, based on local temperature records as
presented in Figure 7. Cure kinetics coefficients of the Kamal and Sourour cure kinetics
equation (12) were obtained by a square root fitting technique applied on experimental DSC
plots of rate of degree of cure in function of degree of cure. Corresponding coefficients
obtained for the LY556 epoxy resin blend are presented in Table (2).
Table 2. Cure kinetics coefficients of the LY556 epoxy resin system for the Kamal and
Sourour model.
m 0.75
n 1.25
a1 1.41093 103 s-1
a2 2.35865434 106 s-1
e1 5917.89 °K
e2 7983.42 °K
A finite difference scheme was used to solve the cure kinetics equation (12). The
temperature input for the simulation is the local temperature of the resin and hence accounts
for local exothermic effects during the curing. This local temperature input in cure kinetics
equation can be either provided by thermocouple probe measurements for experimental data
of local degree of cure evolution, or in case of FEM simulation by the UMAT solving of the
thermal and chemical coupling problem.
Mechanical Behavior Description
Mechanical behavior of the resin during the curing was performed by DMA-TMA tests. Since
the resin was initially liquid, only shear tests were possible to carry out its behavior during the
curing. Shear test results were first obtained as a function of time during the 120°C curing.
These results were then plotted as a function of degree of cure thanks to the degree of cure
evolution during the curing as given by DSC scans or by cure kinetics model. The gelation
point at 55% of degree of cure was observed by DMA-TMA test as displayed in Fig 20. In
this figure, a typical peak around 55% of degree of cure was observed for the loss modulus
evolution at 1Hz., denoting gelation area. Important results are that before gelation, moduli
are very low and this is coherent with the liquid state of the resin. A solid state only appears at
gelation and this is confirmed by strong moduli growth after this point. Nevertheless,
attention is taken to the shift observed for moduli growth as the frequency increases. Moduli
are growing for earlier degree of cure in comparison with the 1Hz. data. This is an artifact
since degree of cure was obtained for static tests and hence can less and less be used for
dynamical tests as shown in Figures 19 and 20. Indeed, gelation start at 55% of degree of
cure, is an intrinsic parameter of the thermosetting reaction on one hand and, on the other
hand, it is not possible that increasing frequencies of DMA-TMA tests may increase cure
kinetics in such a way to make moduli start around 25% of degree of cure. Ideally, dynamical
DSC tests should be performed. These kinds of devices made their appearance in some
research centers but are not available on the market yet.
1.E+03
Elastic shear modulus G' (Pa.)
8.E+02
4.0E+07 G' 1Hz.
G' 10Hz.
6.E+02 G' 20Hz.
3.5E+07
Elastic shear modulus G' (Pa.)
G' 30Hz.
4.E+02 G' 40Hz.
3.0E+07 G' 50Hz.
2.E+02
2.5E+07
0.E+00
0 0.2 0.4 0.6 0.8 1
2.0E+07 Degree of cure
1.5E+07 G' 1Hz.

G' 10Hz.
1.0E+07 G' 20Hz.
G' 30Hz.
5.0E+06 G' 40Hz.
G' 50Hz.
0.0E+00
0 0.2 0.4 0.6 0.8 1
Degree of cure
Figure 19. Elastic shear modulus evolution for LY556 epoxy resin cured at 120°C, before cooling.
2.0E+03
Loss modulus G'' (Pa.)

1.6E+03 G'' 1Hz.
6.0E+07 G'' 10Hz.
1.2E+03 G'' 20Hz.
G'' 30Hz.
5.0E+07 G'' 40Hz.
8.0E+02
G'' 50Hz.
Loss modulus G'' (Pa.)

4.0E+02
4.0E+07
0.0E+00
0 0.2 0.4 0.6 0.8 1
3.0E+07 Degree of cure
G'' 1Hz.
2.0E+07 G'' 10Hz.
G'' 20Hz.
G'' 30Hz.
1.0E+07
G'' 40Hz.
G'' 50Hz.
0.0E+00
0 0.2 0.4 0.6 0.8 1
Degree of cure
Figure 20. Loss modulus evolution for LY556 epoxy resin cured at 120°C, before cooling.
The description of shear modulus as a function of the degree of cure only is critical since
it is well known that it depends also of the temperature (Ruiz and Trochu, 2005 [28]).
However, the aim here is to check the possibilities of the UMAT approach for a given cure to
simulate. Further extension of this approach for any cure will contain temperature
dependency. As experimental data for elastic behavior were accurately reachable by shear
tests for liquid resin at the beginning of the curing, it appears to be more appropriate to
express the elastic constitutive law as a function of shear and bulk moduli.
Hence, in this context, bulk modulus evolution versus degree of cure (K (α)) was
estimated by a mixture rule relation between 3 GPa. for the liquid state and 6.3 Gpa. for the
solid state (Pascault et al., 2002, [59]) as given by:
K (α) = (1-α) K (0) + α K(1) (26)
Where K(0) and K(1) stand for uncured resin state and fully cured resin state
respectively. Elastic shear modulus function of degree of cure was taken as a polynomial fit
of the 1Hz. curve as follows:
0<α<0.45 : G (α) # 10 Pa.

0.45 <α<1 :
(27)
G (α) = -2.14742E6(α)6+4.99257E6(α)5-3.65779E6(α)4 +1.10552E6(α)3
-136059 (α)2+5264.5(α)-16.576 Pa.
Hence elastic constitutive equation was written by help of shear modulus G’ and bulk
modulus K, with a dependency to the degree of conversion α as following where t denotes the
curing time:
2
σij (t) =[K(α)− 3 G’(α)] tr(εe(t)).δij +2G'(α)εije(t) (28)
Specific heat Cp (J/g.K)
In a similar way as for the coefficient of thermal expansion, an easy way for the description of
the epoxy matrix specific heat evolution is to consider that it can be described by a linear
mixture rule relation, weighted by the degree of cure as given by equation (29) :
Cp (α, T) = (1-α) Cp (0, T) + α Cp (1, T) (29)
where Cp (0, T) and Cp (1, T) stand for uncured resin and fully cured matrix temperature
dependent specific heat evolutions. It was assumed that specific heat expressions established
by Bailleul [60] for a similar m10 epoxy system could be acceptable because of the lack of
exact value for the LY 556 epoxy system. Hence,
Cp (0, T) = 0.69413 + 0.003258761.T(°K)
Cp (1, T) = 0.02813 + 0.0043379. T(°K) before Tg
(30)
Cp (1, T) = 1.56808 + 0.00137849. T(°K) after Tg
(J/g.K)
Thermal Conductivity λ (W/m.K)
In the same manner as previously, thermal conductivity was also expressed by a linear
mixture rule relation as follows:
λ (α,T) = (1-α) λ (0,T) + α λ (1,T) (31)
where λ (0,T) and λ (1,T) stand for uncured resin and fully cured resin, temperature
dependent, thermal conductivity evolutions. The thermal conductivity for the uncured LY556
epoxy resin was estimated at 0.255 w/mk at room temperature by Moisala [61]. Temperature
dependency of the thermal conductivity of the LY556 resin was then assumed to be in the
same way as the one established by Bailleul for the m10 epoxy system. Hence,
λ (0,T) = 0.0012857.T(°K) - 0.1219071

(32)
λ (1,T) = -0.0002727.T(°K) + 0.5075534
Heat Flow of the Thermosetting Chemical Reaction (W/m3)
As defined by the DSC analysis, the heat flow φ (t) produced by the chemical reaction
associated to the curing of a thermosetting resin is a linear function of the rate of degree of
cure with a slope corresponding to the enthalpy variation ΔHr of the reaction:
φ (t) = ρ ΔHr(T) dα/dt (33)
Mass enthalpy ΔHr depends on the temperature at which the reaction is done. This
temperature dependency is usually described by a Kirchhoff law that assumes no phase
change during the temperature interval that is considered. However, this modeling is not valid
during the curing since a liquid solid change is observed at gelation. ΔHr(T) was then
extrapolated by a polynomial fit of DSC analysis for the LY556 epoxy system. As explained
in previous section, about glass transition dependency to degree of cure, it is also possible to
plot the remaining reactants enthalpy (DHr) as a function of initial isothermal curing
temperature. ΔHr(T) is a second degree polynomial function of the curing temperature and is
displayed in Figure 21.
2
330 y = -0.00622x + 2.51096x + 44.19772
2
R = 0.95144
280
Enthalpy (J/g)
230
180 Experimental
Polynomial
130
80
20 70 120 170 220
Temperature (°C)
Figure 21. DHr dependency to curing temperature.
Finite Element Simulation
According to previous discussions and simplifications, a modeling approach for the curing
where only the thermal and the chemistry are coupled is considered. Evolution laws for the
coupling between the thermal, the chemistry and the mechanics have highlighted a
dependency on three variables: temperature, degree of cure and rate of degree of cure. Thus,
state variable of the problem will be the temperature, the degree of cure and the time and can
be considered as being the main governing parameters of the curing. The mechanics will be
deduced from these state variables.
From a technical point of view, the finite element analysis for the solving of equation of
heat (21) coupled with the thermal, the cure kinetics and the production of heat of the
thermosetting reaction was developed in a Fortran 90 subroutine with the user material
(UMAT) facility of the finite element program Abaqus® V. 6.51 [62]. State variable such as
temperature and degree of cure, material parameters, strains and stresses during a time
increment are calculated within the model.
The degree of cure was calculated with the cure kinetics model of Kamal and Sourour
(equation 12). The instantaneous heat flow produced by the thermosetting reaction is deduced
from the degree of cure result at the end of the time increment and is applied as heat source in
the UMAT subroutine for the next time increment. This technique allows the taken into
account of a complete coupling between the thermal and the chemistry, and allows the study
of real 3D composite structures.
The cure simulation model is applied to the curing of an LY556 Ciba-Geigy epoxy resin.
The coupling of specific heat and thermal conductivity with temperature and degree of
conversion was introduced by a tabular form in the Abaqus® finite element software. Cure
kinetics equation was solved inside of the UMAT subroutine by an Euler explicit method.
The time increment was provided by the Abaqus® solving program and its maximum value
was fixed according to the maximum time increment allowed for the explicit solving of the
cure kinetics. By the way, chemical and thermal strain increments were deduced.
Results
This section presents simulation results for the curing of the LY556 epoxy resin. The quality
of the simulation was first checked, for its accuracy concerning the thermal and chemical
coupling problem, by comparison of internal temperature prediction with thermocouple
records done in the center point of the matrix during the curing.
The second part of this section presents simulation results concerning internal stress
estimation developed by the curing.
Local Temperature Evolution and Gradients
The curing was experimented in collaboration with the IFREMER institute (French Research
Institute for Exploitation of the Sea). A Pyrex test tube with a diameter of 20 mm filled with
epoxy resin for a height of 25 mm was placed in an oven and heated with a 3°C/min ramp
followed by an isothermal plateau at 120°C. Temperature evolutions in the centre of the resin
and on the outside of the Pyrex test tube were recorded during the curing. A strong
exothermic effect was observed with a peak at around 250°C. This experimental curing was
simulated by the UMAT modeling approach exposed in this section and results obtained are
exposed in Figure 22. The outside temperature of the Pyrex was applied as thermal load for
the simulation of the curing within the text tube. A 8-node thermally coupled axisymmetric
solid, biquadratic displacement, bilinear temperature CAX8T element of the Abaqus®
element library was used for the meshing.
Prediction for local temperature evolution is very satisfying except for the decrease of the
exothermic peak that is done to quickly. This difference is related to heat exchanges between
the matrix and the air above the Pyrex test tube that was not taken into account for the
simulation. In fact air around the test tube is at least at oven temperature and delays the
exothermic peak decrease. It is particularly interesting to note that temperature start and
exothermic characteristic time were well fitted by the model. This validates thermal
parameters modeling on one hand, and a good coupling between heat produced by the
reaction and the heating on the other hand. The model was also validated for polyester resin
curing as presented by Rabearison et al. (2007, [63]).
300
250 Applied
temperature
Local resin
Temperature (°C)
200
temperature
Model
150
100
50
0
0 200 400 600 800 1000 1200 1400 1600 1800
time (s)
Figure 22. Local temperature simulation in the centre of the resin (120°C isothermal curing).
Verre
Pyrex
300
250
Temperature (°C)
200
73
73
77 80
80
77
150
100
Element 73
Element 77
50 Element 80
0
0 200 400 600 800 1000 1200 1400 1600 1800
time (s)
Figure 23. Thermal gradients predicted during the curing of the LY556 epoxy resin.
Once local temperature prediction is validated, thermal gradients, which are developed
during the curing, can be estimated by the model as indicated in Figure 23.
Important gradients are predicted and hence lead to gradients of degree of cure and
gradients of strains. This is one of the basic mechanisms for internal stress development
during the curing. A first estimation of internal stress, in the framework of elasticity, is
proposed in next subsection.
Internal Stress Prediction
The elastic analysis of the epoxy Pyrex test tube structure leads to a first estimation of the
internal stress field developed by the curing as exposed in Figure 24.
1.E+07
9.E+06
8.E+06
7.E+06
Von Mises (Pa.)

6.E+06
5.E+06
4.E+06
3.E+06 Element 73
Element 77
2.E+06 Element 80
1.E+06
0.E+00
0 200 400 600 800 1000 1200 1400 1600 1800
time (s)
Figure 24. Von Mises internal stress prediction.
Internal stress appears significantly around 1100s that corresponds to the exothermic
peak start as mentioned Figure 23. From this point, the gelation reaction starts and matrix
modulus grows quickly as indicated in Figure 19, hence the internal stress growth. The
internal stress level predicted is two times higher than the literature for thermal, chemical and
elastic coupling approaches of Ruiz and Trochu [28], but they did it for polyester resin with a
one-dimensional model.
Anyway, a first validation of the stress level estimation could be provided by the stress
estimation applied on the Pyrex test tube. Indeed, cracks propagations on the test tube walls
were observed experimentally during the curing. As indicated in Figure 25 stress level
calculated for the Pyrex element is much higher than the failure stress for Pyrex.
1.2E+08
1.0E+08
Von Mises (Pa.)
8.0E+07 Pyrex failure stress: 70MPa.
6.0E+07
Element 73
4.0E+07
Element 77
Element 80
2.0E+07 Element pyrex
0.0E+00
0 200 400 600 800 1000 1200 1400 1600 1800
time (s)
Figure 25. Von Mises stress evolution of for Pyrex test tube.
After temperature prediction validation, the Pyrex failure prediction can be considered as
a first validation of the model for the internal stress level developed during the curing.
Hence, significant stress gradients are observed inside of the matrix in formation and an
internal stress level of around 7-8 MPa. is obtained after gelation start.
Discussion
Results obtained from the complete coupling between thermal and non linear chemistry, with
dependent and uncoupled mechanics are satisfying. The finite element modeling approach
based on the UMAT technique appears to be a strong and reliable technique for three
dimensional structures. The three dimensional curing simulation was performed, coupled with
the heat generated by the thermosetting reaction. This coupling was validated by internal local
temperature prediction that fits well with the experiment. The dependent and uncoupled
mechanics assumption seems to be acceptable from this point of view and internal stress
prediction for the matrix have predicted the failure load onto the Pyrex tube. Nevertheless, the
viscoleastic behavior of the matrix in elaboration was not taken into account here. This point
must be developed for precise internal stress prediction, especially at the end of the curing,
after return at room temperature. Relaxation effects cannot be neglected and are important for
residual stress prediction and evolution.
The question of the technique for three-dimensional internal stress prediction was cleared
up. However, only results concerning the curing of a three-dimensional (or thick) matrix
block were considered. As seen in the section about the internal stress problem, internal
stresses act on fiber reinforcement waviness. Fiber waviness is the consequence of a
microbuckling instability that was observed during the hot stage of the curing. The single
fiber specimen appears therefore to be a fine testing structure for cure simulation models that
must be able to reproduce the fiber microbuckling for corresponding cure schedule. This point
is presented in next section of this chapter for fiber waviness simulation.
First Fiber Waviness Appearance Simulation

As presented in the internal stress problem section, fiber waviness is resulting from
microbuckling instability during the curing. This instability is generated by the compressive
load developed by the shrinkage of the resin. This was observed by video records to happen
during the hot stage of the curing. The simulation of this instability will require the
corresponding compressive stress on one hand and on the other hand matrix that surrounds
the fiber must be not able to avoid the buckling instability. Thus, as explained by equation
(2), fiber critical load instability will depend on the ratio between matrix modulus and fiber
modulus. The compressive destabilizing load generated by the curing is thus in competition
with the critical load. An inaccurate cure modeling will then fails for fiber microbuckling
simulation. This section presents therefore simulation results for the curing of a single fiber
embedded in an epoxy resin.
The Single Fiber Specimen Curing
The curing model is applied on a single T300 carbon fiber embedded by a LY556 epoxy
resin. A two dimensional meshing with 8-nodes biquadratic displacement, bilinear
temperature, plane strain element (CPE8T) was used for the Abaqus FEM simulation. A
rectangular matrix shape of 10 mm of length and a width of 7 mm with a thickness of fiber
diameter (7 microns) was meshed. A 8 mm long carbon fiber was meshed with the same
elements and was located 1.75 mm below the top of the matrix. This accounts for fiber
position inside of the matrix as given by the experiment for fiber microbuckling curing
conditions (Jochum et al., 2007 [22]). The single fiber specimen geometry is displayed in
Figure 26.
Half length epoxy matrix

T300 carbon fiber
7 mm width
Figure 26. Finite element mesh of the half single fiber specimen.
This sample was heated with temperature boundary condition applied along its width on

the lower face (normal vector - x2 ) and corresponds to a heating with a ramp of around
5°C/min followed by an isothermal plateau at 138°C. Although this curing condition was
applied for the real experiment on a thick matrix (actually a cylindrical shape with a diameter
of 10 mm, as described by Jochum et al, (2007, [22]), it is important to verify if it can also
develop internal stress for a thin matrix that might induce fiber waviness and, by the way, 2D
FEM simulation are less time consuming for the thermal transient analysis of the single fiber
structure.
Fiber Waviness Results
Fiber waviness was obtained by the simulation during the hot stage of the curing. The
wavelength obtained at the end of the plateau stabilizes around 2mm and the amplitude
around 7 microns. Fiber waviness is shown in Figure 27.
The results are very encouraging and are coherent with the physics of the matrix
surrounding the fiber. The matrix is into a tensile stress state induced by the chemical
shrinkage on one hand and, on the other hand, by the fiber that tries to dilate.
Figure 27. T300 carbon fiber waviness observed by FEM curing simulation (deformation scale
factor : 5).
Discussion
The simulation of the curing of a single fiber specimen with microbuckling curing conditions
observed by Jochum et al. (2007, [22]), despite that it was done with a 2D meshing, leads to
successful results. Fiber instability was observed by the simulation with the UMAT technique
devoted to the predictive model presented in this chapter. Even if results for fiber wavelength
obtained here of around 2 mm are far from those observed with the real experiment (around
115 microns before cooling for a 10 mm diameter cylindrical matrix), it is important to
remark that the simulation done here corresponds to a thin plate of matrix since the thickness
was taken as the fiber diameter. One may compare simulation results with thin laminates fiber
waviness measurement presented in Figure 2 and from this point of view results seem to be
satisfying. However, this kind of comparison can only be qualitative, since, even if small
thickness of matrix were studied in both cases, one cannot make direct comparison between
single fiber results and laminate results, namely for fiber neighboring interactions in the
laminate. Moreover, the simulation was only performed during the curing and the cooling
stage was not studied. This point need material improvement during the cooling for the model
and, due to the thermal mismatch between fiber and matrix, fiber wavelength might certainly
be decreased.
Anyway, fiber waviness was predicted by the simulation and provides a validation of the
modeling approach presented in this chapter. Further material description should be provided,
namely for Tg crossing and for the cooling, to allow a direct quantitative comparison with
fiber microbuckling and quantitative residual stress level prediction.
Conclusion
The thermosetting quality question was presented in this paper. It is related to the internal
stress problem that exits in both thin and thick laminates. Despite of numerous experimental
works for internal stress description, the way of cure simulation appears to be the most
strategic for internal, residual, stress prediction and description. Cure modeling requires
taking into account all the couplings that are involved by the thermosetting reaction. This is
especially crucial for three-dimensional simulation of the curing, which cannot be avoided for
real and complex composites structures. To face this problem, this chapter has presented a
modeling approach for a complete, thermal, chemical, diffusive and mechanical coupling
model. Applicability for 3D-FEM prediction was demonstrated. A simplified version of the
model was proposed to be less time consuming. Internal temperature prediction for 3D matrix
curing was validated. Furthermore, 3D internal stress prediction during the hot stage of the
curing is possible and the obtained level was already validated with an elastic behavior of the
curing. By the way, history of internal stress prediction was successfully tested for the
complex microbuckling instability phenomenon of a single carbon fiber in an epoxy matrix.
Even if material description must still be improved for fine quantitative internal stress
description, the 3D coupling model presented in this chapter appears very promising for cure
modeling and, therefore thermosetting laminates quality prediction.
Acknowledgement
The authors of this paper are grateful to the Brest Metropole Oceanne council of the city of
Brest and the Ensieta graduate school of engineering for their financial support.
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Chapter 4
M ODELLING OF M ULTILAYERED P IEZOELECTRIC

C OMPOSITES∗
Claire David†
Université Paris 6 - Pierre-et-Marie-Curie
Institut Jean Le Rond d’Alembert, UMR CNRS 7190
Boîte courrier n0 162, 4 place Jussieu, 75252 Paris, cedex 05, France
1. Multilayered Piezoelectric Plates

We hereafter study the modelling of composite multilayered piezoelectric plates. Our theory
is based on an hybrid approach, where the mechanical and electrical continuity conditions
are satisfied, as well as the boundary conditions on the top and bottom surfaces of the
structure.
The accuracy of the proposed theory is assessed through investigation of significant
problems, for which an exact three-dimensional solution is known.
1.1. Introduction
The development of the so-called “smart-structures", e.g. made of piezoelectric composites,
require nowadays more and more precision in their design and sizing. The importance of
efficient models has, so far, led to numerous theories.
The first kind of approach is generally based on the assumption according to which the
multilayered piezoelectric structure behaves as a single-layered one.
Tiersten [47], Mindlin [33], Lee et al. [31],[32], have applied Kirchhoff-Love’s theory
to piezoelectricity. Yet, only thin structures are concerned.
First order theories can be found, for single-layered structures, for instance, in Chan-
drashekhara et al. [15].
∗
This chapter is the continuation of my Ph. D. [12], [5], [3]. It generalizes the multilayered shell model to
piezoelectric structures.
In a first time, it was natural to consider the related plate model; thanks to satisfying results, we then considered
the shell model.
†
E-mail address: david@lmm.jussieu.fr
198 Claire David
However, the electric field induced by mechanical efforts is, generally, not taken into
account.
Vatal’yan et al [56] devoted themselves to bilayered ceramic plates. Thanks to expan-
sions into series of the thickness coordinate, Lee et al. [32] obtained the two dimensional
equations of motion, for plates made of piezoelectric crystals.
Yang et al. [58], Yong et al. [59] have generalized these results to multilayered plates.
The problem is that those models do not generally take into account the coupling that occurs
in the equations of motion.
Hybrid theories, with a “single-layered type" approach, and a modelling “per layer"
of the electrostatic potential, have been proposed: Mitchell et al. [34] used a third-order
theory for the displacement field, while taking into account the variations of the electrostatic
potential through the thickness of the plate; Fernandes et al. [21], [22] developed a model
that takes into account refinements of the shear terms, as in Touratier [51].
Other “layerwise models" have been developed, in a first time by Pauley [42]. Pai et
al. [39] have proposed an induced-strain model of multilayered piezoelectric plate model.
Heyliger et al. [25], [26] developed an exact three-dimensional theory, for composite mul-
tilayered plates.
Yet, those models do not simultaneously take into account the continuity conditions for
the mechanical and electrical quantities. One can of course find asymptotic theories, which
enable us to satisfy both kinds of conditions, but they only apply to thin structures [17].
We propose in the following, a two-dimensional theory, more accurate, that enables us
to model thick multilayered piezoelectric structures.
This theory generalizes to piezoelectricity our composite multilayered model, devel-
oped in [12], [3], [5], relating our displacement approach, to a “single-layered" type ap-
proach, continuous at layer interfaces, to quadratic variations through the thickness of the
considered structure, of the electrostatic potential, which is also continuous. The transverse
shear stresses, as well as the electric displacement, under a constant strain, are continu-
ous. Refinements of the shear and membrane terms are taken into account, by means of
trigonometric functions.
Eventually, the conditions on the frontier of the structure, or at layer interfaces, are
satisfied.
The accuracy of the plate model thus obtained is assessed through investigation of sig-
nificant problems, for which a three-dimensional solution is known [25], [26]. Consider a
multilayered piezoelectric plate, made of an arrangement of N layers.
Denote by a the length of the plate, by b its width, by h its thickness, and by V the
volume occupied by the plate (see figure 1).
Notation. The frontier of the plate is made of the reunion of its bottom surface S0 , its top
surface Sh , and its lateral surface A.
Denote by Si the interface between the ith and (i + 1)th layers, and by zi the distance
between S0 and Si .
The reference surface coïncides with the bottom surface S0 .

Modelling of Multilayered Piezoelectric Composites 199
Assumptions 1.1. The transverse shear stresses are supposed equal to zero on the top and
bottom surfaces of the plate.
Notation. The Einsteinian summation convention applies to repeated indices, where Latin
indices range from 1 to 3 while Greek indices range from 1 to 2.
Notation.
V Volume occupied by the plate

h Total thickness of the plate
S0 Bottom surface of the plate
Sh Top surface of the plate
Si Bottom surface of the ith layer
zi Distance between S0 et Si
zi0 Distance between S0 and the mid-surface of the ith layer
A Lateral surface of the plate
(xi ) Cartesian coordinates
Li Lamé coefficients
sk , k = 1, . . . , 6 Strains
σk , k = 1, . . . , 6 Stresses
Cmnpq (i) , or CKL (i) Components of the elastic strain tensor
under a constant electric field constant
0
Differentiation with respect to z
,i Differentiation with respect to xi
. Differentiation with respect to time t
δ Variational operator
ϕ Electrostatic potential o
ϕ1B Electrostatic potential on S0
ϕN +1,B Electrostatic potential on Sh
ϕiB Electrostatic potential on Si
ϕiM Electrostatic potential on the midsurface of the ith layer
ϕiT Electrostatic potential on Si+1
→
−
El , l = 1, . . . , 3 Components of the electrical field E
Dk , k = 1, . . . , 3 Components of the electric field
ekl (i) piezoelectric constants, under a constant strain,
of the ith layer
εkl (i) dielectric constants, under a constant strain,
of the ith layer (components of the dielectric tensor of the ith
layer)
ρ Mass density
ε0 Permittivity of vacuum 1
1 ε0 = 8.85 10−12 F / m
200 Claire David
z Sh
6
6
zN
Layer N
zN −1
µ
x2
h
z2
Layer 2 b
z1
Layer 1
? -
a x1
¾ -
Figure 1. The multilayered piezoelectric plate.
1.2. Mechanical Study

1.2.1. Kinematic Assumptions
→
−
Assumptions 1.2. The displacement field U of any point M (xα, z) of the structure is deter-
→ →
− − − →
mined by its components (Uα , Uz ) in the basis i , j , k , which are approximated under
the following form:
P −1
Uα = uα + z ηα + f (z) ψα + g(z) γα0 + N m=1 (z − zm ) umα H(z − zm ) (1)
Uz = w
where
h π z h πz
f (z) = sin , g(z) = cos (2)
π h π h
and where H denotes the Heaviside step function.
Remark 1.1.
i. The Heaviside step function has been previously used, among others, by Di Sciuva
[18] and He [24].
ii. The use of the sine and cosine functions can be justified as in Touratier [49], by a
discrete layer theory from the three-dimensional modelling of Cheng [16] for thick
plates.
Definition 1.1. The uα are membrane displacements, the γα0 are the components of the
transverse shear stress at z = 0, w is the deflection, the ψα and umα are a priori unknown
functions, which are to be determined using the boundary conditions on the top and bottom
surfaces, as well as at layer interfaces.
1.2.2. Voigt Notation
The anisotropy of the piezoelectric materials requires using the two indices Voigt notation ;
we thus use the correspondance:
( 1, 1 ) ≡ 1 , ( 2, 2 ) ≡ 2 , ( 3, 3 ) ≡ 3
( 2, 3 ) ≡ 4 , ( 3, 2 ) ≡ 4
( 1, 3 ) ≡ 5 , ( 3, 1 ) ≡ 5
( 1, 2 ) ≡ 6 , ( 2, 1 ) ≡ 6
Notation. In the following, capital letters denote a couple of latin indices.
1.2.3. Uncoupled Constitutive Equations
Denote by Cmnkl (i) (or CKL (i) , Voigt notation) the components of the elastic strain tensor,
under a electric field, related to the ith layer, and by skl the components of the strain tensor
(or sI , Voigt notation).
Assumptions 1.3. We use, in the following, the assumption of small strains, which yields:
Uk,l + Ul,k
skl = (3)
2
Remark 1.2. The piezoelectric theory thus obtained is linear.
The uncoupled constitutive equations are:
σmn (i) = Cmnkl (i) skl (4)
or, Voigt notation:

(i) d
σJ = CJK (i) sK (5)
   
σ1 s1
 σ2   s2 
   
 σ3   s3 
 =C   (6)
 σ4   s4 
   
 σ5   s5 
σ6 s6
202 Claire David
1.3. Boundary Conditions

i. Conditions on the top and bottom surfaces of the plate:
The nullity of the uncoupled transverse shear stress on S0 and Sh yields:
( d
σ6−α (1) = 0
d (7)
σ6−α(N ) = 0
The latter system yields:

C6−α (1) {Uα,3(xα , 0; t) + w,α } = 0
(8)
C6−α (N ) {Uα,3(xα, h; t) + w,α } = 0
i. e.:
( P −1
ηα = −w,α − N m=1 umα
P (9)
ψα = 12 N −1
u
m=1 mα
ii. Layer interfaces conditions:

The continuity of the uncoupled shear stress at layer interface between ith and
(i + 1)th layers can be written as:
d d
σ6−α (i) (xα , zi) = σ6−α(i+1) (xα , zi) (10)
i. e.:
1 X 0 1 X 0
i−1 i

C6−α,6−α (i) g0 (zi ) γα0 + (f (zi )−1) um α = C6−α,6−α (i+1) g0 (zi ) γα0 + (f (zi )−1) um α
2 m=1 2 m=1
(11)
The linear system thus obtained enables us to express the umα , m = 1, . . . , N , as
functions of the transverse shears γα0 :
umα = λmα γα0 (12)
where the λmα are real constants, given by the resolution of the above system.
1.4. Final Form of the Kinematic Field

→
−
Proposition 1.4. The kinematic field U of a point M (xα, z) of the plate is given by:
P −1
Uα = uα − z w,α + f (z) ψα + N m=1 umα hα (z) (13)
Uz = w
where the hα are functions of the global thickness parameter z, given by:
N
X −1
1
hα(z) = g(z) + (f (z) − z) + (z − zm ) H(z − zm ) λmα (14)
2
m=1
This kinematic field has been developed in [12], [3], [5].
1.5. Electrical Study

1.5.1. Electrical Assumptions
Assumptions 1.5. The electrostatic potential is approximated under the form:
N
X −1
φ(xα, z; t) = ϕi (xα, z; t) χi(z) (15)
i=1
where the ϕi denote the potentials per layer, and the χi the characteristic functions per
layer:
i 1 si z ∈ [zi , zi+1[
χ (z) = (16)
0 else
Notation. Let us introduce, for each layer:
i. the thickness coordinate ξi , defined by:
2 (zi − zi0 )
ξi = (17)
hi
(see figure 2).
B
ii. the electrostatic potential on the bottom face, Si : ϕi = ϕi(xα , zi; t);
M zi+1 −zi
iii. the electrostatic potential on the mid-surface: ϕi = ϕi (xα, 2 ; t);
T
iv. the electrostatic potential on the top face, Si+1 : ϕi = ϕi (xα, zi+1 ; t);
ξi
6
T
ϕi
Si+1
6
M
hi Oi ϕi
?
Si
B
ϕi
Figure 2. The ith layer.

204 Claire David
Assumptions 1.6. The “potentials per layer" are assumed of the following form:
1 B M 1 T
ϕi (xα, z; t) = ξi (ξi −1) ϕi (xα; t)+(1−ξi 2 ) ϕi (xα; t)+ ξi (ξi +1) ϕi (xα; t) (18)
2 2
B T
Remark 1.3. In so far as: ϕi (xα, zi+1; t) = ϕi (xα , zi; t), the continuity of the electro-
static potential at layer interfaces of the potential is thus automatically satisfied.
B M
For this reason, we choose to keep, as unknowns quantities, the ϕi and ϕi .
B
For future applications, we shall suppose that p values of the ϕi are known.
1.5.2. Uncoupled Piezoelectric Constitutive Law
The uncoupled piezoelectric constitutive law takes the form:
D3 = −ε33 ϕ,3 + e3j sj (19)
1.5.3. Electric Boundary Conditions
Proposition 1.7. The electrostatic potential can be written as:

X B X M
ϕ(xα, z; t) = Qik (z; t) ϕik + Qjl (z; t) ϕjl (20)
ik ∈I jl ∈J
where the Qik , Qjl are polynomial functions of the global thickness coordinate z.
Proof. The continuity of D3 d on the top and bottom surfaces, and at the p layer interfaces
where the value of electrostatic potential is known, lead to a linear system of N + p − 1
B M
equations, which enable us to eliminate some of the ϕi and ϕi .
B M
Notation. Denote by ϕik , ik ∈ I, ϕjl , jl ∈ J, I and J being finite subsets IN, the
remaining unknowns quantities.
1.6. How to Take the Coupling into Account

The Need of Some Correction Factors
The resolution of the boundary problem enables us to obtain the values of the generalized
mechanical and electrical unknowns.
The sole quantity that cannot be obtained without an a posteriori treatment is the coupled
electric displacement.
We recall the coupled constitutive piezoelectric law:
D3 = −ε33 ϕ,3 + e3j sj (21)

The dielectric constants ε33 ϕ,3 are very small compared to the mechanical ones e3j sj .
So, if the final value of the electric displacement is not corrected a posteriori, mechanical
quantities e3j sj are going to be predominant.
Those terms are not continued at layer interfaces (see former section).
Proposition 1.8. The final electrical displacement is obtained, after correction, as:
X
N
D3 f inal (xα , z; t) = −ε33 ϕ,3 + e3j sj − [e3j (k) sj (k) (zk ) χk (z) − e3j (k+1) sj (k+1) (zk ) χk+1 (z)] (22)
k=1
1.7. The Linear Piezoelectric Constitutive Law

1.7.1. Tiersten Equations
→
−
Notation. We recall that s denotes the strain tensor, E the electrical field, C the elastic
strain tensor, under a constant electrical field, e the tensor of piezoelectric coefficients,
under constant strain, and ε the tensor of dielectric constants, under a constant strain.
i, j vary from 1 to 6, k, l from 1 to 3.
Properties. Tensors C, e, ε satisfy the following symmetry properties:
Cijkl = Cklij = Cjikl = Cijlk (23)
eijk = eikj (24)
εij = εji (25)
Proposition 1.9. The linear piezoelectric constitutive law is given by:

σij = Cijkl skl − ekij Ek
(26)
Dk = εij Ej + eijk sjk
or, under double indexation:

σI = CIJ sJ − ekI Ek
(27)
Dk = εkl El + ekI sI
206 Claire David
Remark 1.4. For orthotropic piezoelectric materials, as PVDF polymers, part of the piezo-
electric coefficients vanish; the tensors e and ε can thus be written as:
 
0 0 e31
 0 0 e32 
 
 0 0 e33 
e=


 (28)
 0 e24 0 
 e15 0 0 
0 0 0
 
ε11 0 0
ε =  0 ε22 0  (29)
0 0 ε33
Remark 1.5. Lots of piezoelectric materials, as PZT ceramics, or ZnO crystals, ..., are
transversally isotropic.
By choosing the orthotropy axis parallel to the vertical axis, the resulting simplifications
occur:
e31 = e32 , e24 = e15 , ε11 = ε22 (30)
1.7.2. Two-Dimensional Coefficients

Assumptions 1.10. In the following, the normal stress is assumed to be equal to zero.
Proposition 1.11. Under the assumption of nullity of the normal stress, the linear piezo-
electric constitutive law is given by:

σI = CIJ 2D sJ − ekI 2D Ek
(31)
Dk = εkl 2D el + ekI 2D sI
where:


 CIJ
2D
= CIJ − CI3 C 3J
C33
2D ek3
ekI = ekI − CI3 C33 (32)

 ε 2D = ε + e ek3
kl kl l3 C33
Proof 1.12. The assumption of nullity of the normal stress:
σ3 = 0 (33)
can be written as:

C3J sJ − ek3 Ek = 0 (34)
which enables us to eliminate the normal strain s3 :
ek3 C3α C3,6−α C36

s3 = Ek − sα − s6−α − s6 (35)
C33 C33 C33 C33
Substituting this expressions into (27), we obtain:
σI = CIJ sJ − ekI Ek
= CIα sα + CI,6−α s6−α + CI,6 s6 + CI3 s3 − ekI Ek

ek3 C3,6−α C36
= CIα sα + CI3 Ek − s6−α − s6 − ekI Ek
C33 C33 C33
(36)
C3α C3,6−α
= CIα − CI3 sα + CI,6−α − CI3 s6−α
C33 C33

C3,6 ek3
+ CI,6 − CI3 s6 − ekI − CI3 Ek
C33 C33
1.8. The Two-Dimensional Boundary Problem

1.8.1. Variational Formulation
Hamilton’s Principle yields:
Z t Z Z Z Z
−
→ −
→ −
→ −
→
{σi δsi + Di δϕi }dV + {fv · δ U + W δϕ} dV + fs · δ U dA + (p0 − ph ) dS dt = 0
0 V V A S0
(37)
→
− →
−
where δ denotes a variational operator, fv the density of external volumic forces, fs density
of external lateral forces, p0 and ph the pressures respectively acting on the top and bottom
surfaces of the structure, W the density of external surface electrical forces.
Notation. Let us introduce:
i. the generalized forces:
 Rh

 N1 α = − 0 {Cαj sj − e3α E3} dz

 Rh

 N2
αβ
= − 0 C66 s6 (1 − δαβ ) dz
Rh
N3 α = − 0 {Cαj sj − e3α E3} hα(z) dz (38)

 Rh

 N4αβ = − 0 C66 s6 (1 − δαβ ) hα(z) dz

 Rh
N5 α = − 0 21 {C6−α,6−α s6−α − e2,6−α E2}dz
208 Claire David
( Rh 0
N iB = − 0 E3 ε33 QiB (z)dz , i ∈ I
Rh 0 (39)
N jM = − 0 E3 ε33 QjM (z) dz , j ∈ J
ii. the generalized momentums:

( Rh
M1α = − 0 {Cαj sj − e3α E3} z dz
Rh (40)
M2 αβ = − 0 C66 s6 (1 − δαβ ) zdz
( Rh
α
MiB = − 0 {Eα εαα + ekα sα } QiB (z) dz , i ∈ I
α Rh (41)
MjM = − 0 {Eα εαα + ekα sα } QiM (z) dz , j ∈ J
iii. the generalized mechanical forces:

 Rh

 Fν 1 α = − 0 fν α dz

 Rh

 Fν 2 α = − 0 fν α z dz
Rh
Fν 3 α = − 0 fν α hα (z) dz (42)

 Rh

 Fν 3 = − 0 fν α dz


P = p0 − ph
iv. the generalized electrical forces:

( Rh
W iB = − 0 W QiB (z) dz , i ∈ I
Rh (43)
W jM = − 0 W QiB (z) dz , j ∈ J
iv. the inertia terms:

 Rh

 I1 = − 0 ρ dz

 Rh

 I2 = − 0 ρ z dz

 Rh

I3 = − 0 ρ hα(z) dz
Rh (44)

 I4 = − 0 ρ z 2 dz

 Rh

 I5 = − 0 ρ z hα (z) dz

 Rh

I6 = − 0 ρ z hα 2 (z) dz
Proposition 1.13. The movement equations are given by:


 N1α ,α + N2αβ ,β = I1 α üα − I2 ẅ,α + I3α γ̈α0


 M1 α ,αα + M2 αβ ,αβ = I2 α üα,α − I4 ẅ,αα + I5α γ̈α,α
0
+ I1 ẅ
N3 α,α + N4αβ ,β + N5α = α α 0
I3 üα − I5 ẅ,α + I6 γ̈α (45)

 α

 N iB + MiB ,α = 0 ,i∈I
 α
N jM + Mjm ,α = 0 ,j∈J
Proof 1.14. The movement equations are deduced from Hamilton’s Principle, in conjunc-
tion with the kinematic (13), and the constitutive equations (27), by integration through the
thickness of the plate.
Proposition 1.15. The boundary conditions leading to a regular problem are given by:

 N1α nα + N2αβ nαβ = Fν 1 α ou δuα = 0



 M1α ,α + M2 αβ ,β = Fν 2 α ou δw = 0


N4αβ nβ = Fν 3 α ou δγ 0α = 0
(46)

 M1 nα + M2 αβ nβ
α
= Fν3 ou δw,α = 0

 α

 N iB nα = W iB iB
ou δϕ = 0 , i ∈ I
 α
MjM nα = W jM ou δϕjM = 0 , j ∈ J
1.9. Numerical Validation of the Piezoelectric Plate Model

1.9.1. Free Vibrations of a Single-Layered Plate
Consider, in the following, a single-layered plate ( N = 1), made of PZT4 ceramic, simply
supported, in closed circuit (which means that the electrostatic potential on its top and
B T
bottom surfaces is equal to zero: ϕ1 = ϕ1 = 0) (see figure 3).
z
6
6
h PZT 4 0V
m
?
O
Figure 3. Single-layered piezoelectric plate, in closed circuit
Data 1.16. Material constants of the ceramic PZT4 can be found in tables 1, 2.
Proposition 1.17. The simply supported boundary conditions yield:
w(xα = 0, z; t) = w(xα = a, z; t) = 0 (47)

210 Claire David
Table 1. Independent elastic constants of the PZT4 ceramic (in GP a)
C11 C22 C33 C12 C13 C23 C44 C55 C66

PZT 4 139 139 115 77.8 74.3 74.3 25.6 25.6 30.6
Table 2. Independent piezoelectric and dielectric constants of the PZT4 ceramic ( eij
in C/m2 , εii in nF/m)
e31 e32 e33 e15 ε11 ε22 ε33

PZT 4 −5.2 −5.2 15.1 12.7 13.06 13.06 11.51
Proposition 1.18. The electrostatic potential (20) is approximated as (18)

M
ϕ1(xα , z; t) = (1 − ξ1 2) ϕ1 (xα ; t) (48)
The generalized mechanical unknowns are the membrane displacements uα , the deflection
w, and the transverse shear stresses γα0 .
M
The generalized electrical unknown is ϕ1 .
Assumptions 1.19. The solution is searched under the following form, which characterizes
the propagation of two-dimensional plane waves:


 u1 = A1 e j ω t cos( π ax1 ) sin( π bx2 )


 u2 = A2 e j ω t sin( π ax1 ) cos( π bx2 )
M π x1 π x2
w = B ej ω t sin( π ax1 ) sin( π bx2 ) , ϕ1 = Φ1 e j ω t sin( ) sin( )

 a b

 γ 1
0 = C1 e j ω t cos( π ax1 ) sin( π ax2 )
 0
γ2 = C2 e j ω t sin( π ax1 ) cos( π ax2 )
(49)
and which enables us to satisfy the simply supported boundary conditions (47).
By substituting these expressions into the equations of motion given by equations (13), in
conjunction with the boundary conditions (45), the constitutive law (31) and the displace-
ment field (13), we obtain a linear system in Aα , B, Cα , Φ1 , under the form:
 
A1
 A2 
 
 B 
2
[K1 − ω M1 ]   =0 (50)

 C1 
 C2 
Φ1
The detail of coefficients of the matrices K1, M1 is given in [7].
The system admits a non trivial solution if its determinant vanishes:
det[K1 − ω 2 M1] = 0 (51)
A symbolic calculus tool (Mathematica or Maple) enables us to calculate the free pulsations
of the considered plate, and to compare them to Heyliger’s analytical solution (see Table 3).
Table 3. Free pulsations of the single-layered piezoelectric plate (in rad.s−1 )
Model Exact solution

a
h =4 194297.102 194255.102
335054.102 327663.102
a
h = 10 7771870 7770210
134022.102 133695.102
a
h = 50 15 54370 1554040
2680440 26828.102

j
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 4. Electrostatic normalized potential, single-layered plate, a = 4 h. In gray: exact

solution. In black: our model.
Figures 4, 5 display the variations, as functions of the global thickness coordinate, of the
normalized electrostatic potential:
ϕ(xα, z; t)
ϕ(z; t) = (52)
ϕ(xα = a2 , z = h2 ; t)
for significative values of the plate’s thickness: a = 4 h, and a = 10 h.
Results perfectly fit the exact solution.
212 Claire David

j
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 5. Electrostatic normalized potential, single-layered plate, a = 10 h. In black: our

model.
1.9.2. Free Vibrations of a 5-Layered Plate

Consider, in the following a 5-layered plate (N = 5), the external layers of which are
made of PZT 4 ceramic, with a core made of an arrangement 0 / 90 / 0 of epoxy resin,
simply supported, in closed circuit (which means that the electrostatic potential on its top
B T
and bottom surfaces is equal to zero: ϕ1 = ϕ3 = 0) (see figure 6).
z
6
6 PZT 4
Epoxy 0
h Epoxy 90 0V
Epoxy 0
m
? PZT 4
O
Figure 6. 5-layered piezoelectric plate
h
Data 1.20. The respective thicknesses of the external layers are h1 = h5 = 10 , those of
each of the epoxy resin, h2 = h3 = h4 = 13 810h .
Data 1.21. Material constants of the ceramic PZT4 and the epoxy resin are given in tables
4, 5.
Table 4. Independent elastic constants of PZT4 and epoxy resin (in GP a) .
C11 C22 C33 C12 C13 C23 C44 C55 C66

PZT 4 139 139 115 77.8 74.3 74.3 25.6 25.6 30.6
Epoxy 134.6 14.352 14.352 5.1563 7.1329 3.606 5.654 5.654 5.654
Table 5. Independent piezoelectric and dielectric constants of PZT4 and epoxy resin
(eij in C/m2 , εii in nF/m)
e31 e32 e33 e15 ε11 ε22 ε33

PZT 4 −5.2 −5.2 15.1 12.7 13.06 13.06 11.51
Epoxy 0 0 0 12.7 0.031 0.0266 0.0266
w(xα = 0, z; t) = w(xα = a, z; t) = 0 (53)
Lemma 1.23. Electrical and dielectric properties of the 3 layers of the core of the plate
being identical, they behave, under an electrical point of view, as a single layer.
Lemma 1.24. We thus take into account, for the 5-layered plate, a 3-layered type modelling,
with an elastic core of epoxy resin.
Proposition 1.25. The electrostatic potential (20) is approximated as:
M
ϕ(xα, z; t) = Q2M (z) ϕ2 (54)
where:
M
Q2M (z) = (1 − ξ12 ) λ1M,2M + 12 ξ1 (ξ1 + 1) λ2B,2M χ1 (z)
+ 12 ξ2 (ξ2 − 1) λ2B,2M + (1 − ξ22 ) + 12 ξ2 (ξ
2 + 1) λ
2B,2M χ2 (z) (55)
+ 12 ξ3 (ξ3 − 1) λ2B,2M + (1 − ξ32 ) λ1M,2M χ3 (z)
214 Claire David
Proof 1.26. Symmetries of the problem yield:

B B M M
ϕ2 (xα ; t) = ϕ3 (xα ; t) , ϕ1 (xα; t) = ϕ3 (xα; t) (56)
The approximation of the electrostatic potential (20), (18) becomes thus:
M T
ϕ(xα , z; t) = (1 − ξ1 2 ) ϕ1 (xα ; t) + 12 ξ1 (ξ1 + 1) ϕ1 (xα; t) χ1 (z)
1 B M B
+ ξ (ξ − 1) ϕ2 (xα ; t) + (1 − ξ2 2 ) ϕ2 (xα ; t) + 12 ξ2 (ξ2 + 1) ϕ2 (xα; t) χ2 (z)
21 2 2 B M
+ ξ (ξ3 − 1) ϕ2 (xα ; t) + (1 − ξ3 2 ) ϕ1 (xα ; t) χ3 (z)
2 3
(57)
The continuity of the uncoupled electrical displacement at layer interfaces can be written
as:

−ε33,11 ϕ,31 (xα, z1; t) = −ε33,12 ϕ,3 2(xα , z1; t)
(58)
−ε33,12 ϕ,31 (xα, z2; t) = −ε33,11 ϕ,3 3(xα , z2; t)
M B
We thus have a linear system, which enables us to express ϕ1 and ϕ2 as functions of
M
ϕ2 , under the following form:
(
M M M
ϕ1 = λ1M,2M ϕ2
B M M (59)
ϕ2 = λ2B,2M ϕ2
The generalized mechanical unknowns are membrane displacements uα, the deflection w,
and the transverse shear stresses γα 0.
M
Assumptions 1.27. In the same way as for the single-layered plate, the solution is searched
under the form (167):


 u1 = A1 e j ω t cos( π ax1 ) sin( π bx2 )


 u2 = A2 e j ω t sin( π ax1 ) cos( π bx2 )
M π x1 π x2

 a b

 γ 0 = C1 e j ω t cos( π ax1 ) sin( π ax2 )
 10
γ2 = C2 e j ω t sin( π ax1 ) cos( π ax2 )
(60)
which enables us to satisfy the simply supported boundary conditions (53).
By substituting these expressions into the equations of motion given by equations (13), in
conjunction with the boundary conditions (45), the constitutive law (31) and the displace-
ment field (13), we obtain a linear system in Aα , B, Cα , Φ1 :
 
A1
 B 
[K5 − ω 2 M5 ]  
 C1  = 0 (61)
Φ2

j
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 7. Normalized electrostatic potential, 5-layered plate, a = 4 h. In gray: the exact

Detail of coefficients of matrices K5 and M5 is given in [7].
The system admits a non trivial solution if its determinant vanishes:
det[K5 − ω 2 M5] = 0 (62)
A symbolic calculus tool (Mathematica or Maple) enables then us to calculate the free
pulsations of the considered plate, and to compare them with Heyliger’s analytical solution
[25] (see 6).
Table 6. Free pulsations of the 5-layered piezoelectric (in rad.s−1)
Model Exact solution

a
h =4 194903.102 191301.102
251763.102 250769.102
a
h = 10 1559230 1568100
209479.102 209704
Figure 7 displays the variations, as a function of the global thickness coordinate z, of the
ϕ(xα, z; t)
ϕ(z; t) = (63)
ϕ(xα = a2 , z = h2 ; t)
216 Claire David

D 33
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 8. Normalized electric displacement, 5-layered plate, a = 4h. In gray: the exact
normalized electric displacement:
D3 (xα, z; t)
D3 (z; t) = (64)
D3 (x1 = 0, x2 = a2 , z = h; t)
normalized transverse shear stress:
σ13(xα, z; t)
σ13 (z; t) = (65)
σ13 (x1 = 0, x2 = a2 , z = h2 ; t)
normalized longitudinal shear stress:
σ11(xα, z; t)
σ11 (z; t) = (66)
σ11 (xα = a2 , z = 0; t)
1.10. Applications of the Piezoelectric Plate Model

In the following, we present applications of the piezoelectric plate model; more results can
be found in [7].

Σ 13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 9. Normalized transverse shear stress, 5-layered plate, a = 4 h. In gray: the exact
1.10.1. Bimorph Plate under Mechanical Loading

Consider a rectangular plate, of width a, bimorph 1 , supposed of infinite length, made of
PZT4 ceramic, under cylindrical bending, simply supported, submitted to a force density p
on its top face, in closed circuit (which means that the electrostatic potential on the top and
B T
bottom surfaces is equal zero): ϕ1 = ϕ3 = 0) (see figure 11).
Proposition 1.28. The plate being supposed of infinite length, mechanical and electrical
quantities (stresses, strains, displacements, electric field, electrostatic potential) do not de-
pend on x2.
Assumptions 1.29. Since the component U2 of the displacement field does not play any
part, we shall take:
U2 = 0
Data 1.30. Material constants of PZT4 ceramic are given in tables 1, 2.
Proposition 1.31. The simply supported boundary conditions can be written as:
w(x1 = 0, z; t) = w(x1 = a, z; t) = 0 (67)
1
A bimorph plate is a structure made of two identical materials, but with opposed polarization
axes: e3α2 = −e3α 1, e15 2 = −e151 , e242 = −e24 1
218 Claire David

Σ 11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 10. Normalized longitudinal shear stress, 5-layered plate, a = 4 h. In gray: the
exact solution. In black: our model.
Assumptions 1.32. The force density p is assumed to be simply sinusoidal:

π x1
p (xα, z; t) = p0 e j ω t sin( ) (68)
a
where p0 = 0.05M P a.
Proposition 1.33. The electrostatic potential (20) can be written as:

M
ϕ(xα, z; t) = Q1M (z) ϕ1 (69)
where:
Q1M (z) = (1 − ξ1 2) χ1 (z) − (1 − ξ22 ) χ2 (z) (70)
Proof 1.34. The antisymmetry of the problem yields:

M M
ϕ2 = −ϕ1 (71)
Remark 1.6. The piezoelectric coefficients of both layers being identical, no continuity
conditions are required for the electrical displacement.
The generalized mechanical unknowns are the membrane displacements uα , the deflection
w, and the transverse shear stresses γα0 .
M
The generalized electrostatic unknown is ϕ1 .
z
6
p
? ? ? ? ? ? ?
6
h 0V
j
? O
Figure 11. Bimorph plate under mechanical loading

Σ
13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 12. Normalized transverse shear stress, bimorph plate under mechanical loading,
a = 5 h.
Assumptions 1.35. In the same way as for the single layered plate, the solution is searched
as (167):
 πx πx
 u1 = A1 e j ω t cos( a 1 ) sin( b 2 ) π x1 π x2
π x1 π x2 M
w = Be jωt
sin( a ) sin( b ) , ϕ1 = Φ1 e j ω t sin( ) sin( )
 0 a b
γ1 = C1 e j ω t cos( π ax1 ) sin( π ax2 )
(72)
By substituting these expressions into the equations of motion given by equations (13),
in conjunction with the boundary conditions (45), the constitutive law (31) and the displace-
ment field (13), we obtain a linear system in A1 , B, C1 , Φ1 , of the form:
 
A1
 B 
K2  
 C1  = B2 (73)
Φ1
220 Claire David

Σ
11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 13. Normalized longitudinal stress, bimorph plate under mechanical loading, a =
5 h. In gray: exact solution. In black: our model.
Detail of the coefficients of the matrices K2 and of the vector B2 is given in [7].
Figure 14 displays the variations, as a function of the global thickness parameter z, of the
ϕ(xα, z; t)
ϕ(z; t) = (74)
ϕ(xα = a2 , z = h2 ; t)
σ13(xα, z; t)
σ13 (z; t) = (75)
σ13 (x1 = 0, x2 = a2 , z = h2 ; t)
normalized longitudinal stress:
σ11(xα, z; t)
σ11 (z; t) = (76)
σ11 (xα = a2 , z = 0; t)
normalized longitudinal displacement:
U1 (xα, z; t)
U 1(z; t) = (77)
U1 (xα = a2 , z = 0; t)

j
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 14. Normalized electrostatic potential, bimorph plate under mechanical loading,
a = 5 h. In gray: exact solutio. In black: our model.

U1
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 15. Normalized longitudinal displacement, bimorph plate under mechanical loading,
a = 5 h. In gray: exact solution. In black: our model.
222 Claire David
1.10.2. Bimorph Plate with Imposed Potentials
Consider a rectangular plate, of width a, bimorph, supposed of infinite length, made of

PZT4 ceramic, under cylindrical bending, simply supported, submitted, on its top face, to
an electrostatic potential +V , and, on its bottom face, to an electrostatic potential −V (see
figure 16).
z
6
+V
m
? O
−V
Figure 16. Bimorph plate, with imposed potentials
Proposition 1.36. The plate being supposed of infinite length, the mechanical and electrical
quantities (stresses, strains, displacements, electric field, electrostatic potential), do not
depend on x2 .
j
1
0.75
0.5
0.25
0.2 0.4 0.6 0.8 1z h
-0.25
-0.5
-0.75
-1
Figure 17. Normalized electrostatic potential, bimorph plate with imposed potentials, a =
4 h. In gray: exact solution. In black: our model.

Σ
13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 18. Normalized transverse shear stress, bimorph plate with imposed potentials, a =
5 h.
Assumptions 1.37. Since the component U2 of the kinematic field does not play any part,
we shall take:
U2 = 0
Data 1.38. Material constants of the PZT4 ceramic are given in tables 1, 2.

Σ
11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 19. Normalized longitudinal stress, bimorph plate with imposed potentials, a = 5 h.
w(x1 = 0, z; t) = w(x1 = a, z; t) = 0 (78)

224 Claire David
Assumptions 1.40. The potential V is assumed to be simply sinusoidal:

π x1
V (xα, z; t) = V0 e j ω t sin (79)
a
Figure 20. The multilayered piezoelectric shell.
Proposition 1.41. The electrostatic potential (20) can be written as:

1 M 1 M
ϕ(xα , z; t) = − ξ1 (ξ1 −1) V +(1−ξ1 2 ) ϕ1 (xα ; t)+ χ1 (z) ξ2 (ξ2 +1) V −(1−ξ2 2 ) ϕ1 (xα ; t) χ2 (z)
2 2
(80)
Proof 1.42. The antisymmetry of the problem yields:

M M
ϕ2 = −ϕ1 (81)
Remark 1.7. The dielectric coefficients of both layers being identical, no continuity condi-
tions are required for the electrical displacement.
The generalized mechanical unknowns are membrane displacements uα, w, and the trans-
verse shears γα0 .
M
Assumptions 1.43. As well as for the single-layered plate, the solution is searched as (167):
 πx πx
 u1 = A1 e j ω t cos( a 1 ) sin( b 2 ) π x1 π x2
M
 1 a b
γ0 = C1 e j ω t cos( π ax1 ) sin( π ax2 )
(82)
By substituting these expressions into the equations of motion given by equations (13),
in conjunction with the boundary conditions (45), the constitutive law (31) and the displace-
ment field (13), we obtain a linear system in A1 , B, C1 , Φ1 :
 
A1
 B 
K2  
 C1  = B2 (83)
Φ1
The detail of coefficients of the matrices K2 and of the vector B2 is given in [7].
ϕ(xα, z; t)
ϕ(z; t) = (84)
ϕ(xα = a2 , z = h2 ; t)
σ13(xα, z; t)
σ13 (z; t) = (85)
σ13 (x1 = 0, x2 = a2 , z = h2 ; t)
σ11(xα, z; t)
σ11 (z; t) = (86)
σ11 (xα = a2 , z = 0; t)
2. Multilayered Piezoelectric Shells Modelling

We hereafter study the modelling of multilayered piezoelectric shells. Our theory is based
on the same hybrid approach as previously: the electrical and mechanical continuity con-
ditions at layer interfaces are satisfied, as well as the boundary conditions on the top and
bottom surfaces of the shell.
The accuracy of our theory is assessed through investigation of significant problems,
for which an exact three-dimensional solution is known.
2.1. Introduction
The modeling of piezoelectric shells mostly concerns cases attached to specific geome-
tries (cylindrical, spherical). Toupin [48] studied the static response of a radially polarized
spherical piezoelectric shell. Adelman et al.[13], [14] examined cases involving hollow
piezoelectric cylinders. Sun et al. [45], Karlash [27] studied wave propagation in layered
piezoelectric cylinders. Paul et al. [40], [41] examined free vibration problems. Siao et
al. [44] ] proposed a semi-analytic model for layered piezoelectric cylinders taking into
account a layerwise behavior of the composite.
226 Claire David
Analytic solutions for laminated piezoelectric cylinders were proposed by Mitchell et

al. [35], Xu et al. [57], Heyliger [26], Dumir et al. [20], Drumheller et al. [19]. For
this purpose, Drumheller [19] used classical shell theory for free vibrations of shells of
revolution.
Haskins et al. [23] proposed the development of electrical and mechanical quantities
as expansions of the thickness variable. Tzou et al. [52] proposed the development of
electrical and mechanical quantities as expansions of the thickness variable.
It was done by Tzou et al. [53], this time with a shear-deformation theory. Other
piezoelectric shell models and finite element approximations, based on single-layer models
were also developped by Tzou et al. [54].
A Reissner-Mindlin shear-deformation shell finite element with surface bonded piezo-
electric layers was developped by Lammering [29].
Koconis et al. [28] used a Ritz method for three-layered shells with embedded piezo-
electric actuators. Tzou et al. [54] proposed a coupled theory where the piezoelectric
shells are considered as a layerwise assembly of curvilinear solid piezoelectric triangular
elements.
Heyliger et al. [26] developed a finite-element for laminated piezoelectric shells.
Saravanos [43] used a coupled mixed theory for curvilinear composite piezoelectric
laminates with the first-order shear deformation theory hypothesis and a layerwise approxi-
mation of the electrostatic potential, along with the corresponding finite element for piezo-
electric shells.
We presently extend our piezoelectric plate model to shells. As previously, we asso-
ciate our displacement type approach, which is a “single-layered" one, continuous at layer
interfaces, to quadratic variations through the thickness of the electrostatic potential, also
continuous. The transverse shear stresses, under a constant electrical field, as well as the
electrical displacement, under a constant strain, are also continuous. Refinements of the
membrane and transverse shear stresses are taken into account by means of trigonometric
functions.
Also, the conditions at layer interfaces, where values of the electrostatic potential can
be imposed, are satisfied.
Finally, the piezoelectric boundary value problem is constructed using the consistant
coupled constitutive law, in conjunction with the above displacements and electrostatic po-
tential fields. The proposed piezoelectric shell model is evaluated for significant problems,
for which the exact three-dimensional solution is known [26].
2.2. Mechanical Study

Consider an undeformed laminated shell of constant thickness h. The space occupied by
the shell will be denoted V. The boundary of the shell is the reunion of the upper surface
Sh , the lower surface S0 , and the edge faces A. consisting of an arrangement of a finite
number N of piezoelectric layers.
a denotes the length, b the width, h its thickness, and V the volume occupied by the shell
(see figure 1.10.2.).
Notation.
V Volume occupied by the shell
h Total thickness of the shell
R Radiius of curvature of the shell
R1, R2 Main radii of curvature of the reference surface
S0 Bottom surface of the shell
Sh Top surface of the shell
Si Bottom surface of the ith layer
zi Distance between S0 and Si
zi0 Distance between S0 and the mid surface of the ith layer
A Lateral surface of the shell
(−
→ai ) Covariant basis
(−
→gi ) Covariant basis
→i
−
(a ) Contravariant basis
→
−
( gi ) Contravariant basis
δα β Kronecker symbol
bαβ Covariant components of the curvature tensor
bαβ Mix components of the curvature tensor
(xi ) Curvilinear coordinatess
Li Lamé coefficients
sk , k = 1, . . . , 6 Strains
σk , k = 1, . . . , 6 Stresses
Cmnpq (i) , or CKL (i) Components of the elastic stiffness tensor
under a constant electrical field
0
Differentiation with respect to z
|i Covariant derivation with respect to xi
.
Differentiation with respect to time t
δ Variational operator
ϕ Electrostatic potential
B
ϕ1 Electrostatic potential on S0
B
ϕN +1 Electrostatic potential on Sh
B
ϕi Electrostatic potential on Si
M
ϕi Electrostatic potential on the midsurface of the ith layer
T
ϕi Electrostatic potential sur Si+1
→
−
El , l = 1, . . . , 3 Components of the electric field E
Dk , k = 1, . . . , 3 Components of the electric displacement
ekl (i) Piezoelectric constants, under a constant strain,
of the ith layer
εkl (i) Dielectric constants, under a constant strain,
of the ith layer (or components of the tensor of permittivities of
the ith layer)
ρ Mass density
ε0 Permittivity of vacuum 1
1 ε0 = 8.85 10−12 F / m
228 Claire David
Notation. The frontier of the shell is constituted by the reunion of its bottom surface S0 ,
its top surface Sh , and its lateral surface A.
Si denotes the interface between the ith and (i + 1)th layers, and zi the distance between
S0 and Si .
The reference surface coïncides with the bottom surface S0 .
Notation. The Einsteinian summation convention applies to repeated indices, where Latin
indices range from 1 to 3 while Greek indices range from 1 to 2.
2.2.1. Geometric Considerations for Shells

A point M out of the reference surface being given, let us denote by P the point of the
reference surface closest to M . →
− →
−
Covariant base vectors (−ai ) , (−
→ →
gi ), and contravariant base vectors ( ai ) , ( g i ), are defined
by:
→
−
a1 ∧ −→
a2 →
−
a→ = P , −
→
a = , − →
a1 ∧ −
→
a2 · −
a3 > 0 (87)
α ,α 3 →
− →
−
ka1 ∧ a2 k
( −→
−
a→ β
= δα β
α ·a
→3
− (88)
a = − →
a 3
−
→ −
→ →
gi = M,i , g1 ∧ −
→
g2 · −
g3 > 0 (89)
( −
→
−
g→ β = δ β
α·g α
→3
− (90)
g = g3−
→
Thus:
P = M +z−
→
a3 (91)
Notation. Let us introduce:
aαβ = −
a→ −
→ −
→ − →
α · aβ , gαβ = gα · gβ (92)
Proposition 2.1.
− → −
− →
a→ β β
β = aαβ a , a = a
αβ −
a→
β (93)
− −
→ − → −
→ −
→ → →
−
g→ β −→ β α α −1 β
α = µ α aβ = gαβ g , g = −µ β gβ , g 3 = a3 = −
a = g αβ −
→ a3 (94)
Definition 2.1. The mixed components of the shifter tensor are given by:
µα β = δ α β − z bα β (95)
The covariant components of the curvature tensor are given by:
→3
−
bαβ = −
a→
α,β · a (96)
The mixed components of the curvature tensor are given by:
−
→
bαβ = −−
→
a3,β · aα (97)
Assumptions 2.2. In the following, the curvilinear coordinates (or shell coordinates) are
assumed to be orthogonal, and are such that the curves x1 = constant, x2 = constant
are lines of curvature on the reference surface.
The curves z = constant are straight lines perpendicular to the surface S0 .
R1, R2 denote the principal radii of curvature of the reference surface.
Proposition 2.3. The distance between two points P (x1 , x2, 0) and P 0 (x1 + dx1 , x2 +
dx2, 0) of the reference surface is given by:
ds2 = α1 2 dx12 + α2 2 dx22 (98)
where α1 and α2 are the coefficients of metrics, given by:
∂P ∂P
αl 2 = l = 1, 2 (99)
∂xl ∂xl
Proposition 2.4. The distance between two points M (x1, x2, x3) and M 0(x1 + dx1, x2 +
dx2, x3 + dx3), out of the reference surface, is given by:
ds2 = L12 dx12 + L2 2 dx22 + L32 dx32 (100)
where L1, L2 and L3 denote the Lamé coefficients, given by:
z z
L1 = αl 1 + , L2 = αl 1 + , L3 = 1 (101)
R1 R2
230 Claire David
2.3. Kinematic Assumptions

→
−
Assumptions 2.5. The displacement field U of a point M (xα, z) of the shell, is defined by
→ →
− −
its components (Uα, Uz ) in the covariant basis g α, g 3 , approximated under the form:
P −1
Uα = uα + z ηα + f (z) ψα + g(z) γα0 + N m=1 (z − zm ) umα H(z − zm ) (102)
Uz = w
where:
h π z h πz
f (z) = sin , g(z) = cos (103)
π h π h
where H denotes the Heaviside step function.
As in the previous part, the use of the sine and cosine functions can be justified as in
Touratier [49], by a discrete-layer approach, from the three-dimensional modelling of
Cheng [16] for thick plates.
The uα are membrane displacements, the γα0 the components of the transverse shear
stress at z = 0, w the deflection, ψα and umα a priori unknown functions , which will be
determined thanks to the conditions at layer interfaces as well as on the top and bottom
surfaces.
2.4. Uncoupled Constitutive Law

Let us denote by Cmnkl (i) (or CKL (i), double indexation) the components of the elastic
stiffness tensor, under a constant electric field, of the ith layer, and by skl the components
of the stress tensor (or sI , double indexation).
Assumptions 2.6. We use, in the following, the hypothesis of small pertubations,which

yields:
Vkkl + Vlkk
skl = (104)
2
where:

 Vαkβ = µν α [ Uν|β − bνβ w ]
V = µν α Uν,3 (105)
 αk3
V3k3 = U3,3
Remark 2.1. Equations (105) yield:

 P −1

 Vαkβ = µν α [ uν|β + z ην|β + f (z) ψν|β + g(z) γ 0 ν|β + Nm=1 (z − zm ) umν|β H(z − zm ) − bνβ w ]
 ν 0 0 0 PN −1
Vαk3 = µ α [ην + f (z) ψν + g (z) γα ν + m=1 um ν| H(z − zm ) ]
P −1

 V = w|α + bν α [uν + z ην + f (z) ψν + g(z) γ 0 ν + N m=1 (z − zm ) um ν H(z − zm )]
 3kα
V3k3 = w,3
(106)
Especially:
sα3 = 12 [ Vαk3 + V3kα ]

P −1
= 12 µν α [ην + f 0 (z) ψν + g 0(z) γα0 ν + N
m=1 umν H(z − zm ) ]
P
+ w|α + b α [uν + z ην + f (z) ψν + g(z) γ ν + N
ν 0 −1
m=1 (z − zm ) umν H(z − zm )]
(107)
The uncoupled constitutive law yields:
σmn (i) = Cmnkl (i) skl (108)
i.e., under double indexation:

(i) d
σJ = CJK (i) sK (109)
   
σ1 s1
 σ2   s2 
   
 σ3   s3 
 =C   (110)
 σ4   s4 
   
 σ5   s5 
σ6 s6
2.5. Boundary Conditions

i. Conditions on the top and bottom surfaces:
Proposition 2.7. The zero value of the transverse shear stress on S0 and Sh , under
a constant electric field, yields:
h 0
ηα = −ψα − w|α − bν α [uν + γ ] (111)
π ν
and:
N
X −1
β 0
ψα = d αγ β + fm β α umβ (112)
m=1
where:
(
−1
[ dβ α ] = [ h bβ α − 2 δ β α ] [ 2πh bβ α ]
−1 (113)
fm β α = [h bβ α − 2 δ β α] [δ β α − bβ α zm ]
232 Claire David
Proof. The nullity of the transverse shear stress on S0 and Sh , under a constant elec-
tric field, can be written as:
( d
σ6−α (1) = 0
d (114)
σ6−α(N ) = 0
which yields:

sα3(z = 0) = 0
(115)
sα3 (z = h) = 0
i.e., according to (107):
1 ν h h
sα3 (z = 0) = −δ α [ην + ψν ] + w|α + bν α [uν + γ 0 ν ] (116)
2 π π
and:
1 ν X
N −1
h X
N −1

sα3 (z = h) = µ α [ην − ψν + um ν ] + w|α + bν α [uν + h ην − γ 0 ν + (h − zm) um ν ]
2 m=1
π m=1
(117)
since:
h
f (0) = g 0(0) = f (h) = g 0(h) = 0 , f 0 (0) = −f 0 (h) = 1 , g(0) = −g(h) =
π
(118)
µν α = δ ν α − z bν α (119)
we thus have:
1 h
sα3 (z = 0) = ηα + ψα + w|α + bν α [uν + γ 0ν ] (120)
2 π
and:
1 ν X
N −1
h X
N −1

sα3 (z = h) = µ α [ην − ψν + um ν ] + w|α + bν α [uν + h ην − γ 0 ν + (h − zm) um ν ]
2 m=1
π m=1
(121)
1
sα3 = [Vαk3 + V3kα ]
2 P −1
= 1
µν α [ην + f 0 (z) ψν + g0 (z) γν0 + N
m=1 um H(z − zm ) ]
2 Pν −1
+ w|α + bν α [uν + z ην + f (z) ψν + g(z) γ 0 ν + Nm=1 (z − zm ) um ν H(z − zm )]
(122)
Hence:
h 0
ηα = −ψα − w|α − bν α [uν + γ ] (123)
π ν
and:
N
X −1
ν h 0
−2 ψα + b α ψν n − 2 γ ν + (δ ν α − bν α zm ) umν = 0 (124)
π
m=1
which can be written as:
N
X −1
ψα = dβ α γ 0β + fm β α umβ (125)
m=1
where:
(
−1
[ dβ α ] = [ h bβ α − 2 δ β α ] [ 2πh bβ α ]
−1 (126)
fm β α = [h bβ α − 2 δ β α] [δ β α − bβ α zm ]
By substituting these expressions in (123), we deduce:
N
X −1
β 0 h 0
ηα = −d αγ β − fm β α umβ − w|α − bν α [uν + γ ] (127)
π ν
m=1
We then have, thanks to (122):

sα3 = 12 [ µν α + z bν α ] ην + [ µν α f 0 (z) + bν α f (z) ] ψν
+ [µν α g 0(z)bν α g(z) ] γα0ν
PN −1 ν ν (128)
+ m=1 [µ α + b α (z − zm ) ] umν H(z − zm )
ν
+ w|α + b α uν
i.e.:
ν P −1 β
sα3 = 1
[ µ α + z bν α ] {−dβ ν γ 0β − N m=1 fm ν umβ − w|ν − bλν [uλ + πh γ 0λ]}
2 P
+ [ µν α f 0(z) + bν α f (z) ] { dλν γ 0λ + N −1 λ
m=1 fm ν umβ }
+ [µν α g 0(z)bν α g(z) ] γν0
PN −1 ν
+ m=1 [µ α + bν α (z − zm ) ] umν H(z − zm )
+ w|α + bν α uν
(129)
234 Claire David
ii. Conditions at layer interfaces:

The continuity of the uncoupled transverse shear stress between the ith and (i + 1)th
layer can be written as:
d d
σ6−α (i) (xα , zi) = σ6−α(i+1) (xα , zi) (130)
Thanks to (129), we then obtain a linear system of N − 1 equations, which enables

us to express the umα , m = 1, . . . , N − 1 as functions of the transverse shears γα0 :
umα = λmα γα0 (131)
where the λmα are real constants, given by the resolution of the latter system.
2.6. Final Form of the Displacement Field

→
−
Proposition 2.8. The displacement field U of any point M (xα, z) of the structure is given
by:
Uα = µβ α uβ − z w|α + hβ α γ 0β
(132)
Uz = w
where the hβ α are functions of the global thickness variable z, given by:
N
X −1 n o
h β
hβ α (z) = g(z) δβ α − z b α + [f (z) − z] dβ α + f(m) β α + (z − zm ) H(z − zm ) δβ α λm β (133)
π m=1
This displacement field has been developed in [12], [5], [3].
2.7. Electrical Study; the Linear Piezoelectric Constitutive Law

This section refers to the same results as in the case of the plate (see above)
2.8. The Two-Dimensional Boundary-Value Problem

2.8.1. Variational Formulation
Hamilton’s Principle yields:
Z t Z Z Z Z
→ →
− − −
→ −
→
{σi δsi + Di δϕi }dV + {fv · δ U + W δϕ} dV + fs · δ U dA + (p0 − ph ) dS dt = 0
0 V V A S0
(134)
−
→ →
−
δ being a variational operator, fv the volumic density of body forces, fs the surface density
of body forces on the lateral surface of the shell, p0 and ph the prescribed components of
traction on the top and bottom surfaces, and W the density of electric forces.
Notation. µ denotes the value of the determinant of shifter tensor [µβ α ] at z = 0.

Let us ntroduce:
i. the generalized stresses:
 Rh

 N1 αβ = − 0 {Cλj sj − e3α E3 } µν λ µα ν µ dz

 Rh

 N2 αβ = − 0 C66 s6 (1 − δλβ ) µν λ µα ν µ dz

 Rh
N3 = − 0 {Cαj sj − e3α E3 } µν α bνα + C66 s6 (1 − δαβ ) µν α bνβ µ dz
α
Rh ν α (135)

 N 4 = − 0 C6−λ,6−λ s6−λ,6−λ − ek,6−λ Ek { µ λ h ν,3 + bν λ hα ν } µ dz

 Rh

 N5 α = − 0 {Cλj sj − e3α E3 } µν λ hα ν (z) µ dz

 Rh
N6 α = − 0 C66 s6 (1 − δλβ ) µν λ hα ν (z) µ dz
( Rh 0
N iB = − 0 E3 ε33 QiB (z) µ dz , i ∈ I
Rh 0 (136)
N jM = − 0 E3 ε33 QjM (z) µ dz , j ∈ J
ii. the generalized momentums:
( Rh
M1 αβ = − 0 { Cαj sj − e3α E3 } µν α + C66 s6|νβ (1 − δαβ ) µν α z µ dz
Rh
M2 αβ = − 0 C66 s6 (1 − δαβ ) z µ dz
(137)
( Rh
α
MiB = − 0 {Eα εαα + ekα sα } QiB (z) µ dz , i ∈ I
α Rh (138)
MjM = − 0 {Eα εαα + ekα sα } QiM (z) µ dz , j ∈ J
iii. the generalized external mechanical forces :

 β Rh

 Fν 1 α = − 0 fν α µβ α µ dz

 Rh

 Fν 2 α = − 0 fν α z µ dz
β Rh
Fν 3 α = − 0 fν α hβ α (z) µ dz (139)

 Rh

 Fν 3 = − 0 fν α µ dz


P = p0 − ph
iv. the generalized external electrostatic forces :
( Rh
W iB = − 0 W QiB (z) µ dz , i ∈ I
Rh (140)
W jM = − 0 W QiB (z) µ dz , j ∈ J
iv. the inertia terms:

 Rh

 I1 = − 0 ρ µ dz

 Rh

 I2 = − 0 ρ z µ dz

 Rh

I3 = − 0 ρ hα(z) µ dz
Rh (141)

 I4 = − 0 ρ z 2 µ dz

 Rh

 I5 = − 0 ρ z hα (z) µ dz

 Rh

I6 = − 0 ρ z hα 2(z) µ dz
236 Claire David
Proposition 2.9. The equations of motion are given by:


 N1 αβ |β + N2αβ |β = I1 α üα − I2 ẅ|α + I3 α γ̈α0



 M1 αβ |αβ + M2αβ |αβ = I2 α üα|α − I4 ẅ|αα + I5 α γ̈α|α
0
+ I1 ẅ
N5α |α + N6 αβ |β + N4α = α α 0
I3 üα − I5 ẅ|α + I6 γ̈α (142)

 α

 N iB + MiB |α = 0 ,i∈I

 α
N jM + Mjm |α = 0 ,j∈J
Proof 2.10. The equations of motion are deduced from Hamilton’s Principle, in conjunc-
tion with the kinematics (132), including the constitutive law given by equations (27), by
integration through the thickness of the shell.
Proposition 2.11. The boundary conditions leading to a “regular problem" are:

 α
 N1 αβ nβ + N2αβ nβ = Fν 1 β ou δuα = 0



 M1αβ |β + M2αβ |β = Fν 2 α ou δw = 0

 α
N4αβ nβ = Fν 3 β or δγ 0α = 0
(143)

 M1 αβ nβ + M2αβ nβ = Fν3 ou δw|α = 0

 α

 N iB nα = W iB ou δϕiB = 0 , i ∈ I
 α
MjM nα = W jM ou δϕjM = 0 , j ∈ J
Proof 2.12. The equations of motions can be derived from Principe de Hamilton’s Princi-
ple, the kinematics (132), and the constitutive law (27), through integration on the thickness
of the shell.
2.9. Numerical Validation of the Piezoelectric Shell Model

2.9.1. Associated Plate Model
The plate being a degenerated shell, our shell model is, in a first time, validated by the
related plate model.
2.9.2. Free Vibrations of an Orthotropic Cylindrical Panel

Consider an orthotropic cylindrical panel, supposed of infinite length, made of PZT4 ce-
ramic, under cylindrical bending, simply supported, submitted to a surface force density p,
in closed circuit (which means the electrostatic potential on the top and bottom surfaces is
B T
equal to zero: ϕ1 = ϕ1 = 0).
R denotes the radius of the cylinder, h its thickness, α its central angle, and θ the angular
coordinate (see figure 22).

j
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 21. Normalized electrostatic potential, single-layered panel, R = 4 h. In black: our

model. In gray: exact solution.
Table 7. Independent elastic constants of PZT4 ceramic (in GP a)
C11 C22 C33 C12 C13 C23 C44 C55 C66

PZT 4 139 139 115 77.8 74.3 74.3 25.6 25.6 30.6
Data 2.13. Material constants of PZT4 ceramic are given in tables 7, 8.
w(θ = 0, z; t) = w(θ = α, z; t) = 0 (144)
Proposition 2.15. The panel being supposed of infinite length, the mechanical and electri-
cal quantities (stresses, strains, displacements, electric field, electrostatic potential), do not
depend on x2 .
U2 = 0
Assumptions 2.17. The force density p is assumed to be simply sinusoidal, of the form:
π x1
p (xα, z; t) = p0 e j ω t sin( ) (145)
α
where p0 = 10 N/m2.
238 Claire David
Figure 22. The cylindrical panel.
Table 8. Independent piezoelectric and dielectric constants of PZT4 ceramic ( eij in

C/m2 , εii in nF/m)
e31 e32 e33 e15 ε11 ε22 ε33

PZT 4 −5.2 −5.2 15.1 12.7 13.06 13.06 11.51
Proposition 2.18. The electrostatic potential (20) is approximated as (18):
M
ϕ1(xα , z; t) = (1 − ξ1 2) ϕ1 (xα ; t) (146)
The mechanical generalized displacements remaining unknowns the membrane displace-

ment u1 , w, and the transverse shear γ1 0.
M
The electrical generalized unknown is ϕ1 .
Assumptions 2.19. The solution is searched under the following form,which characterizes
the propagation of harmonic plane-waves:
 πx
 u1 = A1 e j ω t cos( α 1 ) π x1
M
w = B ej ω t sin( παx1 ) , ϕ1 = Φ1 e j ω t sin( ) (147)
 0 α
γ1 = C1 e j ω t cos( παx1 )
which enable us to satisfy the simply supported boundary conditions (159).
By substituting these expressions in the equations of the equilibrium (142), in conjunction

with the boundary conditions (143), the constitutive law (31) and the displacement field
(132), we obtain a linear system in A1 , B, C1 , Φ1 , of the form:

Σ 13
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 23. Normalized transverse shear stress, single-layered panel, R = 4 h. In black: our
model. In gray: exact solution.
 
A1
 B 
K1  
 C1  = B1 (148)
Φ1
Detail of coefficients of the matrix K1 and of the vector B1 can be found in [8].
Figure 21 displays the variations, as a function of the global thickness variable z, of the
α
ϕ(θ = 2 , z; t)
ϕ(z; t) = α h
(149)
ϕ(θ = 2 , z = 2 ; t)
R
for a significative value of h.
Results (in black) are compared to the exact solution of Dumir [20] (in gray).
Results obtained by our model perfectly fit the exact solution.
Figures 23, 24, 25 display the variations, as functions of the global thickness coordinate z,
of the normalized transverse shear stress:
α
σ13(θ = 2 , z; t)
σ 13(z; t) = α h
(150)
σ13(θ = 2 , z = 2 ; t)
R
for significative values of h.
Results (in black) are compared to the exact solution of Dumir [20] (in gray).
240 Claire David

Σ 11
1
0.8
0.6
0.4
0.2
0.2 0.4 0.6 0.8 1 zh
Figure 24. Normalized transverse shear stress, single-layered panel, R = 10 h. In black:

our model. In gray: exact solution.
The model appears to be in good agreement with the exact solution.

As expected, as the shell grows thinner, the results of our model get closer to those of the
exact solution.
Figures 26, 27, 28 display the variations, as functions of the global thickness coordinate z,
of the normalized longitudinal stress:
α
σ11(θ = 2 , z; t)
σ 11(z; t) = α h
(151)
σ11(θ = 2 , z = 2 ; t)
for significative values of the quotient R

h.
As for the transverse shear stress, the model appears to be in good agreement with the exact
solution.
2.10. Applications of the Multilayered Piezoelectric Shell Model
We present, in the following, applications of our multilayered piezoelectric shell model.

For the considered problems, there is no exact three-dimensional solution. Our results can
be interpreted as generalizations, to the “shell case ", of Fernandes’s [21], [22], in the case
of piezoelectric plates.

Σ
13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 25. Normalized transverse shear stress, single-layered panel, R = 100 h. In black:
our model. In gray: exact solution.
2.10.1. Bimorph Shell

Consider a bimorph circular cylindrical panel, supposed of infinite length, made of PZT4
ceramic, under cylindrical bending, simply supported, submitted, on its top face, to a po-
tential +V , while, on its lower face, to a potential −V (see figure 29).
As previously, R denotes the radius of the cylinder, h its thickness, α its central angle,
and θ the angular coordinate (see figure 22).
Data 2.20. Material constants of PZT4 ceramic can be found in tables 1, 2.
w(θ = 0, z; t) = w(θ = α, z; t) = 0 (152)
depend on x2 .
Assumptions 2.23. Since the component U2 of the displacement field does not paly any
U2 = 0
242 Claire David

Σ
11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 26. Normalized longitudinal stress, single-layered circular cylindrical panel, R =

4 h. In black: our model. In gray: exact solution.
Assumptions 2.24. The potential V is assumed to be simply sinusoidal:
π x1
V (xα, z; t) = V0 e j ω t sin( ) (153)
a
M
ϕ(x1, z; t) = (1 − ξ1 2) ϕ1 (x1; t) − 1
2 ξ1 (ξ1 − 1) V (x1; t) χ1 (z)
M (154)
+ (1 − ξ2 2) ϕ2 (x1; t) + 1
2 ξ2 (ξ2 + 1) V (x1; t) χ2 (z)
Remark 2.2. The dielectric coefficients of the two layers that constitute the bimorph being
identical, no continuity conditions at layer interfaces are requested for the electric displace-
ment.
The mechanical generalized displacements remaining unknowns are the membrane
displacement u1 , w, and the transverse shear γ1 0.
M
The electrical generalized unknown is ϕ1 .
the propagation of harmonic plane-waves:
 πx
 u1 = A1 e j ω t cos( α 1 ) π x1
M
w = B ej ω t sin( παx1 ) , ϕ1 = Φ1 e j ω t sin( ) (155)
 0 α
which enable us to satisfy the simply supported boundary conditions(159).

Σ 11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1

10 h. In black: our model. In gray: exact solution.

 
A1
 B 
K1  
 C1  = B1 (156)
Φ1
Detail of coefficients of the matrix K1 and of the vector B1 is given in [8].

α
ϕ(θ = 2 , z; t)
ϕ(z; t) = α h
(157)
ϕ(θ = 2 , z = 2 ; t)
α
σ13(θ = 2 , z; t)
σ 13(z; t) = α h
(158)
σ13(θ = 2 , z = 2 ; t)
2.10.2. Three-Layered Shell, Submitted to a Force Density

Consider a symmetric 3-layered circular cylindrical panel, of infinite length, a circular
cylindrical panel, the external layers of which are made of ZnO oxyde, with a silicium
244 Claire David

Σ 11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1

100 h. In black: our mode. In gray: exact solution.
core, under cylindrical bending, simply supported, submitted to a force density p on its top
face, and in closed circuit (which means that the electrostatic potential on its top and bottom
B T
surfaces is equal to zero: ϕ1 = ϕ1 = 0) (see figure 32).
As previously, R denotes the radius of the cylinder, h its thickness, α its central angle,
and θ the angular coordinate (see figure 22).
Data 2.27. Material constants of ZnO oxyde and silicium Si can be found in tables 9, 10.
Table 9. Independent mechanical constants of ZnO and silicium Si (in GP a)
C11 C22 C33 C12 C13 C23 C44 C55 C66

ZnO 209.7 209.7 210.9 121.1 105.1 42.5 42.5 25.6 30.6
Si 166 166 166 63.9 63.9 79.6 5.654 5.654 5.654
Table 10. Independent piezoelectric and dielectric constants of ZnO and silicium Si
(eij in C/m2 , εii in nF/m)
e31 e32 e33 e15 ε11 ε22 ε33

ZnO −0.61 −0.61 1.14 −0.59 13.06 13.06 11.51
Si 0 0 0 12.7 0.01045 0.01045 0.01045
w(θ = 0, z; t) = w(θ = α, z; t) = 0 (159)

Figure 29. Bimorph shell, with imposed potentials.
j
1
0.75
0.5
0.25
0.2 0.4 0.6 0.8 1z h
-0.25
-0.5
-0.75
-1
Figure 30. Normalized electrostatic potential, bimorph cylindrical panel, R = 4 h.
The generalized mechanical unknowns are the membrane displacements u1 , the deflection
w, and the transverse shear stresses γ10 .
M
depend on x2 .
U2 = 0
246 Claire David
Σ13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 31. Normalized transverse shear stress, bimorph cylindrical panel, R = 4 h.
Assumptions 2.31. The force density p is supposed to be simply sinusoidal, of the form:
π x1
p (xα, z; t) = p0 e j ω t sin( ) (160)
α
where p0 = 10N/m2.
M
ϕ(xα, z; t) = Q2M (z) ϕ2 (161)
where:
M
Q2M (z) = (1 − ξ1 2 ) λ1M,2M + 12 ξ1 (ξ1 + 1) λ2B,2M χ1 (z) 2
+ 12 ξ2 (ξ2 − 1) λ2B,2M + (1 − ξ22 ) + 12 ξ2 (ξ
2 + 1) λ2B,2M
χ (z)
+ 12 ξ3 (ξ3 − 1) λ2B,2M + (1 − ξ32 ) λ1M,2M χ3 (z)
(162)
M B
where λi , λi (i = 1, 2) are real constants, determined by means of the interface conti-
nuity conditions.
Proof. Symmetries of the problem lead to:
B B M M
ϕ2 (xα ; t) = ϕ3 (xα ; t) , ϕ1 (xα; t) = ϕ3 (xα; t) (163)
which enable us to simplify the electrostatic potential:
Figure 32. Three-layered shell.
M T
ϕ(xα , z; t) = (1 − ξ1 2 ) ϕ1 (xα ; t) + 12 ξ1 (ξ1 + 1) ϕ1 (xα ; t) χ1 (z)
1 B M T
+ ξ (ξ − 1) ϕ2 (xα ; t) + (1 − ξ2 2 ) ϕ2 (xα ; t) + 12 ξ2 (ξ2 + 1) ϕ2 (xα; t) χ2 (z)
21 2 2 B M
+ ξ (ξ3 − 1) ϕ2 (xα ; t) + (1 − ξ3 2 ) ϕ1 (xα ; t) χ3 (z)
2 3
(164)
The continuity of the uncoupled electric displacement at layer interfaces yields:

−ε33,11 ϕ,31 (xα, z1; t) = −ε33,12 ϕ,3 2(xα , z1; t)
(165)
−ε33,12 ϕ,31 (xα, z2; t) = −ε33,11 ϕ,3 3(xα , z2; t)
M B
We thus obtain a linear system, which enables us to express ϕ1 and ϕ2 as functions of
M
ϕ2 , under the form:
(
M M M
ϕ1 = λ1M,2M ϕ2
B M M (166)
ϕ2 = λ2B,2M ϕ2
the propagation of harmonic plane waves:
 πx
 u1 = A1 e j ω t cos( α 1 ) π x1
π x1 M
w = Be jωt
sin( α ) , ϕ2 = Φ2 e j ω t sin( ) (167)
 1 α

248 Claire David
j
1
0.5
0.10.20.30.40.50.60.70.80.9 1 zh
-0.5
-1
Figure 33. Normalized electrostatic potential, three-layered cylindrical panel, R = 4 h.
Σ13
1
0.8
0.6
0.4
0.2
0.10.20.30.40.50.60.70.80.9 1 zh
Figure 34. Normalized transverse shear stress, three-layered cylindrical panel, R = 4 h.

 
A1
 B 
K2  
 C1  = B2 (168)
Φ2
detail of the coefficients of the matrix K2 and of the vector B2 is given in [8].
α
ϕ(θ = 2 , z; t)
ϕ(z; t) = α h
(169)
ϕ(θ = 2 , z = 2 ; t)
Σ11
1
0.75
0.5
0.25
0.10.20.30.40.50.60.70.80.9 1 zh
-0.25
-0.5
-0.75
-1
Figure 35. Normalized longitudinal stress, three-layered cylindrical panel, R = 4 h.
α
σ13(θ = 2 , z; t)
σ 13(z; t) = α h
(170)
σ13(θ = 2 , z = 2 ; t)
α
σ11(θ = 2 , z; t)
σ 11(z; t) = α h
(171)
σ11(θ = 2 , z = 2 ; t)
2.11. Conclusion
The latter results constitute, as expected, a generalization of similar ones obtained in the
case of plates by Fernandes [21], [22].
The general aspect of the curves is the same, with, of course, an influence of the curvature.
The fitting between those results, and the fact that the considered problems correspond to
thick shells (R = 4 h), show that our model can efficiently represent piezoelectric struc-
tures, submitted to different kinds of loadings, electric or mechanic.
250 Claire David
Acknowledgment
The author would like to thank Prof. Maurice Touratier, thanks to whom this work exists.
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Chapter 5
CYCLIC DEFORMATION OF
DISCONTINUOUSLY REINFORCED METAL
MATRIX COMPOSITES: A REVIEW
Guozheng Kang*
Department of Applied Mechanics and Engineering, Southwest Jiaotong University,
Chengdu, Sichuan 610031, P.R. China
Abstract
Discontinuously reinforced metal matrix composites (DRMMCs), such as particulate
reinforced metal matrix composites (PRMMCs) and short fiber reinforced metal matrix
composites (SFRMMCs) (especially aluminum alloy matrix composites) are currently being
used and will be used as major structural components in automobiles and aircrafts, which are
often subjected to a cyclic loading, in sooner future. The microstructures of the composites
become very complicated due to a shortened length and randomly oriented distribution of
short fibers and particulates, and then precise prediction for their mechanical performances,
especially for the cyclic deformation process is rather difficult. However, the accurate
prediction to such behaviors is extremely necessary to design and assess the structure
components made from such composites, and some progresses have been made by many
researches recently. Therefore, in this Chapter, recent progresses in the researches about the
cyclic deformation (including the ratcheting behavior produced in the asymmetrical cyclic
stressing) of DRMMCs are reviewed. The content of the review includes the state-of-arts in
experimental observations, numerical simulations and some constitutive models for PRMMCs
or SFRMMCs. The loading modes involved are uniaxial and multiaxial cyclic straining and
cyclic stressing, and the ambient temperature varies from room temperature to high
temperature. The effects of some time-factors on the cyclic deformation of the composites are
also considered. As a conclusion of the review, some suggestions are provided for the future
researches about the cyclic deformation of PRMMCs or SFRMMCs.
Keywords: Metal matrix composites; particulate; short fiber; cyclic deformation; ratcheting
*
E-mail: guozhengkang@yahoo.com.cn.
256 Guozheng Kang
1. Introduction
Discontinuously reinforced metal matrix composites (DRMMCs), such as particulate
reinforced metal matrix composites (PRMMCs) and short fiber reinforced metal matrix
composites (SFRMMCs) (especially aluminum alloy matrix composites) are currently being
used in many automotive applications such as drive-shafts in trucks, brake rotors and liner of
engine blocks etc, since the dispersion of discontinuous particulates and short fibers as well as
whiskers in a metal matrix leads to significant improvements in stiffness, wear and creep
resistance and to a lesser extent, strength, while keeping the mechanical responses of the
composites as nearly isotropic and conserving some of traditional manufacturing techniques
for matrix alloys. The composites may be used as major structural components in automobiles
and aircrafts, which are often subjected to a cyclic loading, in sooner future. However, the
microstructures of the composites become very complicated due to a shortened length and
randomly oriented distribution of short fibers and particulates, and then precise prediction for
their mechanical performances is rather difficult, especially for the cyclic deformation
behaviours of the composites. Since aforementioned structure components are often subjected
to a cyclic loading, the fatigue properties of PRMMCs and SFRMMCs are very important and
have been investigated experimentally to certain extent, where some observations and
discussions for the cyclic deformation behaviours of the composites are involved.
In 2002, LLorca [1] reviewed the progresses in research for the cyclic deformation of
particulate and whisker reinforced metal matrix composites in last two decades partially in his
reviewed paper about the fatigue of the composites. He first outlined the state-in-arts of the
micro-mechanisms of cyclic deformation from the microstructure standpoint, and then
demonstrated the existing numerical simulations for the effects of particulates and whiskers
(or short fibers) on the cyclic deformation processes of the composites by finite element
method from a continuum mechanics perspective. It should be noted that the literatures
referred here were mainly published before 2000. However, research has progressed rapidly
after 2000, and many new experimental phenomena, numerical simulations by finite element
method and theoretical constitutive models have been carried out for the particulate and short
fiber (or whisker) reinforced metal matrix composites. Therefore, in this Chapter the recent
research progresses in the cyclic deformation of particulate and short fiber reinforced metal
matrix composites are reviewed, and main referred literatures are published after 2000. The
main body of this Chapter is divided into three parts, i.e., progresses in experimental
observations, numerical simulations and constitutive models. Finally, as a conclusion of the
review, some suggestions are provided for the future researches about the cyclic deformation
of PRMMCs or SFRMMCs.
2. Progresses in Experimental Observations

2.1. Cyclic Deformation in Cyclic Straining
As reviewed by LLorca [1], before 2000, many experimental observations were carried out
and the cyclic deformation features of PRMMCs or SFRMMCs were discussed even the main
topic of referred literatures was the fatigue behaviors of the composites. It is concluded by
Cyclic Deformation of Discontinuously Reinforced Metal Matrix Composites 257
Figure 1. Cyclic responses of commercially pure Al (a) and its composite reinforced by 20 vol.% SiC
particulates (b) obtained from the symmetrical uniaxial cyclic straining with different plastic strain
semi-ranges. From [1] (originally from [2]).
LLorca [1] that: (1) the cyclic softening/hardening feature of the composites mainly depends
on the original cyclic softening/hardening feature of un-reinforced matrix metals and the
variations of microstructures (such as dislocation density and so on) in the reinforced matrix
caused by the introduction of ceramic reinforcements, such as particulates, short fibers and
whiskers, as shown in Fig. 1. (2) For the composite whose matrix belongs to alloy rather than
pure metal, its cyclic softening/hardening feature depends greatly on the different heat-
treatments endured, as shown in Fig. 2. Fig. 1 and Fig. 2 show the results of cyclic
deformation behaviors obtained from corresponding experiments for the SiC particulate
reinforced pure Al and some commercial Al alloys endured natural age or peak-age heat
258 Guozheng Kang
(a)
(b)
(c)
Figure 2. Cyclic responses of commercially naturally aged 8090 Al-Li alloy (a) and its composite
reinforced by 15 vol.% SiC particulates (b) as well as the peak-aged 8090 Al-Li alloy reinforced by 15
vol.% SiC particulates (c) obtained from the symmetrical uniaxial cyclic straining with different strain
semi-ranges. From [1] (originally from [3]).
treatment, respectively. (3) The cyclic softening/hardening feature of the DRMMCs depend
greatly on the ambient temperature, and in general, the cyclic response of DRMMCs can be
rationalized in terms of the competition between the cyclic hardening mechanism attributed to
the generation of new dislocations and interaction among them and the cyclic softening
processes activated at high temperature. The cyclic hardening is dominant during the first
loading cycles, and after then, cyclic softening usually dominates the mechanical response till
the failure occurs, as shown in Fig. 3. The mechanisms of cyclic softening included the re-
arrangement and the annihilation of dislocations as cross-slip became easier at high
temperature, precipitate coarsening, and the development of damage in the form of interfacial
failure and matrix cavitations. Some other literatures concerning the cyclic deformation of
PRMMCs or SFRMMCs and being published before 2000 can be found in the reference lists
of [1], and some referred literatures in this chapter, such as [5-8].
Figure 3. Cyclic stress responses for the SiCP/2024Al composite at (a) room temperature and (b) 190°C.
From [4].
Besides the referred literatures in [1], many other observations were carried out for the
cyclic deformation of the DRMMCs before 2000, especially for the cyclic responses of the
composites in the biaxial or multiaxial cyclic straining. Xia et al [6] and Meijer et al [7]
performed some proportional and non-proportional biaxial cyclic tests for the 10% and 20%
260 Guozheng Kang
Al2O3P 6061 aluminum alloy matrix composite as received and with the T0 (annealed) and T6
(quenched and artificially aged) heat treatments in the cyclic straining. They observed that
under equibiaxial loading, with significant plastic deformations the annealed composite
experienced a drop in stiffness with increasing cycles, and the composite experienced a large
amount of strain hardening under 90° out-of-phase loads due to the addition of the
reinforcement, as shown in Fig. 4 to Fig. 8.
Figure 4. Uniaxial cyclic stress responses for T0-condition composite: (a) stress-strain curves; (b) stress
range vs. number of cycles. From [6].
Figure 5. Uniaxial cyclic stress responses for T6-condition composite: (a) stress-strain curves; (b) stress
range vs. number of cycles. From [6].
Figure 6. Stress-strain responses of the T0-condition composite in a 90° out-of-phase cyclic test with
strain amplitude of 0.15%: (a) axial stress-strain curves; (b) hoop stress-strain curves. From [6].
Figure 7. Stress-strain responses of the T6-condition composite in a 90° out-of-phase cyclic test with
strain amplitude of 0.225%: (a) axial stress-strain curves; (b) hoop stress-strain curves. From [6].
Figure 8. Continued on next page.

262 Guozheng Kang
Figure 8. Comparison of the stress ranges of equi-biaxial proportional and 90° out-of-phase cyclic tests:
(a) as received condition with strain amplitude of 0.25%; (b) T0 condition with strain amplitude of
0.15%; (c) T6-condition with strain amplitude of 0.225%. From [6].
Ruggles [8] performed some uniaxial and biaxial cyclic tests of a Ti-6Al-4V titanium
alloy reinforced with TiC particles at 538°C and at different strain rates. The results showed
that: (1) for uniaxial cyclic straining, the composite presented cyclically neutral and no
apparent cyclic hardening or softening was observed; however, the responded stress
amplitude depended not only on the applied strain amplitude, but also on the strain rate, i.e.,
the stress amplitude obtained at lower strain rate and with lower applied strain amplitude was
smaller than that obtained at higher strain rate and with higher applied strain amplitude.
Furthermore, the decrease in strain rate also had a significant effect on the cyclic life of the
composite, and resulted in an increasing cycles to fatigue failure. (2) The composite exhibited
cyclic neutral behavior in torsion and the shear stress responses in torsional cyclic tests agreed
(in the Von Mises sense) reasonably well with those in axial cyclic tests with similar effective
strain rate and strain amplitude. Also, the stress amplitudes obtained in axial, torsion and 90°
out-of-phase axial-torsion cyclic tests could be reasonably well correlated with the Von Mises
criterion, and the cyclic life under the out-of-phase cyclic test appeared to be significantly
shorter than in either axial or pure torsion cyclic tests.
After 2000, many new phenomena have been observed for the cyclic deformation
behaviors of PRMMCs or SFRMMCs. For example, Hartmann et al [9] investigated the
cyclic deformation behavior of three metal matrix composites, namely AA6061-T6 reinforced
with 20 vol.% alumina particles and short-fibers, respectively and pure aluminium reinforced
with 20 vol.% short-fibers at temperatures between T=-100°C and T=300°C in uniaxial
symmetrical cyclic straining tests. The results showed that the cyclic stress response exhibited
initial cyclic hardening, subsequent saturation and cyclic softening, depending on the test
parameters for temperatures lower than T=150°C, and both composites with AA6061 matrix
exhibited pronounced cyclic softening feature at high temperature of T=300°C due to the
coarsening of precipitates; moreover, initial cyclic hardening was most pronounced for the
short-fiber reinforced composite with the unalloyed matrix and less pronounced in the case of
particle reinforcement, and the shape of reinforcement phase (particle vs. fibers) influenced
the cyclic stress-strain curves only to a minor degree. Qian et al [10] conducted thermo-
mechanical fatigue (TMF) tests for the 15 and 28 vol.% SiCW/6061Al composites under
temperature cycling between 150 and 300°C and mechanical strain rages of 0.004 to 0.012,
and examined the effects of temperature-load phase and volume fraction of SiC whiskers on
the cyclic deformation of the composites in the TMF. It is shown from Fig. 9 to Fig. 11 that
cyclic softening occurs in both composites during out-of-phase (OP) and in-phase (IP) cyclic
tests, the responded stress ranges of the composite with 28 vol.% SiC whisker is always
higher than that with 15 vol.% SiC whisker, and tensile mean stress is generated during OP
cyclic tests but compressive mean stress is resulted in during IP cyclic tests. There are no
detectable differences in the mean stresses between the composites with two volume fractions
of whiskers. Similar work discussing the effect of thermal cycling on the cyclic deformation
of SiC particulate reinforced cast aluminium alloy composites can be found in [11].
Figure 9. Typical stress-strain hysterses at half life time for the composites in (a) IP and (b) OP cyclic
tests. From [10].
Figure 10. Cyclic stress response curves of 15 and 28 vol.% SiCW/6061Al in (a) IP and (b) OP cyclic
tests. From [10].
264 Guozheng Kang
Figure 11. Cyclic mean stress as a function of number of cycles during (a) IP and (b) OP cyclic tests.
From [10].
Figure 12. Cyclic stress responses in the cyclic straining for (a) Al–TiO2–B2O3 and (b) Al–TiO2–B
system composites. From [12].
Tjong et al [12] provided some results of cyclic softening/hardening features for two
kinds of in situ aluminum matrix composites, i.e., Al–TiO2–B2O3 and Al–TiO2–B system
composites. It is shown in Fig. 12 that both composites exhibit essentially stable cyclic
behavior, i.e., no cyclic hardening or softening at low total strain amplitudes of 0.1–0.4%.
However, Al–TiO2–B2O3 system composite exhibits very slight hardening, up to few cycles
from initial cycling followed by softening in the cyclic straining with total strain amplitudes
of 0.6% and 0.8%.
The cyclic softening/hardening feature of the composites depends greatly on the
properties of the matrix alloys, which had been demonstrated in Fig. 2 and Fig. 12. The work
done by Srivatsan et al [13] supported such conclusion, and the results of SiC particulate
reinforced 2009 aluminum alloy composite showed that cyclic hardening occurred and
proceeded progressively during cycling till the fatigue failure, and the cyclic hardening at
higher temperature was more significant than that at lower temperature, which was different
from the conclusion that the composites presented cyclic softening at high temperatures
obtained in [1] and [9, 14, 15] for other matrix alloys such as 6061-T6, 7005 and 7034
aluminum alloys.
2.2. Ratcheting Behavior in Cyclic Stressing
In the materials subjected to a cyclic stressing with non-zero mean stress, a cyclic
accumulation of inelastic deformation will occur if the applied stress is high enough to
produce inelastic deformation. This phenomenon is namely called as ratcheting or ratcheting
effect. Since many engineering components experience such cyclic stressing with non-zero
mean stress, the ratcheting is very important and should be addressed in the safety assessment
and fatigue life estimation of such structure components. For example, in early 1990’s, the
ratcheting behavior of the nuclear pipes and its detrimental effects on the nuclear reactor
structure were contained in the American ITER design code and ASME NB 32xx code.
However, the ratcheting behavior cannot be directly described by the existing cyclic
constitutive models based on the experimental results obtained in the cyclic straining. The
ratcheting behaviors of different materials should be observed experimentally and described
theoretically. Therefore, in last two decades, it had been extensively studied. The progresses
in experimental observations and constitutive models for the ratcheting of monolithic metals
had been reviewed by Ohno [16-17], and briefly by Abdel-Karim [18] in his review paper
mainly about the shakedown of complex structures and recently done by Chen et al [19, 20],
Kang and his co-authors [21-31], Feaugas and Gaudin [32], Mayama et al [33], Vincent et al
[34], Abdel-Karim [35], Gupta et al [36], Johansson et al [37], Khoei and Jamali [38],
Yaguchi and Takahashi [39, 40] and so on.
For metal matrix composites, Jansson and Leckie [41], Daehn et al [42] and Zhang et al
[43-44] observed the occurrence of ratcheting behavior in the continuous fiber, particulate
and whisker reinforced metal matrix composites, respectively, which is subjected to constant
stress and cyclic temperature. Then, Ponter and Leckie [45-46] explained that it was caused
by the ratcheting of the matrix metals produced in the cyclic thermal stressing with non-zero
mean stress. For the ceramic matrix composites reinforced by metal particulates, Kotoul [47]
provided only one curve of ratcheting strain vs number of cycles. However, the ratcheting
behaviors of the composites have not been discussed systematically in the above-referred
literatures. Recently, Kang [48] and Kang and Liu [49] carried out many uniaxial and non-
proportionally multiaxial cyclic stressing tests for SiC particulate reinforced 6061Al alloy
266 Guozheng Kang
composites at room and high temperatures to discuss the ratcheting behavior of the
composites and its time-dependence (as shown in Fig. 13, Fig. 14 and Fig. 15). The effects of
particulate volume fraction, different heat-treatments, loading levels, ambient temperatures
and some time factors on the ratcheting behavior of the composites were discussed, and some
useful conclusions to the constitutive modeling were obtained. It should be noted that the
ratcheting strain εr shown in the figures is defined as
1
ε r = (ε max + ε min ) (1)
2
where, εmax is the maximum strain and εmin is the minimum in each cycle.
400 1.0
(a) (b)
300
Ratcheting strain ε , %
0.8
Axial stress σ , MPa
200
r
100
0.6
0
-100 0.4
-200
0.2
-300
-400 0.0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 20 40 60 80 100 120 140 160
Axial strain ε , % Number of cycles
Cyclic number N, cycle
N , cycle
Figure 13. Ratcheting results of the composite with Vf =14% in the uniaxial cyclic stressing with varied
mean stress and at room temperature: (a) curves of stress-strain; (b) curves of ratcheting strain vs. cyclic
number. From [48].
0.7
Uniaxial case
Axial ratcheting strain εr , %
0.6 Multiaxial linear case

Multiaxial rhombic case
0.5
0.4
0.3
0.2
0.1
0 5 10 15 20 25 30
Number of cycles N , cycle
Figure 14. Results of multiaxial ratcheting of the composite with Vf =21%. From [49]
0.55
(a)
0.50
Ratcheting strain εr , %
0.45
0.40
0.35
Stressing rate
0.30 -1
12.5MPas
-1
0.25 3.5MPas
0.20
0 5 10 15 20 25 30 35
Number of cyclesNN,cycle
Cyclic number cycle
1.5
(b)
Ratcheting strain ε , %
1.2
r
Hold 60s
0.9
Hold 15s
Without hold
0.6
0.3
0.0
0 5 10 15 20 25 30 35
Cyclic number
Number N , N,
of cycles cycle
cycle
Figure 15. Results of time-dependent ratcheting for the composites at 573K: (a) with Vf=21%, and at
varied stress rate; (b) with Vf=14%, and different holding-times. From [48].
It is concluded from the figures and observations in [48, 49] that: (1) the ratcheting
behavior of SiC particulate reinforced T6-6061Al alloy composites is similar to that of the
matrix alloy in macro-scale, and also depends on current stress level and its loading history.
(2) The addition of SiC particulates into the matrix improves the elastic modulus, static
strength and resistance to cyclic deformation. The ratcheting produced in the composite is
much smaller than that in the matrix and decreases further as the particulate volume fraction
increases. (3) The ratcheting behaviors of the composites have great time-dependence at room
temperature and 573K. The ratcheting strains produced at lower stress rate and with certain
peak stress hold are higher than those at higher stress rate and without peak stress hold. The
larger ratcheting strain is caused by the larger creep strain produced at lower stress rate and
during peak stress hold. The previous creep deformation will restrain the occurrence of the
ratcheting in the followed cyclic stressing, and the previous cyclic stressing will accelerate the
creep strain rate of the subsequent creep. (4) Since the ratcheting behavior of the composites
presents great time dependence, the total ratcheting strain should be composed of the creep
strain due to the viscosity of the composites and the cyclic plastic strain accumulation caused
by the un-closed hysteresis loop under asymmetrical cyclic stressing, and different flow rules
should be employed for the two parts in the constitutive modeling of such time-dependent
ratcheting, respectively. (5) Additional hardening is caused by the non-proportionality of
multiaxial cyclic straining. The ratcheting of the composites depends greatly on the shapes of
268 Guozheng Kang
multiaxial loading paths, and the ratcheting strain mainly occurs in the direction of non-zero
mean stress (such as the axial direction shown in Fig. 14).
It should be noted that the existed literatures mainly concern the time-independent cyclic
deformation of the composites in uniaxial cyclic straining or stressing. Many efforts have still
to be paid for the experimental investigation to the proportional or non-proportional
multiaxial cyclic deformation (especially for the ratcheting behavior) and its time-dependence
of the composites in future research.
3. Progresses in Numerical Simulations

In order to predict the fatigue life of the composites reasonably, a constitutive model
describing the cyclic deformation behaviors of PRMMCs or SFRMMCs is required.
However, such a constitutive model is scarcely reported now, only the researches done by
Doghri et al [50, 51] provided a significant sample, which will be introduced in detail in the
Section 4 of this chapter. Since the complicated micro-structure of the DRMMCs, it is very
difficult to predict their mechanical behavior, especially for their cyclic deformation behavior
by theoretical analyses. Similar to the montonic tensile case for the DRMMCs, finite element
analysis based on the reasonable micromechanical model will play an important role in the
simulation of the cyclic deformation behavior of the composites, and can provide the local
stress and strain fields in matrix, reinforcement and at the matrix-reinforcement interface,
whose distribution, magnitude and evolution rule are necessary to account for the damage
development during cyclic deformation. Some progresses have been achieved in such
numerical simulation and its state-in-arts will be reviewed in detail in the following
paragraphs of this chapter.
3.1. Mono-particle Unit Cell Model
As reviewed by LLorca [1], finite element simulations based on a periodic unit cell model,
representative of the DRMMCs, had been done to study the Bauschinger effect and fully
reversed cyclic deformation in cyclic straining. Such unit cell analyses are based on the
spatial representation, where the composite is idealized as a three-dimensional array of
hexagonal prisms, as shown in Fig. 16. In the simulation, the behavior of the hexagonal
prisms can be approximated by that of axi-symmetrical cylindrical cells. Due to the
symmetry, only one half of cylindrical cell needs to be analyzed, as shown in Fig. 16. The
reinforcements are located at the center of each cylinder and their shape is either spherical or
cylindrical. For cylindrical reinforcement, its axis is prescribed to be parallel to that of unit
cell.
In practical simulation, the reinforcements of three different shapes, i.e., spheres, short
cylinders (whose height equals to its diameter, a good approximation of particles with
irregular shape, sharp corners and lower aspect ratio) and long cylinders with aspect ratio of 5
(representing whisker) are studied [52]. The finite element meshes used in simulations for the
prescribed particle shapes are shown in Fig. 17, respectively, for the cells containing 20 vol.%
of reinforcement. The reinforcements are assumed to behavior as isotropic linear elastic
Figure 16. Composite idealization as a three-dimensional array of hexagonal prisms and the unit cell
used in the finite element simulation. From [1].
Figure 17. Finite element meshes of axi-symmetrical unit cells: (a) sphere, (b) short cylinder and (c)
long cylinder (whisker) reinforcements. From [1].
270 Guozheng Kang
materials, the interface is assumed to be perfect, and the deformation behavior of commercial
high strength Al alloy matrix is represented by an elasto-plastic solid with isotropic hardening
following the incremental theory of plasticity. In addition, it should be noted that the circular
cylindrical cell should be required to remain cylindrical during deformation to ensure the
displacement compatibility between neighbor hexagonal prisms. Thus, the straight lines
bounding each cell must be remained straight during the analysis and form right angles. Some
details about the numerical technique and the precise boundary conditions usually used in the
finite element simulation can be found in [53].
The uniaxial stress-strain response of the composite in the z-direction can be computed
from the unit cell behavior according to
1
Ω ∫Ω
ε = ln(1 + U / L) and σ = Tz dΩ (2)
where U and Tz stand, respectively, for a uniform displacement and the corresponding stresses
on the upper boundary of the unit cell both in the z-direction, while Ω stands for the current
area of the cell face with normal in the same direction [1].
Finally, the mechanical response of the composite under fully reversed deformation in
cyclic straining is obtained by applying an alternating displacement to the upper boundary of
the unit cell, and the results are shown in Fig. 18. It is shown that the simulation reveals the
Bauschinger effect, which should be an intrinsic composite effect, since the isotropic
hardening rule adopted in the simulation for the matrix cannot describe such behavior.
Simultaneously, an apparent cyclic hardening feature is observed for the composite. The
hardening rate is very quick during the first cycles, and then decreases progressively. Finally,
a saturated hysteresis loop is attained.
Figure 18. Simulated results of cyclic stress responses for the composite containing 20 vol.% SiC
particles in cyclic straining: (a) stress-strain behavior during 10 cycles with applied strain amplitude of
1%; (b) saturated hysteresis loops with various applied strain amplitudes. From [1] (originally from
[52]).
Figure 19. Simulated iso-lines of constant effective plastic strain in the matrix for the composite
containing 20 vol.% SiC particles at peak strain point (εmax=1%) after (a) one, (b) three and (c) ten
cycles. From [1] (originally from [52]).
Based on the microstructure distribution of effective plastic strain in matrix and its
evolution during cyclic straining shown in Fig. 19, the mechanisms of cyclic strain hardening
272 Guozheng Kang
in the composite can be readily understood. Plastic strain develops around the particle sharp
corner during monotonic deformation in the first cycle; however, the plastic strain does not
cover the entire unit cell, and their magnitude is not very high. After three cycles, the plastic
strain reaches 0.2 around the particle corner, and plastic strain in excess of 0.05 covers most
of the unit cell (as shown in Fig. 19b). This build-up of plastic strains continues upon further
loading and unloading and plastic strains over 0.2 are spread throughout the matrix after 10
cycles (as shown in Fig. 19c). The increase in the composite flow resistance reflects the strain
hardening of the matrix due to the progressive accumulation of plastic deformation in each
loading cycle. The matrix strain hardening capacity is higher at low strains, and thus the
composite hardens very quickly in the first cycles, as shown in Fig. 18a.
As a result of numerical simulation in [52], it is concluded that reinforcement volume
fraction and shape are expected to be secondary factors, as compared to the matrix hardening
capacity, to determine the cyclic hardening under fully reversed deformation. It is also shown
that the strengthening provided by the spherical particles is smaller than that by short
cylindrical particles and both significantly lower than that obtained by long cylindrical
reinforcements (whiskers).
(a)
(b)
Figure 20. Simulated and experimental results of stress-strain hysteresis loops for the composite in
symmetrical cyclic stressing with stress amplitude of 317 MPa: (a) for the first two cycles; (b) for the
stabilized cycle. From [54].
Figure 21. Simulated distribution of the accumulated plastic strain in the composite after five half-
cycles with elongation amplitude of 1%. From [56].
It should be noted that in the numerical simulation reviewed above, a classical cyclic
plasticity model based only on an isotropic hardening rule is used for describing the cyclic
deformation behavior of the matrix alloys. It is well known that the isotropic hardening rule
cannot describe the Bauschinger effect of the matrix alloy presented in reversed loading. To
overcome this shortcoming, Fouret and Degallaix [54] simulated the cyclic deformation
behavior of a cast metal matrix composite Al-SiCP in symmetrical cyclic stressing by
employing both nonlinear kinematic hardening and isotropic hardening rules for representing
the cyclic deformation of the matrix. It is shown in Fig. 20 that the simulations agree with the
experiments well, and more significant Bauschinger effect is observed in the composite from
the simulated cyclic stress-strain hysteresis loops. Based on the cyclic strain plasticity
originally developed by Putchkov and Temis [55], Fleming and Temis [56] provided some
simulated results of cyclic deformation for 7075 aluminum alloy reinforced by 12 vol.% SiC
particles in fully reversed straining by employing the unit cell containing only one spherical
particle. Fig. 21 shows that two zones (I and F) appear where the accumulated plastic strain is
at a maximum. The first zone, I, is on the interface between inclusion and matrix; and the
second zone, F, is formed on the cylindrical axis at some distance from the inclusion in the
direction of deformation. Such locations are the possible places where fatigue micro-cracks
occur after certain loading cycles.
Recently, based on the finite element implementation of a visco-plastic constitutive
model [21], which describes the ratcheting behavior of cyclic stable metals reasonably, the
uniaxial ratcheting behavior and its time-dependence of SiC particulate reinforced 6061Al
alloy composites were numerically simulated by Kang et al [57-58] at room and high
temperatures, respectively, by employing mono-particle unit cell model. The effects of
particulate volume fraction, particulate shape and some time-dependent loading factors on the
ratcheting of the composites were discussed in detail, and some results can be found in Fig.
22 to Fig. 25. The details about the cyclic constitutive model for the matrix and the finite
element models used in the simulations can be found in the referred literatures [57-58].
274 Guozheng Kang
400 0.6
(a) (b)
300 0.5
Axial stress σ , MPa 200
0.4
100
0.3
0
0.2 Experiments (70MPa/s)
-100 Stressing rate 25MPa/s
Simulations (70MPa/s)
Experiments 1cyc Experiments (25MPa/s)
0.1
-200 Experiments 10cyc Simulations (25MPa/s)
Simulations 1,10cyc
-300 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0 2 4 6 8 10 12
Axial strain ε , % Number of cycles N , cycle
Figure 22. Experimental and simulated results of uniaxial time-dependent ratcheting for the composites
obtained at different stressing rates and without any hold (Vf=21%, at room temperature, 50±280MPa,
μ=0.05): (a) cyclic stress-strain curves; (b) relations of ratcheting strain to number of cycles. From [58]
400 0.8
(a) (b)
300 0.7
Axial stress σ , MPa
200 0.6
0.5
100
0.4
0
Peak stress hold 15s 0.3
Experiments (hold 15s)
-100
Experiments 1cyc 0.2 Simulations (hold 15s)
-200 Experiments 10cyc Experiments (without hold)
0.1
Simulations 1,10cyc Simulations (without hold)
-300 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 2 4 6 8 10 12
Axial strain ε, % Number of cycles N , cycle
Figure 23. Experimental and simulated results of uniaxial time-dependent ratcheting for the composites
obtained with different hold times at peak/valley stress points (Vf=21%, at room temperature and
stressing rate 25MPa/s, 50±280MPa, μ=0.05): (a) cyclic stress-strain curves; (b) relations of ratcheting
strain to number of cycles. From [58].
0.8 1.2
(a) (b)
0.7
1.0
0.6
0.8
0.5
0.4 0.6
0.3
0.4
Experiments 12.5MPa/s Experiments (hold 60s)
0.2
Simulations 12.5MPa/s Experiments (hold 15s)
0.2
0.1 Experiments 3.5MPa/s Simulations (hold 60s)
Simulations 3.5MPa/s Simulations (hold 15s)
0.0 0.0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Number of cycles N , cycle Number of cycles N , cycle
Figure 24. Experimental and simulated results of uniaxial time-dependent ratcheting for the composites:
(a) obtained at different stressing rates (Vf=21%, at 573K, 45±215MPa, μ=0.04, without any hold); (b)
obtained with different hold times at peak/valley stress points (Vf=14%, at 573K and stressing rate
3.5MPa/s, 90±140MPa, μ=0.04). From [58]
3.2. Multi-particle Unit Cell Model
From the researches done by Drugan and Willis [59] and Drugan [60], it is concluded that the
size of mono-particle unit cell is too small to represent the microstructure feature of the
composite in the statistical sense; and multi-particle unit cell is a good candidate for the
reasonable numerical simulation to the cyclic deformation of the composites. In fact, many
multi-particle unit cell models have been established to provide more reasonable simulation to
the deformation of the composites. For example, Gusev [61] employed a three-dimensional
cubic unit cells containing up to 64 spherical inclusions to simulate the elastic behavior of
particle reinforced polymers; Watt et al [62] used unit cells containing approximately 10
particles to study the particle distribution effects in metal matrix composites; Brockenbrough
and Suresh [63] simulated the deformation of the composites using a two-dimensional unit
cell model with the realistic microstructure arrangement of particles within the cell, which
determined from actual composite sections; Terada and Kikuchi [64] employed a three-
dimensional unit cell containing realistic particle distributions to simulate the deformation
behavior of a particle reinforced ceramic matrix composite. It should be noted that only the
monotonic tensile or compressive deformation of the composites is discussed in the above-
referred literatures [59-64]. For the simulation to the cyclic deformation of the composites,
Bruzzi et al [65] provided some results by employing the two-dimensional real geometry and
three-dimensional models with J2 plasticity for the matrix, as shown in Fig. 26, respectively,
and compared the saturated cyclic stress-strain hysteresis loops for the three-dimensional
model obtained by using only isotropic hardening and both isotropic and non-linear kinematic
(NL-Iso-Kin) hardening rules. It is concluded that both models result in cyclic hardening with
the effect more pronounced for the isotropic hardening matrix, and a strong Bauschinger
effect is exhibited for the composite due to the NL-Iso-Kin hardening description for the
matrix and the presence of the particle and the resulting generation of internal stresses.
Furthermore, the effects of internal thermal residual stresses on the cyclic behavior are also
discussed by the numerical simulation with three-dimensional unit cell model, and it is
demonstrated that the thermal residual stresses exert a noticeable influence on macro-scale
cyclic response, even though the cyclic straining reduces their average magnitudes.
0.7
0.6
0.5
0.4
0.3 Sphere
Ellipsoid (a=1.2b)
0.2
Ellipsoid (b=1.2a)
0.1
Cylinder (h=2.0r)
0.0
0 2 4 6 8 10 12
Number of cycles N , cycle
Figure 25. Simulated results of uniaxial ratcheting with stress level of 25±280MPa for the composites
with Vf=14% and different particulate shapes obtained at stressing rate 25MPa/s and room temperature,
μ=0.05. From [58]
276 Guozheng Kang
(a) (b)
Figure 26. Unit cells with realistic particle geometries and distributions: (a) two-dimensional real
geometry; (b) three-dimensional multiple particle geometry model. From [65].
Figure 27. Multi-particle unit cells: (a) RVE containing a random and homogeneous distribution of 30
spheres; (b) cubic RVE used in the numerical simulation. From [66].
Recently, based on the discussion for the size of unit cell done by Drugan and Willis [59]
and Drugan [60], Pierard et al [66] simulated the cyclic deformation behavior of particle
reinforced elasto-viscoplastic composites by employing a cubic unit cell containing several
dozens of particles as shown in Fig. 27, where a random and isotropic dispersion of 30
spherical particles of equal diameter is prescribed. This unit cell has been extensively used by
[67-71] to simulate the deformation response of elastic and elasto-plastic composites, and the
results show that the estimations over different particle realizations present little scatter, and
the average value gathers from the simulation of different sphere realizations is reasonably
close (by a few percentage) to the exact solution. Moreover, these simulations allow a check
of the model accuracy under different loading conditions, such as uniaxial, shear and
multiaxial stress states. The simulated results of cyclic stress response for the composite
under uniaxial cyclic straining with certain applied strain amplitude is shown in Fig. 28, and it
is shown that the numerical simulations have a good agreement with the results obtained by
affine homogenization theory developed by Pierard and Doghri [72]. In the multi-particle unit
cell model, the particle centers were generated using the random sequential adsorption
algorithm [73] which provides a statistically isotropic spatial distribution of the particles [74],
in which the probability of finding a particle at a given position is the same in all directions
and throughout the representative volume element (RVE), as shown in Fig. 27a. The cubic
RVE used in finite element simulation is obtained from those distributions by splitting the
particles intersecting a cube face into the appropriate number of parts (two parts if across one
face, four if across two and eight if across three) and copies to the opposite cube faces. The
details about the finite element models can be found in the referred literatures [66-71].
Figure 28. Numerical (symbols) and affine homogenization (solid lines) results of the uniaxial cyclic
deformation for the composites with particle volume fraction of 30%: (a) at strain rate of 10-3s-1; (b) 10-
6 -1
s . From [66].
As above-reviewed, numerical simulation for the cyclic deformation of the composites is

limited for the uniaxial cyclic deformation behavior, no attempt is achieved for the simulation
of biaxial or multiaxial cyclic deformation of the composites due to its complexity. It is
reviewed by [18] that additional hardening will be caused in the material by the non-
278 Guozheng Kang
proportionally multiaxial loading path. However, finite element implementation of the

constitutive model containing such non-proportional additional hardening effect has not been
achieved, even though some constitutive models have been established to involve such effect
by introducing different definitions of non-proportionality for multiaxial loading path [20, 22,
75-78]. Therefore, many efforts should be paid for the finite element implementation of non-
proportionally multiaxial cyclic constitutive model, and then the numerical simulation to the
biaxial or multiaxial cyclic deformation of the composites.
4. Progresses in Constitutive Models

The modeling predictions for elasto-plastic composites found in the literature were based on
three main approaches, i.e., unit cell finite element simulations as reviewed in Section 3,
mean-field homogenization models to be reviewed in detail in this section, and transformation
field analysis or sub-cell methods which can be referred from the literatures done Dvorak
[79], Aboudi et al [80], Bednareyk et al [81] and Roos et al [82], and the reviewed work done
by Chaboche et al [83].
Mean-field homogenization approaches are mainly based on the Eshelby’s equivalent
inclusion theory [84] and its improved versions, such as Mori-Tanaka model [85, 86], and
now have been extensively employed to provide a constitutive modeling prediction to the
elastic and elasto-plastic deformation behavior of the DRMMCs. Since the aim of this
Chapter is reviewed the progresses in studies for the cyclic deformation behavior of the
composites in the inelastic deformation regime, the literature concerning the thermal-elastic
composites are not included here, and can be found in [87, 88] and the literatures referred
there-in. Considering the plastic strain produced in the metal matrix as a part of eigenstrain in
equivalent inclusion model, Arsenault and Taya [89] predicted the thermal residual stress and
the yield strength of whisker reinforced metal matrix composites, and Tandon and Weng [90]
accounted for the disturbance of the field variables by interaction of inclusions and predicted
the monotonic stress-strain behavior of the composites, respectively, with help of a direct
homogenization approach (such as Mori-Tanaka method). Further researches for the
constitutive modeling of elasto-plastic deformation in the composites can be found in the
work done by Qiu and Weng [91-93], Tszeng [94], Suquet [95], Buryachenko [96], Ponte
Castaňeda and Suquet [97], Dunn and Ledbetter [98]and Ponte Castaňeda [99], and so on,
based on a so-called secant (or total deformation) theory. However, the approaches based on
the secant theory are restricted to monotonic and proportional loadings at the macro level and
in each phase, and cannot provide any description to the cyclic deformation of the
composites.
To overcome this shortcoming, based on the Hill’s incremental tangent approach, an
incremental (or tangent) formulation for two-phase elaso-plastic composites was recently
proposed by Doghri and Quaar [100]. Doghri and Quaar [100] showed that the proposed
tangent formulation is capable of simulating the following deformation aspects with
reasonable accuracy, computer time and memory: (1) any rate-independent model for either
phase (even the inclusions can be elasto-plastic); (2) unloading and cyclic loadings; (3) any
multiaxial stress state; (4) structures made of composite materials. Therefore, in the next
paragraphs, it is necessary to outline the tangent formulation developed by Doghri and Quaar
[100].
4.1. Tangent Formulation
In this subsection, only the outline of the tangent formulation developed by Doghri and Quaar
[100] is rewritten, the details can be found in original literature.
4.1.1. Homogenization Approach and Its Incremental Formulation
For a two-phase composite, the matrix (phase 0) has volume V0 and volume fraction v0=V0/V,
where V is the volume of the RVE; and the inclusions (phase 1, assumed to be the same
shape, orientation and stiffness) have a total volume V1 and volume fraction v1=1-v0. Define
the following volume averages in RVE:
1
V ∫V
< f >≡ f ( x )dV (3)
1
< f >Vr ≡
Vr ∫
Vr
f ( x )dVr , r=0, 1 (4)
where, integration is carried out with regard to micro-coordinates x in RVE. It should be

noted that a bold character represents a second-order tensor and a bold capital character
represents a fourth-order tensor, here and hereafter.
It is easy to check that the averages over the entire RVE, the matrix phase and the
inclusion phase are related by
< f >= v1 < f >V1 + (1 − v1 ) < f >V0 (5)
The strain averages per phase are related by a strain concentration tensor B as follows:
< ε >V1 = B :< ε >V0 (6)
where, (:) represents tensor product contracted over two indices. Various homogenization
approaches provide different expressions of strain concentration tensor B. Then, the average
strain for each phase can be related to the macro-strain <ε> by
< ε >V0 = [v1B + (1 − v1 )I ]−1 :< ε > (7)
< ε >V1 = B : [v1B + (1 − v1 )I]−1 :< ε > (8)
Based on the Eshelby’s equivalent inclusion theory, under a remote uniform strain ε , the
strain field inside the ellipsoid is uniform and related to the remote strain by
ε( x ) = H( I , C0 , C1 ) : ε ∀x ∈ (I ) (9)
280 Guozheng Kang
where, I means the inclusion, C0 and C1 represent the stiffness tensors of the matrix and
inclusions, respectively; and the single inclusion strain concentration tensor H is
H( I , C0 , C1 ) = {I + E( I , C0 ) : [(C0 ) −1 : C1 − I]}−1 (10)
The fourth-order tensor E(I, C0) is Eshelby’s tensor and depends on the geometry of
inclusion and the stiffness of the matrix. For any homogenization approach defined by B, the
macro-stiffness C is given by
C = [v1C1 : B + (1 − v1 )C0 ] : [v1B + (1 − v1 )I ]−1 (11)
For Mori-Tanaka model [85, 86], there is
B = H( I , C0 , C1 ) (12)
4.1.2. Incremental Homogenization Formulation
An extension of homogenization models from linear elasticity to rate-independent non-linear

behavior is provided by Hill’s so-called incremental formulation [101] which uses the fact
that stress and strain rates are related by:
σ& ( x, t ) = C r (ε ( x, t ), t ) : ε& (x, t ) ∀x ∈Vr , r = 0, 1 (13)
However, a major difficulty is that the tangent operators Cr are not uniform per phase,
even if each phase’s material is homogeneous. With help of a fictitious reference material
ˆ (t ) , it goes
with uniform tangent moduli C r
σ& ( x, t ) = C
ˆ (t ) : ε& ( x, t )
r ∀x ∈Vr , r = 0, 1 (14)
For Mori-Tanaka homogenization model, it gives
< σ& >= C :< ε& > (15)
and
< ε& >V1 = H( I , C

ˆ ,C
0
ˆ ) :< ε& >
1 V0 (16)
C = [v1C
ˆ : H( I , C
ˆ ,Cˆ ) + (1 − v )C
ˆ ] : [ v H( I , C
ˆ ,Cˆ ) + (1 − v )I]−1 (17)
1 0 1 1 0 1 0 1 1
4.1.3. Tangent Operator and Its Isotropic Part
For elasto-plastic materials, at least two tangent operators, i.e., continuum and consistent one,
can be defined, which is very important in the numerical simulations since the
homogenization formulations adopted depend explicitly on the expressions of tangent
operators. Where, “consistent” means the tangent operator is consistent with the proposed
constitutive model and its integration algorithm, and then consistent tangent operator can be
referred as algorithmic tangent operator, too.
For J2 elasto-plasticity, the tangent operators are:
(2μ )2 dR
“continuum” one Cep = Cel − n ⊗ n, h = 3μ + >0 (18)
h dp
σ eq ∂n ∂n 1 3 dev
“consistent” one Calg = Cep − ( 2 μ ) 2 ( Δp ) , = ( I − n ⊗ n) (19)
σ eq ∂σ ∂σ σ eq 2
tr
3 dev (σ )
where, Cel is elastic modulus tensor, n = , “dev” means the deviatoric part of
2 σ eq
tensor, μ is the shear modulus, p is accumulated plastic strain, and R represents isotropic
hardening. σ eqtr is a trial (elastic predictor) value of equivalent stress σ eq .
For Chaboche’s cyclic plasticity model [102], [103] gives:
(2μ )2 dR 3
“continuum” one Cep = Cel − n ⊗ n, h = 3μ + + a − bn : X (20)
h dp 2
“consistent” one
( 2 μ ) 2 ( Δp ) ∂n (2 μ )2 ( Δp )b 1 (21)
Calg = Cmod − − [ 3 X n − ( X n : n) n ] ⊗ n
[1 + 1.5g ] ∂β [1 + 1.5g ](1 + bΔp )2 β eq h a lg 2
where, X is a back stress, and β≡dev(σ)-X, and other details can be found in [100].
As mentioned by [100], good predictions are obtained only when Eshelby’s tensor is
computed not with an anisotropic tangent operator (Calg or Cep) but with isotropic moduli
(Ciso). The general expression of the isotropic moduli is
Ciso = 3κ t I vol + 2 μt I dev (22)
where, κt and μt are tangent bulk and shear moduli, respectively. Moreover, for a spherical
inclusion with isotropic moduli, the calculation of Eshelby’s tensor only needs the tangent
Poisson’s ratio vt:
282 Guozheng Kang
3κ t − 2 μt
vt = (23)
2(3κ t + μt )
The isotropic tangent operator can be extracted from the anisotropic operator by different
ways, as stated in [100], and its practical form for the J2 elasto-plasticity or Chaboche’s cyclic
plasticity is deduced and given in [100].
(a) For MMC
(b) For PMC
Figure 29. Comparison of different predictions for the cyclic deformation behavior of the composites:
(a) MMC; (b) PMC. From [100].
Based on the incremental homogenization models outlined above, Doghri and Ouaar
[100] provided some simulations for the cyclic deformation behaviors of a particle reinforced
metal matrix composite and a particle reinforced polymer matrix composite. It is seen from
Fig. 29 that the predictions provided by the homogenization models are in good agreement
with the numerical simulations by finite element method.
4.2. Improved Tangent Formulations
The tangent formulation proposed by Doghri and Quaar [100] is validated only for the case
when the reinforcement is spherical inclusion. After then, Doghri and Friebel [104] proposed
an improved version of the numerical algorithms and considered the cases with non-spherical
inclusions, such as short fibers and platelets. For original tangent formulation [100], a direct
(single step) homogenization procedure based on an extension of Mori-Tanaka model was
adopted, which has the required symmetries only if all the inclusions are aligned and similarly
shaped. It implies that the original tangent formulation cannot be directly used to simulate the
deformation behavior of the composites containing the inclusion with non-uniform orientation
defined by an orientation distribution function. To overcome such shortcoming, the original
tangent formulation was extended by Doghri and Tinel [105], and they proposed a new two-
step homogenization procedure, as shown in Fig. 30. The improved tangent formulation can
deal with any rate-independent deformation behavior of any phase and the cases under cyclic
or non-proportional loading conditions.
Figure 30. Two-step homogenization procedure. First step: the RVE is decomposed into a set of
pseudo-grains and each one is homogenized. Second step: homogenization over all pseudo-grains.
From [105].
In elasto-viscoplasticity, there is no one-to-one correspondence between stress and strain

rate through a so-called continuum tangent operator such as it exists in elasto-plasticity,
which results the Hill’s incremental formulation of elasto-plastic composites cannot be
rigorously used; however, with help of an algorithmic tangent operator derived from a
consistent linearization of the time-discretized constitutive models, a Hill-type incremental
formulation can be used in the case of elasto-viscoplasticity. Unfortunately, as observed in
various simulations, such approach gives too stiff responses and can even violate a rigorous
284 Guozheng Kang
upper bound. It is seen from the work done originally by Molinari [106] and more recently by
Masson and Zaoui [107] and Masson et al [108] that a so-called affine formulation seems to
give softer and more realistic predictions. Therefore, Pierard and Doghri [109] proposed an
enhanced affine formulation to predict the monotonic tensile and uniaxial cyclic deformation
behavior of a particle reinforced metal matrix composite. In the affine formulation, each
phase’s elasto-viscoplastic constitutive model is linearized into a fictitious linear thermo-
elastic relation defined in the Laplace-Carson space (obtained by Laplace-Carson
transformation), and at this stage, classical homogenization schemes (such as Mori-Tanaka
model) valid in thermo-elasticity can be applied (in thermo-elastic homogenization, a tangent
operator is still used). A special care is necessary for the implementation of the method in
order to obtain accurate estimates of the integrals involved and handle the numerical Laplace-
Carson inversion. It is seen from Fig. 31 that the predictions by enhanced affine formulation
are in good agreement with the numerical results by finite element method.
Figure 31. Comparison of affine formulation with finite element analysis. From [109]
As reviewed-above, many new constitutive models for the DRMMCs have been proposed
in order to predict their deformation behaviors (containing cyclic deformation behavior) more
accurately, with help of new homogenization formulations and tangent (or secant) operators
for local constitutive relations. However, some major improvements have still to be done in
the future work, especially for the prediction to the cyclic deformation behavior of the
DRMMCs presented in proportional and non-proportionally multiaxial cyclic loading. For
example, the ratcheting behavior of the composite occurred in asymmetrical cyclic stressing
and observed by [48, 49] has not been simulated by such models yet. More reasonable cyclic
constitutive models which can describe the cyclic deformation behavior of the matrix metal
should be introduced into the micromechanical theory of the composites.
5. Conclusions and Suggestions

In recent years, a significant progress has been made in the study on the cyclic deformation
behaviors of DRMMCs. Some new phenomena have been observed to the composites by
uniaxial and multiaxial cyclic tests. For example, a ratcheting behavior (i.e., cyclic
accumulation of inelastic deformation) occurs in the composites subjected to an asymmetrical
cyclic stressing, and presents a remarkable time-dependence. Based on the proposed mono-
particle and multi-particle unit cells, the cyclic deformation behaviors, including the
ratcheting, of the composites have been extensively simulated by finite element method.
Some numerical results, especially for those obtained by multi-particle unit cell are in good
agreement with the corresponding experimental results. Moreover, the mechanism of cyclic
hardening/softening features presented in the composite has been revealed by the detailed
microstructure observation and with help of micromechanical finite element analysis.
Recently, many new constitutive models for the DRMMCs have been proposed with help of
new homogenization formulations and tangent (or secant) operators for local constitutive
relations in order to predict the cyclic deformation behavior of the composites. However,
some major improvements have still to be done in the future work, especially for the
prediction to the cyclic deformation behavior of the DRMMCs presented in proportional and
non-proportionally multiaxial cyclic loading.
As a conclusion of the review, the following suggestions are presented about the further
research:
(1) Experimental observation to the proportional and non-proportional multiaxial cyclic

deformations (especially for the multiaxial ratcheting behavior) of the DRMMCs and
their time-dependence at room and high temperatures, as well as their micro-
mechanism.
(2) Numerical simulations for the cyclic deformation of the composites under
proportional and non-proportional multiaxial cyclic loading conditions with help of
multi-particle unit cells.
(3) Development of new constitutive model considering the prediction of uniaxial and
multiaxial ratcheting by introducing newly developed cyclic plastic or viscoplastic
models into the homogenization formulation. The models based on the Ohno-Wang
kinematic hardening rule [110] are good candidates.
(4) Numerical simulations with more reasonable micro-mechanical unit cells which can
reflect the microstructure feature of the composite in the higher enough extent. The
unit cell containing few dozen inclusions is a good candidate.
(5) Considering the non-uniform stress or strain filed in phases. The multi-scale method
should be a good candidate.
(6) Check the capability of other homogenization formulations (except the Mori-Tanaka
and Double Inclusion models reviewed in this Chapter) to simulate the cyclic
deformation behavior of the composite, and propose a new and more reasonable
homogenization formulation.
286 Guozheng Kang
Acknowledgement
Financial supports of the Project of New Century Excellent Talents in University (NCET05-
0796), Fok Ying Tung Education Foundation (91007) and Sichuan Youth Science and
Technology Foundation (05ZQ026-028), China, are gratefully acknowledged.
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Chapter 6
BIODEGRADABLE POLYMER COMPOSITES
Long Yu1,2*, Steven Petinakis1, Katherine Dean1 and Ling Chen2

1
CSIRO, Materials Science and Engineering, Australia
2
Centre for Polymers from Renewable Resources, ERSPSP, SCUT, China
1. Introduction
Like most conventional polymers, biodegradable polymers are rarely used by themselves,
because most of them have relatively poor mechanical and thermal properties, and therefore
reinforcement techniques using fibers or fillers are particular important.
Natural fibers (e.g. cotton, flax, hemp, jute) have been widely used in polymeric materials
to improve mechanical properties, and can generally be classified as bast, leaf or seed-hair
fibers. Cellulose is a major constituent derived from vegetable fibers, and applications for
cellulose fiber-reinforced polymers have again come to the forefront with the current focus on
renewable raw materials [1–3]. Hydrophilic cellulose fibers are very compatible with most
natural polymers. The reinforcement of starch with cellulose fibers is a perfect example of a
composite produced by polymers from renewable resources (PFRR).
The reinforcement of polymers using fillers is common in the production and processing
of polymeric materials. The interest in new nanoscale fillers has rapidly grown over the last
two decades, since it was discovered that a nanostructure could be built from a polymer and
layered nanoclay. These new nanocomposites have shown dramatic improvements in
mechanical properties at low filler content. Reinforcement with fillers is particularly
important for natural polymers, since most of them have the disadvantages of lower softening
temperatures and lower modulus. Furthermore, the hydrophilic behavior of most natural
polymers offers a significant advantage, since it provides a compatible interface with the
nanoclay. These new composites are extending the utilization of biodegradable polymers into
new value-added products.
*
E-mail address: long.yu@csiro.au
294 Long Yu, Steven Petinakis, Katherine Dean et al.
2. Biodegradable Polymers
2.1. Natural Polymers
The study and utilization of natural polymers is an ancient science, with typical examples
such as paper, silk, skin and bone art easily found in museums around the world. However,
the availability of petroleum at lower cost and the biochemical inertness of petroleum-based
products have proven disastrous for the natural polymers market. Recently, after a lapse of
almost 50 years, the significance of eco-friendly materials has been realized again, and these
ancient materials have rapidly gained attention, primarily due to environmental issues and the
shortage of oil. Modern technologies provide powerful tools to elucidate microstructures at
different levels, and to understand the relationships between structures and properties. These
new levels of understanding provide opportunities to develop materials for new applications.
However, the inherent biodegradability of natural polymers also means that it is important to
control the environment in which the polymers are used, to prevent premature degradation.
For example, the water solubility of many natural polymers increases their degradability and
the speed of degradation, therefore limiting their application. Another limitation of many
natural polymers is their lower softening temperature. Apart from natural rubber, starch,
cellulose, protein and chitin have attracted great interest.
2.2. Synthetic Polymers from Bio-derived Polymers
The evolution of synthetic polymers using monomers from renewable natural resources
provides a new direction in the development of biodegradable polymers. One of the most
promising polymers in this regard is polylactic acid (PLA), because it is derived from
agricultural products and is readily biodegradable. Lactide is a cyclic dimer prepared by the
controlled depolymerization of lactic acid, which in turn can be obtained by the fermentation
of corn, sugar cane and sugar beat [4,5]. Although PLA is not a new polymer, better
manufacturing practices have improved the economics of producing monomers from
agricultural feedstocks, and as such PLA is at the forefront of the emerging biodegradable
plastics industry..
2.3. Polymers from Microbial Fermentation
In nature, a special group of polyesters is produced as internal carbon and energy storage by a
wide variety of micro-organisms, as part of their survival mechanism. Poly(β-
hydroxybutyrate) (PHB) was first mentioned in the scientific literature as early as 1901, with
detailed studies beginning in the 1920s [6,7]. Over the next 30 years, PHB inclusion bodies
were studied primarily for academic purposes. The energy crisis of the 1970s was an
incentive to seek naturally occurring substitutes for synthetic plastics, which accelerated the
research and commercialization of PHB. The brittleness of PHB was improved through the
copolymerization of β-hydroxybutyrate with β-hydroxyvalerate [8,9]. This family of
materials, known as PHBV, was first commercialized in 1990 by ICI, but its high cost
remains the major barrier to its widespread usage.
Biodegradable Polymer Composites 295
2.4. Synthetic Aliphatic Polyesters
Many aliphatic types of biodegradable polyesters are obtained by lactone ring-opening

polymerization. The following chemical formula shows the general structure of biodegradable
aliphatic polyesters:
–[– O – R– CO –]n–
whereby the structure of a polyester depends on the structure of R. The most prominent
biodegradable polyester is polycaprolactone (PCL), which is commercially synthesized by
ring-opening polymerization of ε-polycaprolactone. Poly(lactic acid) (PLA) is a commercial
biodegradable polyester that has been widely used in packaging, and also as a biomedical
material in drug delivery systems and scaffolds.
3. Natural Polymer Composites

3.1. Mineral Filler-Reinforced Natural Composites
Mineral fillers have been widely used in conventional polymers to improve mechanical
properties and to reduce costs. For example, Wilhelm et al. [10] used a mineral clay as a filler
to improve the mechanical properties of glycerol-plasticized Cará starch films. Dynamic
mechanical analyses showed that the composite films gave rise to three relaxation processes,
attributable to a transition of the glassy state of the glycerol-rich phase, to water loss
including the interlayer water from the clay structure, and to the starch-rich phase. A film
with 30% w/w of clay showed an increase of more than 70% in the Young’s modulus
compared to non-reinforced plasticized starch. Both X-ray diffraction (XRD) and infra-red
spectroscopy showed that glycerol could be intercalated into the clay galleries and that there
was a possible conformational change of starch in the plasticized starch/clay composite films.
Clay exfoliation occurred in unplasticized starch/clay mixtures. Nanoclay-reinforced starch-
based materials will be discussed in the following section.
3.2. Fiber-Reinforced Natural Composites
Fiber-reinforced plastics have successfully proven their value in various applications because
of their excellent specific properties, e.g. high strength and stiffness, and low weight. One of
the most important advantages of using natural fibers to reinforce natural polymers is their
compatibility, since both exhibit polar behavior. Wollerdorfer and Bader [2] investigated the
influence of plant fibers such as flax, jute, ramie, oil palm fibers and fibers made from
regenerated cellulose, on the mechanical properties of biodegradable polymers. Riedel and
co-workers [3,11] produced so-called biocomposites by embedding natural fibers (e.g. flax,
hemp, ramie) into a biopolymeric matrix made of derivatives from cellulose, starch, lactic
acid etc. Bledzki and Gassan [1] reviewed a number of composites reinforced with cellulose-
based fibers, and evaluated the physical and chemical treatment methods that improved the
adhesion between the cellulose fibers and conventional polymers. The different treatments
changed a number of properties of the natural fibers, such as the degree of hydrophilicity, so
that the moisture effects in the composite could be reduced. To produce hydrophobic
properties in natural fibers, a special treatment – termed acetylation – was introduced.
3.3. Cellulose Fiber-Reinforced Starch-Based Materials
Starch reinforced with cellulose is a typical scenario in natural polymer composites. These
materials have the advantages of being renewable, biodegradable, abundantly available and
inexpensive, and as such they have attracted much attention over the last two decades. As
with many other fiber-reinforced composites, improving mechanical properties is one of the
major driving forces for the use of cellulose fibers to reinforce starch-based materials.
Wollerdorfer and Bader [2] reported that the performance of composites reinforced with
thermoplastic wheat starch exhibited strength 4 times greater than without fibers, with the
reinforcement of cellulose diacetate and starch blends resulting in a strength increase of 52%
and 64%, respectively. Enhanced properties were obtained using various natural cellulosic
fibers, such as sisal, cotton, bamboo, jute, straw, kenaf and wood.
Compared to inorganic fillers, natural fibers offer a number of benefits, including:
renewable natural resource, an abundance and variety of fibers , low energy consumption, low
cost, low density, high specific strength and modulus (desirable fiber aspect ratio), high sound
attenuation, relative ease of processability (due to their flexibility and non-abrasive nature,
which allow high filling levels, resulting in significant cost savings), and their relatively
reactive surfaces (which can be used for grafting specific groups) [12]. The various
processing methods for producing starch-based materials are reviewed in the following
section.
3.3.1. Extrusion
Ganjyal et al. [13] reported on the formation of starch acetate/corn fiber foams prepared by
extrusion. Corn starch was acetylated to introduce thermoplastic properties. Corn stalks were
treated with sodium hydroxide to remove the lignin and to obtain purified cellulose fibers.
Starch acetate was blended with treated fibers at concentrations of 0, 2, 6, 10 and 14% (w/w)
and extruded at 150°C in a co-rotating twin-screw extruder with 12–18% w/w ethanol content
and 5 wt% talc as a nucleating agent. They found that fiber incorporation at the lower
concentrations enhanced the physical properties of the foams, and that fiber contents greater
than 10% decreased expansion, and increased density and shear strength. Good compatibility
between starch and corn fiber was observed. Shogren et al. [14] reported that mechanical
properties were further improved with the use of chemically modified starches and additives
such as aspen fiber and monostearyl citrate. They found that modified starches improved
flexibility and aspen fiber imparted strength, while monostearyl citrate improved water
resistance.
3.3.2. Injection Molding

Funke et al. [15] reported on different types of starch that were processed in blend systems
with natural plasticizers and commercial fibers using conventional extrusion and injection
molding techniques. Blend systems with 2–7% fibers resulted in increased tensile strength
and water resistance of the resultant products. Averous et al. [16] studied the interactions
between leaf wood cellulose fibers and plasticized wheat starch matrices. After extrusion and
injection molding, the properties of different thermoplastic starch (TPS)-based composites
were analyzed. Dynamic mechanical thermal analysis showed a strong evolution of the main
relaxation temperature, which could be linked to the existence of cellulose/starch interactions
resulting in a decrease in starch chain mobility. This phenomenon was consistent with the
evolution of mechanical behavior. Scanning electron microscopy (SEM) also correlated this
hypothesis. Similar results were also found for starch-based materials reinforced with
lignocellulose fibers [17] processed using extrusion and injection molding. The results were
consistent with static mechanical behavior, which varied according to filler content (up to 30
wt%), natural fiber (cellulose versus lignocellulose) and fiber length (from 60 μm to 1 mm).
The addition of cellulose fillers also improved the thermal resistance of these biocomposites.
3.3.3. Hot-Press Molding and Foaming

Romhány et al. [18] reported on TPS-based composites containing flax fibers in
unidirectional and cross-ply arrangements, produced by hot pressing using the film stacking
method. The mechanical response and failure mode of the composites was strongly dependent
on the flax content and the flax fiber lay-up. It was established that the tensile strength
increased with increasing flax fiber content (up to 40 wt%), but remained almost constant
above that value. In the case of a composite with 40 wt% unidirectional fiber reinforcement,
the tensile strength was three times greater than that of the pure starch matrix, i.e. the flax
fiber increased the tensile modulus of the pure starch by several orders of amplitude.
Matsui et al. [19] produced composites consisting of a mixture of 90% cassava bagasse
(non-extracted starch) and 10% Kraft paper. Kraft paper was used as a source of long fibers,
in order to improve the mechanical properties of the composites, which had similar
characteristics to the molded fiber packaging produced using recycled paper, as used in egg
boxes. However, cassava bagasse has advantages over recycled paper, in view of the fact that
it is obtained from a renewable resource.
Alvarez et al. [20] reported on biodegradable polymers based on starch reinforced with
short sisal fibers, at a range of fiber contents of 5–15 wt%. Equations obtained from
microscopic mass balances for diffusion in solids were used to predict the absorbed humidity
in both components (sisal fibers and biodegradable polymer) and in the composites as a
function of time. Different model predictions of the composite diffusion coefficients as a
function of filler concentration were also examined, and were found to be in agreement with
the experimental results.
Curvelo et al. [21] used cellulosic fibers from Eucalyptus urograndis pulp as
reinforcement for TPS, in order to improve mechanical properties. The composites were
prepared with regular corn starch plasticized with glycerin and reinforced with short
cellulosic fibers (16% w/w) from bleached pulp. The fibers were added directly to the TPS in
an intensive batch mixer set at 170°C. The mixture was hot pressed to 2–3 mm thick plates,
from which specimens were cut for mechanical testing. The composite showed an increase of
upto 100% in tensile strength and more than 50% in modulus compared to the non-reinforced
TPS. SEM imaging of fractured surfaces revealed very good adhesion between the fibers and
the matrix. The results obtained clearly showed the advantages of reinforcing TPS with
cellulosic fibers – a natural, cheap and abundant material. Carvalho et al. [22] characterized
compounds of conventional corn starch and glycerol reinforced with cellulose fibers using
high-performance size exclusion chromatography. The compounds and composites were
prepared in an intensive batch mixer at 150–160°C, with glycerol and fiber contents of 30–50
wt% and 1–15 wt%, respectively. The results showed that an increase in glycerol content
reduced starch degradation, whereas an increase in fiber content led to increased degradation.
The changes in the chromatographic profiles were more pronounced in the high molecular
weight fraction, corresponding to amylopectin. The polydispersity index of the matrix was
lower than that of native starch, due to selective breakage of large amylopectin molecules as a
result of shear-induced fragmentation.
Lawton et al. [23] studied the effects on mechanical properties of the addition of aspen
fiber to baked corn starch foams. Foam batters were made with fiber contents ranging from
2.5 to 45 wt%, and starch/fiber composite foam trays were formed by heating a batter inside a
closed mold. The trays were stored at different relative humidity (5, 20, 50, 81 and 93%) for
one week prior to mechanical testing. It was found that the strength of the foam trays
increased with increasing fiber content, up to a fiber content of about 15 wt% (15–30 wt%
fiber content had no significant impact on tray strength; >30 wt% fiber content resulted in
lower tray strength. The lower tray strength was thought to be due to the lack of uniform fiber
distribution at high fiber content. Displacement of the trays at break was also affected by fiber
content.
4. Biodegradable Polyester Composites

4.1. Fiber-Reinforced Polylactic Acid Composites
PLA, which can be derived from natural feedstocks such as corn starch, is one of the most
promising biodegradable polymers. PLA can be processed by conventional methods such as
injection molding, blow molding and film forming operations, since it has a glass transition
temperature (Tg) of 55–65°C and a melting temperature of 150–175°C. Because of its similar
or, in most cases, superior mechanical properties, PLA has attracted much interest as a
replacement for petrochemical polymers such as polypropylene and polyethylene, particularly
in the area of single-use packaging applications. However, PLA exhibits low toughness due to
its brittle nature, and, in order to overcome this, it is useful to incorporate natural fillers into
the polymeric matrix. It has already been stated that the incorporation of natural fillers into
polymer matrices can optimize mechanical properties, however, from an economical
viewpoint, the ready availability and lower cost of natural fillers can result in more cost-
competitive composites [24,25].
Oksman et al. [26] studied the incorporation of cellulose fibers as reinforcement in PLA.
Due to the brittle nature of PLA, triacetin was used as a plasticizer in the matrix (as well as in
PLA/flax composites) to improve impact properties. Plasticizers can be used during
processing to lower the viscosity of the matrix polymer, thus aiding filler dispersion in the
matrix polymer. Fiber dispersion is a critical factor to be considered during the development
of biodegradable natural fiber composites. Shibata et al. [27] evaluated the use of short abaca
fibers in the development of biocomposites using biodegradable polyesters, and found that
strength and modulus increased with decreasing fiber diameter for both untreated and treated
abaca fiber. Wollerdorfer and Bader [2] and Plackett et al. [28] investigated the influence of
plant fibers (e.g. flax, jute, ramie, oil palm) and fibers made from regenerated cellulose on the
mechanical properties of biodegradable polymers.
Huda et al. [29] evaluated the use of recycled cellulose in the development of “green”
composites, using PLA as the matrix and recycled cellulose from newsprint. The physico-
mechanical properties of the composites, as well as the morphological properties, were
investigated as a function of varying amounts of recycled cellulose.
Mathew et al. [30] conducted a study aimed at developing PLA-based high-performance
nanocomposites using microcrystalline cellulose (MCC) as reinforcement. The study focused
on achieving the best possible dispersion of the MCC within the PLA during processing.
Comparisons were also made using wood flour and wood pulp as an alternative
reinforcement. Tserki et al. [31,32] investigated the usefulness of lignocellulosic waste flours
derived from spruce, olive husks and paper, as reinforcement in biocomposites using PLA as
the matrix, and concluded that while mechanical properties such as tensile modulus were
enhanced, strength and toughness may not necessarily be improved. This can be attributed to
several reasons. For example, due to the hydrophilic nature of natural fillers, compatibility
with the hydrophobic polymer matrix can be problematical [33]. However, a variety of
chemical and physical treatments can be utilized to improve fiber–matrix adhesion in
biodegradable polymer composites, such as acetylation [34], isocyanate treatment [35] and
esterification [36].
Eco-toxicity is an important factor to consider when developing polymer composites
from renewable resources. Isocyanate compounds such as methylene diisocyanate (MDI) may
not be regarded as a viable treatment method for natural fibers, because their decomposition
in water can result in the formation of diamines, some of which are suspected of being
carcinogenic or a possible cause of hepatitis in humans. As reported in the literature, an
alternative is lysine-based diisocyanate (LDI). Lysine is a naturally occurring amino acid with
two amino groups and one carboxylic group, and it can react with hydroxyl groups in
cellulose, forming an isocyanate bridge, which can then readily react with the carboxylic and
hydroxyl groups of the matrix polymer. Lee and Wang [37] reported the use of LDI as a
coupling agent in the development of biodegradable polymers produced from PLA/bamboo
fibers and poly(butylene succinate) (PBS)/bamboo fibers. Eco-composites made from PLA,
PBS and corn starch with a designable interface have also been prepared by reactive
processing using LDI and hexamethylene diisocyanate (HDI) as coupling agents [38].
MDI has been used in the compatibilization of PLA and starch blends, and Wang et al.
[39] discovered that blends of PLA with 45% wheat starch and 0.5% MDI resulted in
composites with the highest tensile strength. They also showed that moisture absorption
increased as a function of increasing starch content. Water absorption can influence the
mechanical properties of composites, and it is interesting to note that the highest strength
recorded in the blends studied by Wang et al. was achieved at 45% water content. This can be
attributed to two major reasons. Firstly, the level of water in a blend can aid in the processing
of PLA, whereby the water behaves as a plasticizer. Secondly, the viscosity of the PLA at this
water content level may be sufficient to allow optimum dispersion of the starch particles
within the PLA matrix. However, in order to use such materials in commercial applications,
such as for short-term packaging, the surfaces of end-products would require waterproofing,
otherwise the degradation rate of such materials would be too rapid.
4.2. Fiber-Reinforced Polycaprolactone Composites
Both short and long cellulose fibers have been used to reinforce polycaprolactone (PCL). Lee
and Ohkita [40] studied wood flour (WF)/PCL composites prepared by knead processing,
using PCL-graft-maleic anhydride (PCL-g-MA) as a compatibilizer. At 5% PCL-g-MA,
tensile strength and Young’s modulus increased from 13 to 27 MPa and from 581 to
1011 MPa in WF/PCL (50/50 w/w) composites, respectively. Elongation at break increased
from 4 to 7% and from 3 to 6% in the WF/PCL and the WF/PBSC composites, respectively.
Tensile strength was further increased with increasing WF content in the presence of PCL-g-
MA. Furthermore, thermal flow temperature and melt viscosity were increased, and water
absorption and thickness swelling of the composites were improved with the addition of PCL-
g-MA.
Arbelaiz et al. [41] studied composites of biodegradable PCL and short flax fiber
bundles. In order to improve the fiber/matrix adhesion, a PCL-g-MA compatibilizer was
prepared in an internal mixer. Dicumyl peroxide was used to initiate the grafting reaction of
the MA onto the PCL polymer. Composites fabricated with flax fiber bundles and a PCL-g-
MA matrix showed the highest tensile and flexural strength. An SEM study of fractured
surfaces confirmed the adhesion improvement between the flax fiber bundles and the PCL-g -
MA matrix.
Corden et al. [42] introduced a novel manufacturing technique for long-fiber composites,
primarily being developed as bone substitute for use in maxillofacial reconstructive surgery,
however, the technique could be adapted to other areas where bio-absorbable composite
materials may be used. The development of a totally bio-absorbable long-fiber composite
material would facilitate a two-stage degradation, whereby the matrix material would degrade
first, leaving a scaffold structure of degradable fibers, which would be absorbed at a later
stage. Corden et al. polymerized caprolactone monomer in situ within a tool cavity to produce
a net-shape molding. Inclusion of a fiber preform within the tool cavity, which was
impregnated with the liquid monomer, produced a long-fiber composite material. The
produced PCL with a range of molecular weights using this liquid molding technique to
assess the physical and biocompatibility properties compared to commercially available PCL.
The results showed that high-quality PCL with a narrow molecular weight distribution and
properties similar to commercially available PCL can be produced using the technique.
Polymerization of the monomer around a woven fiber preform made of a PLA/poly(glycolic
acid) copolymer (vicryl mesh) produced a bio-absorbable long-fiber composite material.
Since hydrophilic cellulose fibers (CF) and hydrophobic PCL are generally immiscible,
interfacial adhesion cannot occur without the use of compatibilizers or coupling agents, and
various techniques have been developed to improve the interface between CF and PCL. Kim
et al. [43] reported on PCL/starch/pine-leaf composites with possible application as
biodegradable food-packaging materials. The silane coupling agent used led to much better
interfacial compatibility between the PCL matrix and the filler, resulting in composites with
better physical properties. Teramoto et al. [44] studied composites of PCL with 10 wt%
untreated or acetic anhydride-treated (AA-) abaca fibers, with a particular emphasis on their
biodegradability, and found that neither untreated nor AA-abaca had a pronounced affect on
weight loss, because PCL itself has a relatively high biodegradability. Funabashi and Kunioka
[45] reported on PCL/CF composite samples prepared by direct molding during
polymerization from CL monomers. Samples were produced by mixing CL liquid with
yttrium triflate as a catalyst and 2-propanol as an initiator, followed by the addition of CF to

various levels. Sample mixtures were put into plastic tubes and heated at various temperatures
(60–120°C) for various times (6–48 h). After cooling, composites were removed from the
tubes and cut into column-shaped specimens, in which the CF was homogeneously dispersed.
The maximum strength (13 MPa) and modulus (65 4MPa) were recorded for composites
incorporating 34% fiber content. These values were greater than those recorded for samples
without CF.
Since PCL is a semi-crystalline polymer, additional substances could affect its
crystallization behavior. Cyras et al. [46,47] used differential scanning calorimetry (DSC) to
study the crystallization kinetics of PCL/starch materials reinforced with sisal fiber (SF).
They found that the activation energy of the crystallization process was 4.3 and 4.0 kJ/mol for
PCL/starch and PCL/starch/SF composites, respectively, i.e. the induction time of
crystallization and the crystallization rate were not significantly influenced by the presence of
SF. Simulations of the temperature and relative degree of crystallinity developed across the
thickness of PCL/starch/30%SF molded samples under different cooling conditions were
carried out, and gradient-less crystallinity profiles were obtained at a constant wall
temperature of 283 K and at sample thicknesses less 10 mm. On the other hand, when cooling
at a constant cooling rate, paired degree of crystallinity pieces were obtained only at
thicknesses less than 2 mm.
4.3. Fiber-Reinforced Poly(Hydroxybutyrate) Composites
PHB has been blended with other polymers to reduce inherent brittleness, as well as to reduce
the high production costs associated with microbial polyesters. The miscibility, crystallization
behavior, physical properties, biodegradation and degree of biodegradability of microbial
polyester-containing blends are all significantly affected by the nature of the blend
components, and cellulose derivates have attracted much interest for their compatibility with
PHB.
Zhang et al. [48] investigated the miscibility, crystallization, melting behavior and phase
morphology of PHB and ethyl cellulose (EC) blends prepared by casting films. The blends
showed composition-dependant Tg; the temperature position increased with a decrease of
PHB content, and it reached a maximum value for the EC component. After melt quenching
or cooling via DSC, only a low temperature Tg was found, corresponding to that of the PHB
phase in the blends. This Tg remained almost unchanged at about 5 or 9°C for all the blends.
The hydrogen bonding of the hydroxyl groups of EC was found to be stronger than that of the
hydroxyl group in EC with carbonyl groups in PHB. Unlike the PHB component, the blends
displayed no crystallization when cooled from the melt during the DSC non-isothermal
crystallization runs.
Maekawa et al. [49] studied the phase behavior and crystallization kinetics of binary
blends of PHB/cellulose propionate (CP). The results showed that the blends were miscible,
as evidenced by a single composition-dependant Tg, a depression of the equilibrium melting
temperature of PHB, and a decrease in the spherulitic growth rate of the PHB component. A
study of the tensile properties showed an improvement in the ductility of PHB after blending
with CP.
El–Shafee et al. [50] studied different blends of PHB with cellulose acetate butyrate
(CAB) produced by solution casting from chloroform solutions. The PHB/CAB blends were
found to be miscible in the melt state, as evidenced by a single Tg for each composition, a
depression in the equilibrium melting point of PHB, and a marked reduction in the spherulitic
growth rate of PHB in the blends. The phase structure of the blends in the solid state, as
revealed by single-angle X-ray scattering, was characterized by the presence of a
homogeneous amorphous phase situated mainly in the interlamellar regions of crystalline
PHB, and consisting of CAB molecules and non-crystalline PHB chains. Similar results were
also reported by Wang et al. [51], who found that with an increase in CAB content, the degree
of crystallinity and the melting temperature of the PHB phase decreased, broadening the
narrow processability window of PHB. They also report that as the elongation at break
increased from 2.2 to 7.3%, the toughness and ductility of the PHB improved.
Shanks et al. [52] studied natural fiber/biopolymer composites using flax and PHB. The
biopolyesters consisted of the homopolyester PHB and its copolymers with 5 and 12% 3-
hydroxyvalerate (PHV). The adhesion between the fibers and the polyesters was found to be
better than for analogous polypropylene composites. Wetting of the fibers by the polyesters
was observed using SEM. Nucleation was increased by the fibers and by a silane coupling
agent used as an adhesion promoter. The melting temperature was influenced by the
optimized adhesion and copolymerization. The bending modulus was increased in the
composites and dynamic mechanical analysis revealed a storage modulus, with a smaller
component as the loss modulus. The maximum in the loss modulus curve was taken as Tg,
and this increased in the composites. The influence of the silane coupling agent was found to
be beneficial to the material properties of the biopolyester/flax composites. An earlier study
by the same authors [53] showed that flax and PHB had good interfacial adhesion, however
this was decreased when plasticizers were present, because some plasticizer migrated from
the flax to the PHB and caused complex changes in the glass transition, crystallization and
crystallinity of the PHB.
Avella et al. [54] reported on the thermal and mechanical behavior of the
biotechnological polyester PHBV reinforced with wheat straw fibers. In order to improve the
chemico-physical interactions between the components, the reinforcing agent was submitted
to pretreatment with high-temperature steam, leading to fibers that were richer in cellulose
and more reactive. The addition of straw fibers was found to increase the rate of PHBV
crystallization, while it did not affect the crystallinity content. Furthermore, comparison of the
mechanical properties have shown that the composites exhibited higher Young’s modules and
lower values of both stress and strain to break than the neat matrix of PHBV. Le Digabel et al.
[55] report a reinforcing effect with the use of lignocellulosic fractions from wheat straw as
natural fillers in composites with biodegradable polyester (poly(butylene adipate-co-
terephthalate)).
5. Multilayer Composites
An inherent problem with the use of natural polymers (e.g. TPS) as biodegradable materials is
their sensitivity to moisture. One approach toward solving this problem is to laminate them
with water-resistant, biodegradable polymers. Of the different techniques for lamination,
coextrusion or multilayer extrusion has many advantages, such as the entire process is
completed in a solvent-free single step.
5.1. Multilayer Extrusion
Multilayer extrusion has been widely used in the past to combine the properties of two or
more polymers into one single multilayered structure [56–59]. Much progress in multilayer
extrusion has been made and new technology provides capabilities to co-extrude materials
with viscosity ratios up to 40:1. It is also possible to co-extrude materials with melt
temperature differences as high as 80°C without causing damage or thermal degradation to
heat-sensitive materials. The layer thickness can also be adjusted to produce minimal skin
layers of 2%.
Mitsoulis [60] conducted a numerical simulation of multilayer coextrusion flows of
polymer melts used in producing multilayered plastic sheets. Viscosity and other material
properties data for typical melts and the adhesives applied in co-extrusion were used.
Industrial designs were employed for the feed-block geometry and multi-manifold vane flat
dies. The analysis was based on the lubrication approximation theory, which treats the flow
locally as fully developed, and which uses a Newton–Raphson iterative scheme to solve the
equations for a pressure-drive flow of a number of layers (N ≤ 11). For a given total flow rate
ratio (or correspondingly total sheet thickness and individual layer thickness), the solution
provides the interface locations and individual pressure drops that each extruder has to
supply. The shear stresses at the channel walls are checked as a criterion for proper design.
The die design or melt combinations are altered to produce smooth shear stresses with no
humps or discontinuities at the points of confluence. Adiabatic temperature rises are also
computed based on the pressure drops in the system. This type of analysis provides
qualitative insight into the proper design and melts combinations for multilayer sheet co-
extrusion.
Wang et al. [58] studied the effects of extrusion and formulation variables on the
structure and properties of starch/polyester laminates. Three-layer polyester/starch/polyester
sheets were prepared using a twin-screw extruder for the starch/water center layer, a single-
screw extruder for the outer polyester layers, and a feed-block and coat-hanger-type sheet
dye. Overall sheet and coating thicknesses were more uniform as the coating polymer
viscosity decreased, the starch melt viscosity increased and the feed-block/die temperature
increased. Peel strengths were 1–2 orders of magnitude higher for high molecular weight PCL
compared to low molecular weight PCL, and the high peel strengths were associated with
rough, wavy interfaces (interfacial instability). The addition of a plasticizer such as glycerol
and sorbitol to the starch decreased peel strengths. Peel strengths varied little between the
types of polyester coating, except perhaps for PLA and polyesteramide, which were more
difficult to peel. Some possible applications of laminated starch include food packaging and
the controlled release of drugs and pesticides.
5.2. Starch/Polyester Multilayer Composites
One of the key issues in the development of multilayer composites is the interfaces between
materials. Multilayer films based on plasticized wheat starch (PWS) and various
biodegradable aliphatic polyesters have been prepared through flat film co-extrusion and
compression molding [61]. PLA and PHBV were chosen as the outer layers of the stratified
polyester/PWS/polyester film structure, with the main aim of significantly improving the
mechanical performance and moisture resistance of the PWS. Since no specific compatibilizer
or tie layers were incorporated, the properties of the subsequent films relied solely on the
compatibility between the respective materials. The effects of glycerol content in the PWS,
polyester type and film composition on the mechanical properties and adhesion strength of
multilayers were investigated, and the conditions for optimal product performance were
examined. These multilayer films may be suitable for applications in food packaging or other
disposable items.
Gattin et al. [62] developed a coextruded starch/PLA polymeric film with a Young’s
modulus at 2340 MPa, elongation at break at 50% and contact angle at 118°. Mineralization
of the material’s carbon content was carried out using the appropriate ISO standard
experimental methods. Regardless of the biodegradation medium used, the percentage of
mineralization was better than the required 60% value for the definition of a biodegradable
material. Moreover, repartitioning of the material’s carbon between the various degradation
products was quantified throughout the duration of experimental runs. The presence of starch
was found to facilitate the biodegradation of the polylactic component, especially in liquid
media.
6. Biodegradable Nanocomposites
Since the pioneering work by the Toyota group [63–65], polymer nanocomposites have
attracted an increasing amount of attention. In particular, polymer/silicate nanocomposites
have been shown to exhibit significant improvements in mechanical properties compared with
pure polymers or conventional composites [66]. The inclusion of well-dispersed nanosilicates
in polymers has led to a vast array of changes, including increased storage modulus, increased
tensile and flexural properties, and decreased permeability and flammability [66,67]. In
general, there are three different types of polymer/layered silicate nanocomposites, namely:
intercalated nanocomposites in which the insertion of polymer chains into a layered silicate
structure occurs in a crystallographically regular fashion, with a repeat distance of a few
nanometers, regardless of the polymer-to-clay ratio;
intercalated nanocomposites in which intercalated and stacked silicate layers flocculate to
some extent due to the hydroxylated edge–edge interactions of the silicate layers and
exfoliated nanocomposites in which the individual silicate layers are separated in the polymer
matrix by average distances that depend only on the clay loading [67].
6.1. Natural Polymer/Nanoclay Composites
6.1.1. Starch/Nanoclay Composites

A number of researchers have presented work in the field of starch nanocomposites. Park et
al. [68,69] reported on the preparation and properties of gelatinized starch/montmorillonite
(MMT) clay nanocomposites using both naturally occurring sodium MMT and a number of
alkyl ammonium-modified clays. XRD and transmission electron microscopy (TEM) showed
an intercalated structure in the starch/sodium MMT, however the modified clays appeared
either unchanged or agglomerated. Park et al. [68] found that starch/unmodified sodium
MMT nanocomposites exhibited the greatest increase in modulus for all the clays used. They
also investigated the effect of clay content on the barrier properties of the nanocomposites,
and found that increasing clay content led to an improvement in barrier properties [69].
Huang et al. [70] reported on TPS/MMT-reinforced glycerol composites that had been
formed using melt extrusion. SEM showed well-dispersed MMT platelets, while Fourier
transform infra-red spectroscopy indicated that cooperation existed between the MMT and
starch molecules, whereby hydrogen bonds had formed between the reactive hydroxyl groups
of MMT and the hydroxyl groups of the starch molecules. They also reported significant
improvements in mechanical and thermal properties.
Wilhelm et al. [10] have also investigated the formation of starch/clay nanocomposites,
using a Ca2+ hectorite. Solution cast starch/clay nanocomposites showed no XRD peaks due
to the first basal spacing, indicating almost total exfoliation in the starch matrix. Although
this was a good result, starch does require some kind of plasticizer to reduce brittleness.
When glycerol was added by itself to the clay, the interplanar distance increased to 18.5Å,
however a peak at 9.3Å also appeared, corresponding to the d-001 spacing for the dehydrated
clay.
Fischer and Fischer [71,72] investigated a number of experimental pathways in their
study of starch/clay nanocomposites, including the dispersion of Na+ MMT clay in water,
followed by blending in an extruder at 85–105°C with a premixed powder of potato starch,
glycerol and water. The resulting material appeared to be fully exfoliated and exhibited a
reduction in hydrophilicity, and improved stiffness, strength and toughness.
Another group of starch-based nanocomposites are those that incorporate biodegradable
polyesters. McGlashan and Halley [73] studied the dispersion of nanoclays in a number of
different biodegradable starch/polyester blends. The crystallization temperature of the
nanocomposite blends was found to be significantly lower than the base blend, probably due
to clay platelets inhibiting order, and hence crystallization, of the starch and polyester. The
best dispersions were found in the 30 wt% starch blends, and the level of delamination
depended on the ratio of starch to polyester and the amount of organoclay added.
Kalambar and Rizvi [74] also investigated starch nanocomposites and successfully made
starch/PCL blends in the presence of MMT nanoclay. Reactive extrusion results showed that
the addition of a modified nanoclay at 3 wt% increased elongation almost fourfold over that
of neat starch/PCL blends. The nanocomposites displayed better solvent-resistant properties
because of the resistance to diffusion offered by the clay platelets in the polymer matrix.
6.1.2. Protein/Nanoclay Composites

Dean et al. [75–77] studied a number of plasticized soy protein/clay nanocomposites and,
through the use of high-powered ultrasonics, produced an exfoliated-type nanocomposite that
exhibited significantly improved modulus. They have developed a unique technology to
exfoliate nanoclay using a clean additive (water) and clean energy (ultrasonics). As water is
commonly used in the processing of many natural polymers, and as it interacts strongly with
the ions generally found in the intergallery spacing of layered nanoclays, ultrasonics can be
used to produce tiny bubbles, which can collapse violently, releasing significant energy that
can be used to exfoliate clay.
6.2. PLA Nanocomposites
A number of researchers have developed polylactide-based nanocomposite materials. Ray et

al. [78] prepared PLA/organically modified layered silicate nanocomposites by melt
extrusion. The effect of oligo(-caprolactone) as a compatibilizer in the nanocomposites was
investigated, focusing on morphological analyses and mechanical property measurements. An
intercalated nanocomposite was produced that exhibited improvements in material properties
in both solid and melt states.
Pluta et al. [79] investigated PLA/MMT nanocomposites by studying dispersions of
modified and unmodified MMT prepared by melt blending. XRD showed that the affinity
between the organo-modified clay and the PLA was sufficient to form an intercalated
structure in the nanocomposite. Thermogravimetric analysis showed that the PLA-based
nanocomposites exhibited improved thermal stability in air.
Ray et al. [80] also investigated PLA/MMT nanocomposites, in which the MMT was
modified with trimethyl octadecylammonium cation and used as an organically modified
layered silicate in the nanocomposite preparation. All nanocomposites exhibited
improvements in practical material properties such as storage modulus, flexural modulus,
flexural strength, heat distortion temperature and gas barrier properties, compared to neat
PLA. The biodegradability of neat PLA and a representative PLA/MMT nanocomposite was
also studied under compost, and the nanocomposite material displayed a significantly
increased rate of biodegradation.
Chang et al. [81] studied the dispersion in PLA of two organoclays (a hexadecylamine-
modified MMT (C16-MMT) and hexadecylamine-modified fluorinated mica (C16-Mica)).
Solution intercalation was used to produce nano-dispersions of the organoclays in the PLA.
Increased tensile strength and modulus were observed up to a maximum clay content of 4
wt% C16-MMT. In contrast, the initial modulus and tensile strength of the nanocomposites
containing C16-Mica increased continually with increasing clay content up to 8 wt%.
Chang et al. [82] also compared C16-MMT to dodecyltrimethyl ammonium bromide-
modified MMT and the commercially available Cloisite 25A in the preparation of PLA
nanocomposites. From morphological studies using TEM, most clay layers were found to be
dispersed homogeneously in the matrix polymer, although some clusters or agglomerated
particles were also detected. The authors also found that the degradation temperature (at a 2%
weight loss) of the PLA nanocomposite films with C16-MMT and Cloisite 25A decreased
linearly with increasing organoclay content. The O2 permeability values for all the
nanocomposites for clay loadings up to 10 wt% were less than half the corresponding values
for pure PLA, regardless of organoclay used.
A number of authors have also studied the dispersion of both unmodified and organically
modified MMT in poly(ethylene glycol) (PEG)-plasticized PLA [83,84]. Paul et al. [83]
found that at constant filler level, MMT organo-modified by bis-(2-hydroxyethyl)methyl
(hydrogenated tallowalkyl (HTA) ammonium cations produced the greatest increase in
thermal stability. Increasing the amount of clay was shown to delay the onset of thermal
degradation of the plasticized polymer matrix. They also showed via wide-angle X-ray
scattering and DSC analysis that competition existed between the PEG and PLA for
intercalation into the interlayer spacing of the clay.
6.3. PCL Nanocomposites
Lepoittevin et al. [85] reported on nanocomposites of PCL prepared melt blended with natural
Na+ MMT or MMT modified by HTA-based quaternary ammonium cations, such as dimethyl
2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Similar
systems have also been reported by Hasook et al. [86]. Di Maio et al. [87] investigated the
isothermal crystallization of PCL/clay nanocomposites at different clay concentrations, using
DSC and rheometry, and the results showed that the well-dispersed organoclay platelets acted
as nucleating agents in the PCL matrix, as confirmed by a significant reduction of the
crystallization half-time.
Di et al. [88] investigated melt-blended PCL hybrids with two types of organoclays:
Cloisite 30B (30B) and Cloisite 93A (93A). They found that the PCL/30B hybrids formed
nanocomposite structures as a result of the strong interaction between the organic modifier in
30B and the PCL, whereas the PCL/93A hybrids formed micro-composite structures. The
performance of PCL/30B nano-composite film as a barrier to air permeation was significantly
improved compared to pure PCL and PCL/93A micro-composites at low organoclay
concentration. Also, the permeability coefficient increased with increasing organoclay
content, which could be attributed to the more tortuous gas-permeation pathway caused by
organoclay exfoliation. Both tensile modulus and tensile strength were increased in PCL/30B
nanocomposites even at low organoclay content, and without the decrease in strain at break
associated with pure PCL. The significant improvements in both barrier performance and
mechanical properties in PCL nanocomposites could be attributed to the fine dispersion of
30B organoclay platelets in the PCL matrix, and the strong interaction between the organic
modifier in 30B and the matrix molecules. The barrier properties of similar systems were also
investigated by Gorrasi et al. [89].
Recently, Shibata et al. [90] reported that dibutylamine-terminated ε-caprolactone
oligomers with number-averaged molecular weights (Mn) of 500, 1300 and 2200,
respectively, were synthesized by ring-opening polymerization of ε-caprolactone initiated by
2-(dibutylamino)ethanol in the presence of tin(II) 2-ethylhexanoate. Nanocomposites based
on PCL and caprolactone oligomer-treated montmorillonites (CLO-Ms: CLOL-M, CLOM-M,
and CLOH-M) were prepared by melt intercalation. The tensile strength and modulus of
PCL/CLO-M composites increased with increasing molecular weight of CLO and increasing
inorganic content. The tensile modulus of PCL/CLOH-M nanocomposites with an inorganic
content of 5.0 wt% was three times higher than that of a control PCL. Among the PCL/CLO-
M composites, PCL/CLOM-M had the highest crystallization and melting temperatures.
Kalambur and Rizvi [91] developed a reactive extrusion process in which high amounts
of starch (approx. 40 wt%) could be blended with PCL, resulting in tough nanocomposite
blends with elongation properties approaching that of 100% PCL. Strength and modulus
remained the same as starch/PCL composites prepared by simple physical mixing without any
crosslinking. SEM showed improvement in starch/PCL interfacial adhesion in reactively
extruded blends with crosslinking, compared to without crosslinking. Dynamic mechanical
analysis showed changes in primary α-transition temperatures for both the starch and PCL
fractions, reflecting crosslinking changes in the nanocomposite blends at different organoclay
contents. Kalambur and Rizvi [92] also studied the rheological behavior of reactively
extruded starch/PCL nanocomposite blends using an off-line capillary rheometer. Power law
models for blends with different nanoclay volume fractions were developed using appropriate
correction factors.
In addition to nanoclays, other nanoparticles have been used to reinforce PCL, such as
silica [93], tetra isopropyl ortho titanate [94] and Mg/Al hydrotalcite [95], and have also been
found to significantly improve mechanical properties.
7. Conclusion
Although the study and utilization of natural polymers is an ancient science, the use of these
materials has rapidly evolved over the last decade, primarily due to environmental issues and
the shortage of oil. Modern technologies provide powerful tools to elucidate microstructures
at different levels, and to understand the relationships between structures and properties in
polymeric blends. However, much more research is required before arriving at ideal
polymeric blends and composites from renewable resources. The techniques used to
composite these materials can significantly improve their mechanical properties, however
they may have limited impact on another weaknesses such as moisture sensitivity. A
promising alternative technology is multilayer extrusion.
Some aliphatic polyesters have been recognized for their biodegradability and their
susceptibility to hydrolytic degradation. Biodegradable polyesters such as PLA and PCL have
attracted much attention because they are commercially available, and have very low or no
toxicity. However, the high price and relative poor mechanical performance of these
biodegradable aliphatic polyesters remain key issues limiting their general application. Fiber-
reinforcement techniques are of significant interest, and although aliphatic polyesters and
hydrophilic natural fibers are thermodynamically immiscible, leading to poor adhesion
between the two components, various compatibilizers and additives are being studied to
improve their interfacial characteristics, such as the interfacial adhesion.
The future growth and sustainability of biodegradable composites as replacements for
petroleum-based plastics are reliant on continued research, in particular in the fields of
compatibilizing mechanisms, surface modification and advanced processing techniques.
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Chapter 7
COMPOSITE MATERIALS STUDIED AT A MOLECULAR

SCALE. USE OF FLUORESCENT LABELS
Javier Gonzalez-Benito
Departamento de Ciencia e Ingeniería de Materiales e Ingeniería Química, Universidad
Carlos III de Madrid, Avda. Universidad 30, 28911- Leganés, Madrid, Spain
Abstract
Among other factors, properties of composite materials depend on the type of adhesion
between their constituents since they are a function of the ability to transfer loads from the
matrix to the reinforcement. There are many studies about surface modification of
reinforcements to improve their adhesion with matrices trough the creation of more or less
complex interphases. In fact, mechanical properties and ageing of composites can greatly
change as a consequence of the different structures and morphologies generated in the
interphase. There are several theories that try to explain the mechanisms responsible of the
composites performance; however, in most of the cases, the “interphases” are not enough
understood because it is experimentally very difficult to obtain information at a nanoscopic
and/or molecular scale; for instance: i) structural information; ii) dynamic behaviour and iii)
ageing phenomena.
Due to the difficulty in knowing this interfacial structure, most of the researchers have
focused their efforts to study the structure and properties either the polymeric matrix or the
reinforcement surface and, subsequently, they have related them to the behaviour in service of
the composites. However, although the nature of the reinforcement surface affects the final
structure of the interphase and therefore, the final properties of the composites, it is of great
interest to know how the coupling region interacts with the polymer matrix in order to acquire
the basics necessary to obtain in the future composites with tailor made interphases and
therefore controlled properties. Therefore, the necessity of optimizing experimental methods
to collect information at a molecular scale from specific sites like coupling regions and
interphases is evident. A possibility to overcome this is the use of fluorescent labels since, in
many cases, without modifying the properties of the system, it is possible to have enough
fluorescence signal importantly affected by the immediate surrounding (local polarity,
rigidity, pH …) of the label.
This work tries to summarise important aspects about the use of the fluorescent labels
chemically bonded to specific sites such as interfaces in composite materials to get
information about its molecular structure, its dynamics and the accessibility of small
molecules like water.
316 Javier Gonzalez-Benito
1. Introduction
1.1. Polymer Matrix Composites and Interfaces
A commonly accepted definition for composite materials corresponds to those formed by two
or more constituents which are physically delimited from one another. Polymer matrix
composite materials are constituted by a polymer, either thermoplastic or thermoset, both
sometimes conveniently modified and a reinforcement material (glass, carbon, polyaramide,
polyethylene, etc.) generally in the form of continuous fibres or fabric although nowadays
micro and nanoparticle are having a special attention. The intelligent combination of those
materials is characterized, among other factors by: a) presenting synergism; b) allowing
anisotropy control and c) presenting interfacial regions with specific properties which greatly
condition the final properties of the composite.
One of the most important factors affecting the properties of the composite materials is
the kind of adhesion between their constituents [1-3]. For example, in the case of mechanical
properties, they are a function of the ability to transfer the loads applied from the matrix to the
material used as the reinforcement [4]. In the case of polymers reinforced with different
oxides (glass fibres, silica, alumina, titania micro or nano-particles) the most common method
to improve the adhesion between the polymer matrix and the reinforcement is to use silane
coupling agents which could conveniently modify the reinforcement surface [2].
Silane coupling agents are organosilicon compounds with, in general, a double
functionality (see Figure 1). One of them, X, represents alkoxy groups or chlorine that can be
hydrolysed yielding, depending on the silane, from one to three silanol groups that
subsequently can condensate with silanols, aluminols, etc. of the reinforcement surface and
each other to generate a more o less crosslinked structure attached all-around the
reinforcement (Figure 1).
Figure 1. Use of silane coupling agent to attain a chemical attachment between a polymer matrix and an
inorganic reinforcement.
Composite Materials Studied at a Molecular Scale. Use of Fluorescent Labels 317
On the other hand, the second functionality of the silane, Y, represents a non-
hydrolysable organofunctional group such as amino, mercapto, etc. that can react or
effectively interact with the functional groups of the matrix. For instance, in the case of
epoxy-based composites, amino silanes are typical because of the addition of amine
hydrogens to the epoxy ring.
In the last years, big efforts have been done in order to understand the relationships
between the interfacial structure and the final properties of the composites. Although the
problem filler/polymer matrix has been treated in many articles, up to now, it has not been
solved yet. Due to the difficulty to study the interfacial structure in the final composite, most
of the researchers have focused their works, either to the study of the structure and properties
of the polymer matrix, or to the study of the structure in the coatings used to surface modify
the reinforcements for, subsequently, relating them to the final properties and behaviour in
service of the composites under consideration [1,5-10]. However, although in fact the
structure of those coatings affects the final structure of the interface and therefore, the
properties of the composite material, it is of great interest to know how the coupling region
interacts with the polymer matrix to finally generate the interphase.
To the author knowledge, up to now, very few are the works focused to the study of new
composite materials with tailor made interfacial structures and even morphologies which
were susceptible of yielding particular properties. Due to this, it is still necessary to study
those systems with more deepness conducting them to the influence exerted by the nature of
the filler surface (surface treatments) on the polymer matrix. Depending on the nature of the
filler surface, its higher or lower affinity with one of the components of the matrix can
generate a particular structure or morphology at the interphase that, at the same time, might
induce specific properties in the composite material.
Through the interphase, from the surface of the filler to the polymer bulk, structure and
properties gradients appear which may enormously influence the final properties of the
composite. Those regions usually are influenced by the kind of filler, its surface modification,
the polymer matrix and the conditions of preparing the composite (curing conditions in the
case of termosetting matrices). Due to this, it is necessary to have a clear vision about the
mechanism or mechanisms through which those interphases are generated: i) chemical
reactions in the coupling region; ii) miscibility degree between the surface coating of the filler
and the polymer matrix; iii) preferential diffusion of one of the components of the matrix to
the filler surface (additives, precursor monomers in the case of in-situ generated polymers,
polymers in the case of polymer blends and blocks in the case of block copolymers) [11,12].
Among others, these are the effects that may cause the morphology and/or the structure of the
filler/polymer interphase to be very different from that of the proper polymer used as the
matrix [12-14].
It is generally accepted that the interfacial region in this sort of materials has a thickness
from a few nanometers to several hundreds of them [15]. However, the important rigidity
variations observed by Iglesias et al. [16] in glass fibres/epoxy matrix composites when
different fibre coatings are used suggest that, in some cases, the interfacial region must be
even larger than what it was though. In fact, Van Assche et al. [17] and González-Benito [14]
with different methods obtained results that confirmed the existence of one interphase in the
micrometric scale. Van Assche et al. [17], using microthermal analysis determined the glass
transition temperatures along the interphase of an epoxy/silica composite seeing progressive
changes in a region of tens of microns. On the other hand, González-Benito [14] using FTIR
imaging also observed in a region of tens of microns that the structure of the epoxy polymer
in a glass fibre/epoxy matrix composite changes gradually along a perpendicular direction to
the long axe of the glass fibre. This result was assigned to stoichiometric variations in the
reactive system as a function of the distance respect to the glass fibre surface due to the effect
exerted by the glass fibre surface. Besides, Palmese and McCullough [11,18] reached similar
conclusions for an epoxy-amine reactive system with carbon fibres without coating. They
showed the existence of a preferential adsorption of one of the reactive precursors to the
surface of the carbon fibres. This phenomenon seems to be the origin of a non stoichiometric
epoxy-amine composition in the interfacial region leading therefore to well distinct properties
to the matrix bulk far away from the surface of the fibre.
It seems again that a deep knowledge of the coupling region in a composite and the
changes that may occur on it during the interphase creation so as along the composite life is
crucial to understand the interfacial structure and properties and therefore the final properties
of the composite material. However, is really difficult to study that specific region (coupling
region) due to its small size (less than 10 nanometers). An interesting way to affront this
challenge is the use of fluorescent labels due to the great deal of information that can be
extracted from it although many times the interpretation of fluorescence was not easy.
1.2. Fluorescent Labels
Fluorescent labels are those molecules or groups of atoms (fluorophore) chemically bonded to
specific sites which present the capability of emitting photons of UV/Vis light, h·ν’ (h is the
Planck`s constant and ν’ is the frequency of the emitted radiation) after absorbing photons of
UV/Vis radiation, h·ν, of higher frequency ν or lower wavelength than the emitted one, ν’.
Actually, the fluorescence occurs as a radiative release of energy when the fluorophore in its
first (electronically) excited state S1 reached by absorption of one photon returns to its ground
state, S0. Taking into account that the excess in energy acquired after absorption of light can
be released by other means as the non-radiative processes, the final fluorescence quantum
yield can be defined as
kf
Φf =
∑ki
i
where kf is the rate of fluorescent emission and ∑k i

i
is the sum of all rates of excited state
decay. Other rates of excited state decay are caused by mechanisms other than photon
emission and are therefore usually called "non-radiative rates".
The basic idea of using fluorescent labels in specific sites of materials can be find in that
the physico-chemical characteristics of these sites are reflected in the fluorescent response of
the fluorophore [19]. As an example, the whole process of using fluorescent labels can be
summarized by the scheme shown in Figure 2. To explain the scheme of Figure 2 one could
say that a fluorophore located in a site in which it was surrounded by blue A groups will emit
blue light (lower wavelength) while a fluorophore located in a site in which it was surrounded
by red B groups will emit red light (higher wavelength). Therefore, the interpretation of the
spectra obtained may offer local information about the system under study.
Due to its extraordinary sensitivity, the amount of label necessary to get enough
fluorescent signal is so low to assume that not general perturbation in the system under study
is introduced. Besides, the use of fluorescence is a very sensitive and non-destructive method
to follow whatever changes appearing in the nanoscopic region where the label is located. In
fact the use of the fluorescent response from labels has become a very powerful tool for
following changes in its surroundings such as polarity and rigidity [20-28].
Some studies have proposed that an enhancement in the microviscosity of the medium
leads to a decrease in the non-radiative decay rate and, consequently, an increase in the
fluorescence quantum yield [27]. Other studies use the increase in the fluorescence intensity
that comes from the chemical changes in the fluorophore [29,30]. However, these methods do
not eliminate the effect of intensity variations arising from external factors, such as lamp
intensity, optical alignment, excitation area and temperature variations and, due to this, other
methods for fluorescence analysis have been considered. Neckers and co-workers [31,32]
reported the use of fluorescence probes (fluorophores without chemical attachment) for
monitoring the curing process of acrylate monomers with an intensity ratio method,
Lemmetynen and co-workers [33-35] developed another intensity ratio method in which the
ratios of the low-to-high-intensity changes in the emission bands were used to determine the
degree of curing processes and González-Benito and co-workers considered the use of the
first moment of the emission bands to investigate rigidity and polarity changes in different
kinds of polymer systems [25, 36,37].
Figure 2. Scheme of the process of using fluorescent labels to get information about specific sites in
materials (M is the fluorophore and M* the excited fluorophore).
In the following sections are presented, as examples, different studies that can be carried
out in composites by using the fluorescent response of a fluorophore. In all of then the effect
of the nature of glass fibres surface in the interfacial properties of epoxy based polymer
matrix composites has been evaluated.
1.3. Sample Preparation
To obtain different surfaces in the glass fibres, heat cleaned glass fibres were reacted with
three aminosilanes: 3-aminopropyltriethoxysilane (I), APTES; ii) 3-
aminopropylmethyldiethoxysilane (II), APDES and iii) 3-
aminopropyldimethylmonoethoxysilane (III), APTES.
O-CH2-CH3 O-CH2-CH3
H2N-CH2-CH2-CH2-Si O-CH2-CH3 H2N-CH2-CH2-CH2-Si O-CH2-CH3
O-CH2-CH3 CH3
I II
CH 3
H2N-CH2-CH2-CH2-Si O-CH2 -CH3
CH3
III
In this way three different coatings with different structures are expected. In particular,
taking into account the different functionality of the silane, the structure shown in Figure 3 for
the coatings seems to be most reasonable: monomeric, linear and crosslinked structures when
monoethoxy, diethoxy and triethoxy are used respectively.
Figure 3. Coating structures that might be obtained using aminosilanes with different functionality.
To have local information of specific regions in the composite (interface and matrix bulk)
two sets of samples were prepared. Those for which the fluorophore was attached exactly to
the glass fiber surface, and those with the fluorescent label located in the matrix bulk
(Figure 4).
Figure 4. Specific location of the fluorescent label a) coupling region and b) matrix bulk.
a) Interface labelling
First of all, any filler that is going to be used in a composite is silanized with silanes with
a particular nonhydrolizable functional group, Y (see Figure 1) and then the Y functionalized
filler is reacted with a particular functional group of the selected fluorophore. As an example,
the amino groups coming from aminosiloxane coating can be reacted with the sulfonyl group
of the Dansyl fluorophore via the formation of a very stable sulphonamide group [41]
(Figure 4).
Figure 4. Scheme for the interface labelling process.
b) Matrix labelling
In this case, it is once more only necessary to find a fluorophore with a functional group
susceptible of reaction with a particular group of the polymer used as the matrix. In the case
of diepoxy-diamine based matrices only one of the reactive components of the thermoset is
usually labelled. For example the epoxy group of Diglycidilether of bisphenol A, a typical
epoxy component in epoxy based thermosets, can be reacted with the amino group of the
fluorophore dansyl cadaverine [37], the reaction is schematically shown in Figure 5.
Figure 5. Labelling of Epoxy based matrices.
2. Results and Discussion

2.1. Use of Fluorescence to Monitor Cure Processes in Composites
There are many studies which have shown the use of intrinsic or extrinsic fluorescence (by
means of fluorescence probes and labels) as a very good method for monitoring
polymerization processes at a molecular scale, in situ and in a non destructive way [24,29-
34,36,38-44]. Among the different photophysical characteristics of the chromophores used for
monitoring cure processes, or polymerizations in general, those associated to changes shape
of the fluorescence spectra such as, an intensity ratio [31, 33, 34-36,42] or the first moment of
the fluorescence emission band [35-38,41] are preferred since they are generally unaffected
by experimental conditions. However, many works have used just the fluorescence intensity
to monitor the polymerization processes. Generally, in addition to quenching phenomena,
variations in the fluorescence intensity can be due to: i) a microviscosity enhancement of the
medium which leads to a decrease in the non-radiative decay rate and consequently a
substantially increase in the fluorescence quantum yield [24] or ii) chemical changes of the
fluorophore [30]. However, these methods do not eliminate the effect of intensity variations
arising from those external factors mentioned.
There are certain fluorescent groups, such as dansyl and derivatives (DNS)
[33,35,36,41,44-47], that show appreciable shifts in their fluorescence emission bands
depending on the polarity and/or rigidity of their surroundings (solvatochromism). Therefore,
their spectral shift seems to be a good photophysical parameter to monitor whatever the
changes appearing at a molecular scale in polymeric systems; for instance, the physico-
chemical changes along a cure reaction and even a phase separation if one of the components
that phase separates has intrinsically or extrinsically (label or probe) the fluorescent group.
To optimize processing conditions of thermosetting materials, among other things, it is
necessary to model the kinetics of the reaction by monitoring, if possible, non-destructively
and in situ the chemical conversion during the cure process. Due to this, many scientists have
tried to attain these objectives, particularly in the case of epoxy resins. Although several
techniques have been shown to be adequate to monitor the cure process in epoxy-based
materials, FTIR [48–51] and DSC [51–54] have been probably the most widely used.
However, they show some limitations. First of all, they seem to have low sensitivity at high
conversions [51] and, additionally, DSC does not offer the possibility of monitoring the cure
process non-destructively. On the other hand, FTIR and DSC provide information from the
whole system and it is not possible to monitor the cure process in specific sites of interest, for
instance, interfacial regions. To overcome these difficulties, the use of fluorescent response
from probes or labels is being revealed as a very easy and feasible tool.
In fact, some attempts have been made to model the epoxy curing at the interface of
glass/epoxy matrix composites, either using glass plates [15] or doing the experiments in real
systems formed by glass fibres and an epoxy matrix [41,43,55].
As an example, it is interesting point out the study carried out by D. Olmos et al. [41] in
which the fluorescence response of the dansyl chromophore was used to study the kinetics of
epoxy cure processes in glass fibre/epoxy matrix composites. They compared the results
obtained when the fluorescent label is chemically bonded to the glass fibre surface with those
obtained when the fluorophore is chemically bonded to the matrix bulk, studying additionally
the effect of the glass fibre coating. Two glass fibre surface treatments were investigated
since commercial E-glass fibres were surface coated with APTES and APDES.
In Figure 6, as an example, the typical evolution of the dansyl fluorescence spectrum with
epoxy curing at constant temperature is shown when the fluorophore is in a glass fibre/epoxy
composite.
Figure 6. Typical evolution of the dansyl fluorescence spectrum with epoxy curing at constant
temperature when the fluorophore is in a glass fibre/epoxy composite.
Two phenomena can be clearly observed in the spectra of Figure 6 as the cure reaction
progresses: i) an increase of the fluorescence intensity and ii) a blue shift of the fluorescence
band. Assuming that in this system only two photophysical phenomena account for the
deactivation of the excited state of the dansyl chromophore; fluorescence and thermal
deactivation by collisions (other photophysical phenomena such as quenching, non-radiative
energy transfer, cross-system, etc., are considered negligible), an enhancement of the

fluorescence intensity when polymerization advances is usually explained by an increase of
the viscosity [24, 32, 35-37,40,41]. Particularly, to monitor the evolution of the Dansyl band
the phtophysical parameter so called the first moment of the fluorescent band, <ν>, was
chosen since the fluorescence band can be considered as a distribution of energies or
wavenumbers, ν, so this parameter should reflect the averaged band shift during the cure
process. Therefore, representing the values of this parameter, or other related with it, as a
function of curing time, an epoxy-amine cure process “in-situ” and non-destructively can be
monitored, either in the composite interface or in the matrix bulk.
Figure 7 shows the correlation of the extent of reaction in terms of fluorescent, α ν ,
between the epoxy curing exactly at the interface (fluorescent label localized at the interface),
α νi , and the epoxy curing in the epoxy bulk (fluorescent label localized in the epoxy bulk),
α νB . Regardless of the surface coating, two regions can be observed: the first one points a
higher reaction rate at the interface and was explained considering that, when the epoxy resin
penetrates the interface, the increase in the viscosity is faster because of a higher local
concentration of the amino groups while, the second one, points a lower reaction rate at the
interface, indicating that when the reaction at the interface starts to be controlled by diffusion
(the reaction rate decreases), the reaction in the bulk still continues to be chemically
controlled. On the other hand, comparing the cure behaviour as a function of the silane
coating, it was observed a faster interfacial reaction when APDES is used and this result was
explained in terms of a more opened structure for this coating [41].
Figure 7. Fluorescent extent of epoxy reaction when fluorescent label is localized at the interface, α νi ,
as a function of the fluorescent extent of reaction when fluorescent label is localized in the epoxy bulk,
α νB , in glass fibre/epoxy composites for two differently silanized fibres, APDES and APTES (cure
temperature 40ºC).
2.2. Use of Fluorescence to Study Thermal Relaxation Phenomena Exactly at

Composite Interfaces
It is well known that in polymer composite materials is necessary, among other things, to
know the dynamic behaviour or any magnitude related with it, for instance the glass transition
temperature, of the interfacial region. In terms of rigidity it should be interesting to avoid a
sharp transition between the reinforcement and the matrix. Therefore, the interface should
have intermediate properties with respect to the properties of the constituents of the
composite. One way to modify the interfacial properties may be by changing the molecular
structure of the coupling region, for example, by changing the molecular structure of the
surface coating in the reinforcement if a silane has been used as the coupling agent. However,
due to the low weight fraction of the coupling region, the conventional techniques of thermal
analysis are not adequate to study thermal transitions at the interface.
Van Assche et al. [17], using microthermal analysis were able to determine the glass
transition temperatures as a function of the distance to the surface of the reinforcement in a
silica/epoxy composite in the microscale. However, due to their high sensitivity and site
specificity, the use of fluorescent probes and labels could be a good alternative if more local
information is required.
In general, luminescent methods are based on the dependence of the fluorescent emission
intensity on temperature (radiative and non-radiative constant rates) when that dependence is
related to the thermal relaxation processes of the polymer [56–62]. However, other authors
have tried to use other photophysical parameters that in principle are less subjected to
experimental problems [62,63]. For instance, Lenhart et al. [63], analyzing the band shift of
dimethylaminonitrostilbene (wavelength at the maximum of the emission band) as a function
of temperature, studied an apparent glass transition of the interfacial region formed by a glass
microscope coverslit and an epoxy polymer. On the other hand, Albalá et. al. [62] studied
local thermal transitions in real epoxy/silica composites using the fluorescence arising from
the dansyl group chemically bonded to specific sites.
In the last case referenced [62], the composite material was labelled either in the interface
or in the matrix bulk and the fluorescence changes were studied as a function of temperature.
In that way, it was possible to study differences between the polymer dynamic in those
regions and additionally the influence of the surface nature on the thermal phenomena
detected by fluorescence at the interfaces.
Albalá et al. [62] compared the fluorescence evolution of the dansyl label with
temperature for three samples: i) APTES-S-DNS (silica/epoxy composite where the silica was
previously silanized with APTES and labelled with dansyl fluorophore); APDES-S-DNS
(silica/epoxy composite where the silica was previously silanized with APDES and labelled
with dansyl fluorophore) and APTES-M-DNS (silica/epoxy composite where the silica was
previously silanized with APTES and the epoxy matrix labelled with danyl fluorophore). The
first moment of the emission band was used to follow possible changes in the fluorescence
with the temperature and it could be observed (Figure 8) specific discontinuities on the curves
that were associated to thermal relaxations and concretely to glass transitions considering the
concordance observed with the glass transition temperature of the epoxy matrix obtained by
differential scanning calorimetry.
Figure 8. Top, first moment of the dansyl emission band, <ν>, as a function of temperature for the
samples APTES-S-DNS, APDES-S-DNS and APTES-M-DNS, APTES-I, and APDES-I and bottom,
DSC trace of sample APTES-M-DNS.
After comparing results of thermal transitions it was suggested that: i) there is a higher
rigidity (the discontinuity occurs at higher temperature) in the interfacial region than in the
matrix bulk and ii) the APDES coating yields a more rigid coupling region than the APTES
coating due to higher interpenetration between the epoxy based matrix and the more opened
APDES polysiloxane coating.
2.3. Use of Fluorescence to Monitor Water up Take Exactly at the Interfaces

of Composite Materials
Although few works have accounted with the study of water uptake in composites [64–67]
and there is an extensive literature about the nature of the reinforcement surfaces (in
particular when silanes are used as coupling agents) [68,69], it is necessary to treat more
deeply the role of the interphase in that process and, more specifically, how the nature of the
reinforcement surface affects the water absorption.
Several techniques and methods have been used to monitor the water absorption in
epoxy-based materials. Probably, the gravimetric analysis is the most common method to
follow the water absorption in epoxy systems [70–75]. Although this method is very easy to
perform, it generally can not be carried out in situ and give information about the whole
process without distinguishing between different kinds of water in the system. Another
technique used to monitor the water uptake in epoxy systems is Fourier transformed infrared
spectroscopy either in the medium range [76,77], FT-MIR, or in the near range [76,78-80],
FT-NIR. In these cases, among the advantage of monitoring the water absorption in situ, the
analysis of the IR spectra in both ranges allowed the assignment of bands coming from
different kinds of water [76]. On the other hand, in the last years the time-resolved FTIR
spectroscopy is being revealed as a good method to distinguish more easily the different
contributions to the water absorption bands [71,81–84]. Besides, another interesting way of
monitoring in situ the extent of water ingress in epoxy system is to use dielectric relaxation
measurements [70,85,86]. However, any of these methods does not seem to be useful as a
non-destructive method to ‘in situ’ monitor the water absorption in the epoxy resins when
they are in service. In addition, these methods allow measuring the water content of the whole
system and, therefore, they are not useful when the determination of the water absorption in
specific sites such as interfaces is required.
Again, the use of fluorescence response from a group chemically bonded to specific sites
seems to be the best way to follow this kind of processes. In fact, the emission coming from
dansyl labels has been demonstrated to be useful to monitor the water uptake in different
kinds of epoxy resin formulations [87] and in glass fibres/epoxy composites [47].
Figure 9. Fluorescence spectra for a glass fibre dansyl labelled/epoxy composite at different immersion
times.
D. Olmos et al. [47] using the fluorescent response of dansyl label studied the effect of
the nature of the glass fibre surface in the water absorption of glass fiber/epoxy composites.
Different interphases in the composites were created by using three silanes to coat the glass
fibres: APTES, APDES and APMES and the process of water absorption was compared with
that of the neat epoxy without glass fibres. Comparison of results obtained as by gravimetry
as FTIR with those obtained from dansyl moiety chemically bonded to the silane coupling
agents allowed to follow the arrival of water at the interfaces. It was observed that the
presence of silanized fibres induces changes in the process of water absorption of the epoxy
decreasing the relative gain of mass at equilibrium. These results suggest that the glass fibre
surface yields a change in the structure of the epoxy matrix in comparison with that of the
polymer without reinforcement. On the other hand, the accessibility of water to the interphase
was seen to be considerably delayed respect to that of the polymer matrix. Moreover,
although the relative amount of water absorbed by the interface (nanometers) depends on the
nature of the glass fibre surface, the differences observed do not correspond with those
observed for the global absorption of water by the whole specimens. One possible explanation
of these results may be the increase of the interphase (tens of micrometers) crosslink density
the lower the functionality of the silane is: a higher crosslinking density should yield less free
volume to be occupied by water molecules during the water absorption process.
As an example, Figure 9 shows how the fluorescence band of dansyl label located at the
interface of a glass fiber/epoxy composite changes after immersing a composite specimen in a
bath of water during a particular immersion time.
3. Conclusions
Fluorescence response from chemically bonded fluorophores (for example dansyl label) has
been revealed as a very effective tool to monitor whatever changes appearing in specific sites
in composite materials such as those occurring during cure processes, thermal transitions and
water absorption. However, the main conclusion that can be extracted from this work can be
summarized as follows:
i) Fluorescence from dansyl located at the glass fiber/epoxy interface reflected that the
kind of reinforcement treatment clearly affects the epoxy curing process exactly in
that region.
ii) Fluorescence from fluorophores located at specific sites has revealed that there
seems to be differences between apparent Tg’s at the interface and in the epoxy
matrix of silica/epoxy systems. The first moment of the emission band was very
useful in determining glass transitions independent of the local site (interface or
epoxy bulk).
iii) It has been demonstrated that the presence of silanized fibres induces changes in the
process of water absorption of the epoxy resin in glass fibres/epoxy based
composites. Particularly, the fluorescence experiments reflected that the
accessibility of water to the interphase is considerably delayed respect to that of the
polymer matrix.
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Chapter 8
THERMAL AND WEAR STUDIES

OF POLYMER-FULLERENE COMPOSITES
Aleksei O. Pozdnyakov1,2, and Klaus Friedrich3,4*

1
Institute of Problems of Mechanical Engineering,
St. Petersbourg, Russia
2
Ioffe Physico-Technical Institute, St Petersbourg, Russia
3
Institut für Verbundwerkstoffe GmbH, Technisches Universität Kaiserslautern,
Kaiserslautern, Germany
4
AMME, The University of Sydney, Sydney, Australia
Abstract
Numerous polymer-nanocarbon composite applications, e.g., electroluminescence,
rheology, tribology, and thermal ignition are being continuously documented. This provides
firm impetus for studies of the structure and properties of such composites. Their properties
exhibit complicated relationships to electronic and vibrational subsystems of the polymer
matrices in presence of fullerene molecules. This chapter gives an example of a comparative
study of the thermal behavior of several polymers and their respective polymer-fullerene C60
composites. The influence of fullerenes on macroscopic tribological behavior of polyimide-
fullerene composite is analyzed.
1. Introduction
Studies of friction and wear find firm impetus both in the industrial needs to control these
phenomena and in their scientific relevance to many areas of physics and chemistry.
Tribology is the scientific domain involving the research of complicated interplay between
friction, wear and lubrication of materials subjected to a relative motion against another
counterpart. The study of polymer and polymer composites’ tribology has also to account for
many processes simultaneously evolving at the friction couple interface in tribological
*
E-mail adress for Aleksei O. Pozdnyakov: ao.pozd@mail.ioffe.ru, E-mail adress for Klaus Friedrich:
klaus.friedrich@ivw.uni-kl.de
334 Aleksei O. Pozdnyakov and Klaus Friedrich
situations [1]. The changes of the properties of the interface layers due to friction heat
generation are of high relevance to these processes. At least two major thermal effects may be
expected to result from tribological events at the friction interface. One of them are changes
in viscoelastic properties of the polymer upon frictional heating of the mating materials.
Another effect is expected when the friction temperature reaches temperatures at which
thermal degradation of the polymer is not negligible anymore. Both of these processes are
obviously in strong relation to the response of the polymer material at the friction interface to
the intense shear stresses developed upon friction. In the real tribological situation, all the
processes mentioned above contribute to the overall behavior of the polymer material under
shear conditions developed upon dry polymer-metal sliding. Note that the multi-parametric
nature of tribological events leads to the necessity of neural networks approaches to handle
the tribological data [2]. Of relevance to the problems discussed is, in our opinion, the
tribological study of the polymers known to withstand high temperatures. Among them are
highly thermally stable polyimides (PI) [3]. Indeed, their tribological behavior is acceptable in
practical friction conditions [4-8].
Of high current interest is the research of polymer nanocomposites [9]. Many papers
currently also emerge that are devoted to the tribological research of PI and PI
nanocomposites [10-13]. An introduction of a nanosized filler (or several different fillers) into
the polymer matrix in order to optimize its behavior is a common practice. The behavior of
the composite under shear is well known to differ from that of the neat matrix. The response
of the composite to the external forces depends on many peculiarities of the polymer-filler
system, e.g. the nature of the filler-filler and filler-matrix interactions, dispersion state of the
filler, etc. [14]. A good filler (or a combination of various fillers) is supposed to improve the
wear parameters of the composite as well as to immediately minimize (or at least sustain) the
friction coefficient of the material system. This problem is a serious task for further science of
materials in this area. Symmetrical cage-like molecules of carbon, i.e. fullerenes (Fu), present
new challenge to the research of the dispersion state of the particles in polymers due to the
molecular nature of this new filler (molecular diameter of fullerene C60 is less than one
nanometer) compared to usual fillers like, e.g., carbon or glass fibers (whose diameter is in 10
μm range). The dispersion state of Fu molecules is expected to result in new properties of the
composites because the size of the single Fu molecule is close to that of local free volume
fluctuations in some bulk polymers. Therefore, the better the dispersion is the larger number
of Fu-polymer molecular contacts can be achieved. Strong electron acceptor properties of the
Fu molecules suggest their interaction with electron-donor media and, therefore, probable
additional effects on the properties of the matrix containing electron-donor moieties [15]. The
PI precursors that is polyamic acid (PAA) provide the sites for Fu-polymer interactions due,
e.g., to the presence of amine groups known to be good electron donors.
The general outline of the tribology of polymer composites given above shows that the
role of Fu in the friction and wear of polymer composites can be very complicated. Up to now
there is no definite explanation of this role, and even main governing mechanisms of Fu
influence on these properties is not established. In this chapter we are attempting to
demonstrate some examples of the research in this field. Many details of the tribological
experiments described below can be found in our earlier work [8].
Thermal and Wear Studies of Polymer-Fullerene Composites 335
2. Friction and Wear of PI and PI-C60 Composites

Sliding wear experiments described in the chapter were carried out with a flat-on-ring
configuration, employing a rotating steel cylinder (German Standard 100Cr6, HRC62,
Ra~0.13 μm) pressed against a rectangular, polymer coated steel plate having a size of
~18x70x4 mm3. The sample surfaces were polished and degreased prior to coatings’
deposition. Subsequently, they were coated with PI or PI-C60 composite coatings having a
thickness of about 50÷70μm. A geometry of the wear testing machine used study is shown in
Fig. 1. The wear and friction test conditions were applied by setting a normal dead weight (L)
and by rotating the cylinder at a linear sliding velocity (V). The initial normal contact
pressures, P, calculated by using finite element approach (for details see [8]) were roughly
estimated to be around 12MPa, considering the current coating-substrate dimensions and
L~5N, as used in the experiments described below. However, in this experimental geometry
the wear of the material results in a continuous decrease of the nominal macro-contact
pressure. Specific volume wear rates (wear factors) were calculated using the expression:
k=w/(L⋅d), where w is wear volume after the test, d is sliding path length, L – normal load.
Since the wear groove had a cylinder segmented shape, the wear volume was calculated from
the width of the wear groove b, length of the groove A, radius of the cylinder R using simple
geometrical formula.
Figure 1. Geometry of the friction experiment and IR image of the friction pair used in our research.
The cylinder is pressed by dead weight with load L over the flat sample and is rotating around its axis
with a constant speed. The real coating to substrate thickness ratio (0.01 cm/0.4 cm ~0.02) is lower than
→
that shown in the figure. V shows the linear sliding velocity component used in the experiment
→
( V ~1 m/sec). Normal load, L, used in the experiment = 5 N. Time of friction ~ 30 minutes. Tflash
approximately shows the maximum value of the temperature at the very interface which may attain the
temperatures of significant PI thermal decomposition (see text for explanation).
Dry friction conditions used in the experiments are characteristic of the real operating
conditions of the friction pair, and are characterized by high normal pressures and high
sliding velocities at the friction macro-contact. This, in turn, results in high levels of specific
(for the contact area) friction energy: J ~ μ·P·V, where μ is friction coefficient. For realistic
dry friction conditions the value of J well exceeds 1 MWatt/m2 (e.g. for V>1m/sec, P>2MPa
and μ >0.5). The basic channel of friction energy dissipation is usually considered to be
through heat production. In terms of the so called “flash temperature concept”, valid for a thin
interface layer between two solid bodies and the band shaped heat source moving along it, the
friction generated temperature can therefore be estimated by an engineering relationship,
developed by Block [16] : T ~ J ⋅ t , where t is time during which any point of the
flash
surface is exposed to frictional heating. One indeed finds that a similar relationship for the
2⋅J χ ⋅t
interface temperature increment: ΔT = ⋅ (λ and χ are thermal conductivity and
λ π
heat diffusion coefficient of the material into which the heat flux is diffused and t – time)
∂T(z, t) ∂ 2 T(z, t)
satisfies the one dimensional heat diffusion equation −χ⋅ = 0 (see Fig.
∂t ∂z 2
1 for the model geometry) for semi-infinite solids in contact, with an initial temperature
condition inside the material of T(z,0)=To, and a time independent boundary condition for
frictional heat flux at the boundary between the material and the heat source:
∂T(z, t)
−λ⋅ = J [17]. During continuous sliding over the same macro-contact area, as
∂z z =0
realized in our experiments the contacting bodies do gradually heat up. The time and spatial
behavior of temperature fields generated upon friction depends on the size, shape and material
properties of the bodies, as well as the external environment (e.g. humidity) etc. Since for a
given experimental setup the prediction of this behavior is a great problem, one has to rely on
certain estimates of this behavior. An approximate pattern of the temperature field is
illustrated in Fig. 1 as an infra red color image taken in our experiments during sliding. The
spatial distribution of the thermal field around the contact zone is non-uniform and shows a
gradual decrease of temperature from the maximum value at friction interface towards the
rotating cylinder and towards the substrate. An additional important observation is the high
temperature “tongue” oriented in the direction of friction (to the left). This tongue obviously
propagates far from the contact zone. The nature of this phenomenon may be, for example,
explained by the formation of highly overheated wear debris particles emanating from the
interface in the sliding direction. Though we are not undertaking the complete analysis of the
thermal events developed in the contact zone, we can note that the temperature values
monotonously decrease from the maximum value at the interface down to lower values
(ultimately room temperature) far from the interface. The typical dependence of temperature
values obtained from color IR images on the distance in the direction perpendicular to the
cylinder is shown as a bold curve in the figure; it resembles, though qualitatively, the
dependencies obtained by solution of the above heat diffusion equation. The real temperatures
generated in the very thin interface layer can be estimated to be close to the PI decomposition
temperatures (~400oC). This estimate is reasonable since for the PI discussed here the infra
red spectra of the wear debris formed even at milder friction conditions contain (according to
the data of Lai et. al. [18]) the remanents which have been ascribed to the breakdown of imide
bond. It is interesting to note, that, even for complicated tribological events developed in our
experiments (Fig.1), the average temperature in the vicinity of the contact zone approximately
follows the t temporal scaling [8]. This scaling holds good for the initial period of sliding,
deviating from this trend on prolonged friction (this deviation is more pronounced for higher
P,V conditions), probably signaling the metal-metal contact spots formation at the later
periods of sliding. For wear measurements it was found also reasonable to choose (see details
in [8]) the initial stage of experiment where stable P values are preserved. This wear regime is
logically termed as “steady state” and is used below for comparative purposes. It is again
worth noting that the tribological experiment even in fairly simple contact geometry is a
complicated thermophysical problem [19] which should account for additional elementary
processes of the tribological event (this may lead, e.g, to the certain modifications of the
above discussed diffusion equation) in order to perform a quantitatively valuable wear
experiment. The analysis of the wear of the PI coatings given below is restricted to the
discussion of certain valuable effects obtained for given P, V parameters at the above
described “steady state” of wear process.
In this chapter we discuss the results of tribological studies of Poly[N,N’-
bis(phenoxyphenyl)-pyromellitimide]. We used poly[pyromellitic dianhydride-co-4,4'-
oxydianiline] amic acid (PMDA-ODA, Aldrich, 575801, ca. 15 wt.% sol. in 1-methyl-2-
pyrrolidinone (NMP)); fullerene C60 (522500, Aldrich, sublimed, 99.9%); toluene (650579,
Sigma-Aldrich, Chromasolv plus, for HPLC 99.9%); 1-methyl-2-pyrrolidinone (270458,
Aldrich, 99+% HPLC grade). PMDA-ODA is an aromatic polyimide having the following
structural formula:
O O
N N O
n
O O
PMDA-ODA can be prepared via thermal cycloimidyzation of the PAA [20] produced
from a condensation polymerization of pyromellitic dianhydride and oxydianiline. This
reaction sequence can be used for the Fu introduction in different ways. One of them is an
introduction of Fu into diamine or anhydride prior to blending the reactant solutions. Another
is an introduction of the Fu into the as synthesized polyamic acid (PAA). In our study we
have used the latter way of Fu introduction, i.e. Fu introduction into PAA precursor of
PMDA-ODA. PAA is a 15 wt. % NMP solution. The C60 powder was added to this solution
and was kept after stirring for about a month in the refrigerator. The rated volume content, f,
of C60 in the dry PI matrix was ~0.05. After the storage the PAA-C60 solution looked like a
good C60 solution in NMP (brownish color) contrary to the yellowish colored neat PAA
solution. However, note that due to sedimentation it was difficult to rigorously control the
actual C60 content inside the composite samples. Note also that neither FTIR (results below)
nor near edge X-Ray absorption fine structure spectroscopy [21] did not enable to discern the
presence of C60 in the coatings studied here.
150 150
100 100
dm/dt, rel. units

m. rel units
50 50
endo
0 0
0 200 400 600 800 1000

T, oC
Figure 2. DTGA curves on PAA (dashed line) and PAA-C60 (solid line). DSC run for the heating of the
neat as imidized PI film preliminary imidized in air to ~320oC is shown by bold line with an arrow
pointing to the direction of the endothermic heat effect. DSC measurements were performed under
nitrogen flow conditions with the aid of a Mettler DSC831e.
DTGA data (Fig. 2) show that the mass loss of the PAA and PAA-C60 samples takes
place in two distinct stages: ~100-400oC and ~500-700oC. The high temperature stage (~500-
700oC) is supposed to correspond to the decomposition of the PI matrix. In the low
temperature stage, on the other hand, the weight loss is due to the main product of the
imidization (water) and solvent molecules. This curve peak has a sharp front and a slowly
descending “tail” in the higher temperature range approaching the zero level at about 400oC.
The DSC curve for as-imidized PI (at ~ 320oC in air conditions) is also included in the figure
as a bold line (heat effect is shown by the arrow). It can be seen that the DSC exhibits a broad
endothermic process which converts at higher temperatures into an exothermic process. This
transition may be supposed to be in relation to a certain ordering process of the material
structure. Indeed, according to the morphological study of isotropic PMDA-ODA (see e.g.
[22] and references therein) the increase in the initial imidization temperature results in an
overall growth in the lateral packing of the chains and a reduction in the amplitude of the
density modulation. It was also shown [22] that up to imidization temperatures of 350oC the
WAXD was characterized by a single sharp reflection arising from the projection of the 1.8
nm monomer unit onto the chain axis. It was also emphasized that it is far from being
crystalline, although some order exists in these specimens. At further heating above 350oC
this reflection sharpens and intensifies indicating additional lateral ordering and formation of
highly disordered crystals [22]. Our own SAXS and WAXD results, though obtained for
another PI matrix, namely PDFO-PPh-PRM [23,24], indicate that the PI-C60 composite
morphology and its thermal variation upon imidization is sensitive to the presence of Fu. The
explanation for this effect may be an existence of certain interaction between PAA or PI
molecules with strong electron acceptor Fu molecules. More detailed characterization of the
morphology of PMDA-ODA/Fu composites should be a matter of further studies.
1,4
1,2
1,0
0,8
h
0,6
0,4
0,2
0,0
200 400 600 800 1000 1200 1400 1600 1800 2000
-1
cm
Figure 3. FTIR spectra of the PI (dotted line) and PI-C60 (solid line) films (thickness ~70 μm) as-
imidized at ~320oC. The spectra were recorded with the aid of a Nicolet Fourier transform infrared
spectrometer in the absorption mode. The resolution of 2 cm-1 and a number of scans of 50 was found to
provide an optimum noise/intensity ratio and was used in the study.
Prior to the analysis of the wear data, FTIR data on PMDA-ODA and PMDA-ODA/C60
coatings should be considered. First note that the imidization degree may be crucial for the PI
properties. Therefore we start with FTIR spectra of the coatings studied. Fig. 3 shows a
typical FTIR spectrum of the PI films treated at 320oC in air, i.e. at the temperatures slightly
above the low temperature shoulder seen on the DTGA curve (Fig. 2). FTIR spectra for both
PI and PI-C60 composite films coincide very well, and they are in a good agreement with the
FTIR data given elsewhere for PMDA-ODA polyimide [25]). Heating the samples up to
420oC does not lead to measurable differences in the peak positions, though fine effects may
be expected in more thorough studies. The analyses of FTIR spectra provide firm grounds for
assuming that at ~320oC imidization reactions in this PI are almost completed, although
chemical changes can still be expected at higher temperatures. This comes from the
inspection of the DSC curves (Fig. 2) of PMDA-ODA which exhibit the presence of a certain
exothermic process starting at about 320oC. The results obtained show that this can be
attributed to the onset of such complicated chemical transformations.
Type of the wear

Type of experimental
Wear surface morphology surface
conditions
and of the debris
V~ 1-2 m/sec
P~ 5 N
μ~0.3±0.05
Lower imidization Flat wear surface
temperatures
Mainly irregular
spherical shape wear
debris
V~ 0.5-1 m/sec
P~ 5 N
μ~0.4±0.05 Flat and wavy wear
Higher imidization surface
temperatures
Irregular spherical
shape wear debris
+
Needle like wear
debris
V~ 0-0.5 m/sec
P> 5 N
μ~0.4±0.05 Flat wear surface
Higher imidization with cracks
temperatures
Irregular spherical
shape wear debris
+
Needle like wear
debris
Figure 4. Typical SEM images of the wear groove surfaces of PI and PI-C60 coatings heat treated at
320oC and 420oC. The arrows indicate the sliding direction of the steel counterpart. The inset in the
photo shown in the third raw shows typical needle like wear debris particles.
The analysis of the wear grooves shows different wear patterns for coatings treated at
different temperatures as well as tested at different P, V conditions. The typical (but of course
not the only) 3 wear surface morphologies have the following characteristic features (Fig. 4).
These morphologies are either flat (Fig. 4, first line in the table), wavy (Fig. 4 second line in
the table) or exhibit surface cracking patterns (Fig. 4 third line in the table). Additionally, note
that at higher V the friction coefficient, μ, was somewhat lower but this effect is difficult to
explain due to the very complex thermophysical nature of the processes involved. The shapes
of the wear debris particles are also sensitive to the wear conditions. In accord with our
previous observations [8] for the PI coatings heated at higher temperatures, the wear debris
(see inset in the left top part of the picture shown in the third column of Fig. 4) has a needle-
like shape, similar to fine rollers. The more round shaped debris is usually observed for the
coatings imidized at lower temperatures. Though the question of ascribing the given surface
morphology and wear debris type is still not yet quantitatively solved (see also the
Introduction for the discussion of the multiparameter nature of tribological experiment) we,
however, allow ourselves to give an idea of these interrelations through comparison of
different wear surface morphologies (Fig. 4). The conditions of wear test, for which the given
wear surface morphology and wear debris is predominant, are specified in the first column of
the table in Fig.4. In the third column of Fig. 4 we give also an approximate correlation
between the wear surface morphology and the corresponding debris. The size of the needle-
like wear debris particles expressed, e.g., as the ratio between the length to the width of the
particle, usually obeys log-normal distribution. We do not present the results of calculations
here but note that the concrete distribution is dependent on the friction conditions. Since the
shapes of the wear debris may bear important information on the mechanisms of wear, these
distributions may be further used for obtaining additional information on the PI wear process.
The measurements of wear of the PMDA-ODA based coatings carried out in our studies
may be summarized as follows. The wear volume measurements, as calculated from the
widths of the cylinder segment shaped wear grooves, show that the wear factor of the coatings
covers a range of k~5÷70·10-5 mm3/N·m at the steady regime of wear. The lowest values
exhibit the PI/C60 coatings imidized al higher temperatures (~420oC). Intermediate values (~
30·10-5 mm3/N·m) correspond to neat PI imidized at higher temperatures (~420oC). Maximum
values (~ 60·10-5 mm3/N·m) correspond to both neat and composite PI coatings imidized at
lower temperatures (~320oC). Interesting to note that the range of ~ 30·10-5 mm3/N·m was
also observed in [18] for PMDA-ODA/attapulgite hybrid materials. In the case of this work
the decrease in k was referred to the presence of the filler only. This emphasizes the
importance to further consider for thermal effects during the PI preparation in the study of the
composites. Further, k values obtained for PMDA-ODA are about 100 times higher than the k
values for the PI studied in our earlier work, i.e. DPhO-PPh-PRM [8]. Nevertheless, it is
important that the morphological patterns of these different PI formulations have much in
common. A decrease of wear was observed for both types of coatings when imidized at
higher temperatures, signaling the importance of the structural build-up at high imidization
temperatures in the wear behavior of PI, irrespective of their molecular structure.
Concluding the discussion of wear properties of PI and PI-Fu composites, we note that
thermomechanical performance of these materials revealed by wear tests obviously exhibits
correlations with the preparation conditions of the samples, especially at high imidization
temperatures. We are therefore expecting that more detailed study of thermomechanical
properties with more sophisticated methods, such as, e.g. dynamical thermomechanical
analysis, should be fruitful in establishing the quantitative interrelation of macromolecular
dynamics under different shear rate and temperature conditions in the presence of Fu
molecules to the complicated tribological events. These questions are a matter of further
research.
3. Thermal Properties of Polymers and Polymer-C60 Blends as

Revealed by Thermal Gravimetry Analysis
According to the results presented above, under practically realistic experimental conditions
one observes a measurable influence of Fu molecules (even at a low volume fraction) on the
tribological behavior of the composites. The search for a way to improve this effect leads to
the necessity to understand the mechanisms of the structural behavior of Fu molecules inside
the polymer matrix. The probable influence of Fu molecules on the mechanical and
tribological properties of the polymer-fullerene composites (PFC) is based on polymer-Fu
interactions. The extent of the latter should be directly related to the dispersion state of Fu
molecules. In the case of a complete molecular dispersion, the interfacial area will be very
large (even at low Fu content in the matrix) due to the high specific surface area (= particle
surface area/particle volume) of the nanoparticles. For spheres, this value is: 6/d, where d is
the particle diameters. The nanoparticle regime suggests that in PFC the role of free volume
of the given polymer matrix in the properties of the composite is important. In order to make
more insight into the latter problem we have made a thermal gravimetry study of several
PFCs. For the purpose of this study, polymer matrices with different physical properties have
been chosen. Polydimethylsiloxane (PDMS) is a flexible chain polymer with low Tg~126 K.
Poly[methyl methacrylate] (PMMA) and polystyrene (PS) are amorphous polymers with
Tg~400 K and 378 K, respectively [26]. Note here that for PMDA-ODA used in the above
described wear studies the existence of Tg is speculative [3]. The following materials have
been used: PMMA Fluka, standard Mw=500000; PS Fluka, 81414, standard Mw=500000;
PDMS fluid, viscosity 100000 cSt at 25oC (Silicone Oil Dow Corning Corp 200R).
PS-, PDMS- and PMMA-C60 suspensions were prepared by co-dissolution of the polymer
and C60 (522500, Aldrich, sublimed, 99.9%) solutions in toluene. The C60 content in toluene
before mixing with a polymer solution amounted to the equilibrium solubility of C60 in
toluene at room temperature (2.9 mg/ml [27]). Polymer-Fu solutions were cast onto the
degreased and dried glass slides for the coatings formation. Two rated volume C60
concentrations (f ~ 0.05 and 0.12 C60 in dry polymer) were used in the study. Note again that
due to sedimentation it was difficult to rigorously control the actual C60 content inside the
composite samples. The coatings were dried in air for several days at about 80oC. The dried
coatings with a thickness of about 30 μm were carefully detached from the glass slides and
used in TGA measurements as prepared.
All measurements were performed by using a Mettler TG50 apparatus. Polymer samples
weighing 5–10 mg were placed in open ceramic Al2O3 pans and heated according to a linear
program with a heating rate, β, of 25 K·min–1. High β values were chosen to increase the
signal-to-noise ratio in the temperature range corresponding to C60 sublimation, due to the
low C60 content inside the polymer matrices. The heating was performed from room
temperature up to 1000oC in the atmosphere of flowing nitrogen, at a flow rate of 30 ml·min-1.
The experimental values of sample mass (m) were registered with a step of 0.833 K. A
smoothing method that performs a local polynomial regression around each data point was
used for differentiating sample mass versus time dependencies, m(t), for a given heating
regime, T(t), to obtain dependencies of the first derivative dm(t)/dt. The results are presented
in the form of m versus T (TGA curves) and dm/dt versus T (DTGA curves)
dependencies. Integrations were performed using a trapezoid rule. Note that all the samples
exhibited almost 100 % mass loss after heating to 1000oC under the experimental conditions
used in the study. For convenience, the TGA curves are presented in the form of the
percentage of the sample mass to the initial sample weight (prior to heating). If not otherwise
specified DTGA data presented below are recalculated from the raw TGA data (normalized
sample mass versus time dependencies).
Figure 5. TGA and DTGA spectra of PDMS and PDMS-C60 composite (a), PS and PS-C60 composite
(b), PMMA and PMMA-C60 composite (c). Thin lines – neat polymer. Dotted lines: polymer-C60
composites with the rated 5 mass. % C60 content inside dry polymer. Thick lines: polymer-C60
composite with the rated 12 mass. % C60 content inside dry polymer. Dashed line – TGA curve for neat
Fu.
Fig. 5 shows the experimental TGA scans of PDMS (a), PS (b), PMMA (c), and their
composites with C60 as well as TGA curve for neat fullerene C60. The observed influences of
C60 on the TGA curves of the polymers are: 1) the changes in shape of the mass loss curve
corresponding to the degradation of the matrix, 2) appearance of the high temperature stage of
weight loss laying well above the degradation temperatures of the matrix but close to those of
neat Fu (above 650oC).
DTGA curves shown also in Fig. 5 indicate that in the case of PDMS-C60 composite one
observes a two-stage DTGA curve for low Fu content inside the matrix, contrary to the single
stage DTGA curve for neat PDMS. An increase in C60 content in the matrix causes an
increase in the intensity of the high-temperature DTGA peak. In the case of PS-C60
composite, the single stage character of the DTGA curve observed for a neat PS is preserved.
However, the peak position evidently shifts along the temperature axis. At low C60 content the
peak is shifted to higher temperatures. At higher C60 content one observes a shift of the peak
position to a temperature which is even lower than that observed for neat PS. For PMMA-C60
composite the single stage character of the DTGA curve observed for the neat PMMA is also
preserved, similar to the case of PS-C60 composite. The peak position shifts to higher
temperatures in presence of Fu compared to neat PMMA sample. However, for PMMA
composite one observes small dependence of peak position on the C60 content.
The thermal decomposition of the polymer matrices studied in our work have already
been a matter of numerous works. The general features of thermal decomposition of these
polymers in the bulk can be considered are as follows. In nitrogen, PDMS decomposition is a
single stage depolymerization process leading to elimination of cyclic oligomers [28]. PS
degrades mainly due to a random scission process giving rise to degradation products
consisting of a mixture of monomer, dimer and trimer [29]. Thermal degradation of PMMA is
a depolymerization process initiated at defect sites of the macrochain (e.g. head-to-head
linkages and vinilydene end groups). The mechanisms of thermal decomposition for PS and
PDMS are quite complicated and the analysis of the kinetic data of thermal decomposition is
a problem arising from both the complexity of the degradation mechanisms and the ways of
handling TGA and DTGA data. The kinetics of decomposition reactions are usually described
dα
by equation = k(T) ⋅ f(α ) , where f(α) is the reaction model, R is the extent of reaction,
dt
k(T) is the Arrhenius rate constant, T is the temperature, and t is the time. As it is noted, e.g.,
in [30], the treatment of the experimental data has to circumvent the errors arising from both
the experiment and the process itself (e.g. different parallel processes of thermal degradation).
To obtain a kinetic description of our thermal gravimetry curves, we made the assumption
that the degradation of the neat polymers proceeds through a single stage first order reaction
(f(α)=1-α, Mampel or first order model) and the Arrehnius rate constant is described by the
− U/RT(t)
relation k(T) = k ⋅ e , where ko is preexponential factor and U is the activation
o
energy. Straightforward fitting (not shown) with the solutions of the first order equations for
DTGA data of neat polymers is found to be very good for the whole process. For such an
dα (t)/dt
ideal process the dependence of ln ( ) versus 1/T(t) is close to linear. The slope of
1 − α(t)
these curves is proportional to U. Due to the above described errors of the experiment
(especially if the signal-to-noise ratio is low) the dependencies of this type deviate from a
linear one, even for an ideal single stage mechanism of the process. From the slope of the
dα (t)/dt
dependencies of ln ( ) versus 1/T(t) constructed for neat polymers, the values of U
1 − α(t)
are found to be well described by normal distribution around the mean value for all
conversions. The estimated kinetic parameters obtained from these mean values are as
follows: PMMA k=2⋅1013[sec-1]⋅e-196[kJ/mol]/RT, PS k=3⋅1030[sec-1]⋅e-456[kJ/mol]/RT, PDMS
k=109[sec-1]⋅e-173[kJ/mol]/RT. In the case of PFCs the distribution strongly deviates from the
normal one with an increase of conversion. These observations suggest that in our
experimental conditions, the thermal degradation pattern of the neat polymers is close to a
first order single stage process. The analysis of the DTGA curves for PS and PMMA
composites (Fig. 5) indicates a more symmetric shape of the curves, compared to those of
neat polymers. This may imply, e.g., that for these samples the order of the reaction is above
unity. However, in the heating condition chosen in our experiment (fairly high heating rate β
= 25 K·min–1), with a purpose of increasing the signal to noise ratio in the temperature range
of Fu sublimation, the effects of heat lag may be expected for bulky samples, having a linear
size (L) of ~ 1 mm. Indeed, the analysis of mass loss processes due to desorption evolved
upon heating the sample may, in general terms, be considered in the context of the diffusion-
dC
reaction equation: = D ⋅ ∇ 2C + ψ , where C is the concentration of penetrant molecules,
dt
ψ - source term, representing a supply of the diffusing species originating in the sample from
the polymer decomposition reaction [31]. The latter term is considered to be the reaction
kinetics one intends to reveal from the experiment. The quantitative analysis of the equation
needs, along with the appropriate boundary and initial conditions, knowledge about the
temperature behavior of the diffusion coefficient and the real temperature distribution inside
the material upon heating. The uncertainties in these input data may lead, for example, to an
unusually high estimates of the value of activation energy for the PS decomposition. Further
detailed analysis of the actual degradation kinetics needs a study of smaller amounts of the
material with a purpose of decreasing the factor L2/D, where D is diffusion coefficient. This
needs more sensitive experimental approaches [32].
From the thermal gravimetry experiments one can, however, deduce that the strongest
effect of Fu on the PFC thermal behavior is observed for the PDMS matrix. PDMS is the
polymer with the lowest Tg among those studied in this work. This property is associated with
an increased free volume fraction of the polymer and a corresponding higher diffusivity of
penetrant molecules inside the matrix. TGA data suggest that inside the PDMS matrix the Fu
molecules are more uniformly dispersed, so that an increased number of molecular matrix-
filler contacts is attained. The latter may be the reason for the enhancement of complicated
degradation reactions of the matrix in the presence of Fu molecules as revealed by high
temperature stage of PDMS-C60 composite degradation. It can also be due to the desorption of
well dispersed Fu molecules (Fig 5) [33]. Though the actual decomposition reactions
developed at this degradation stage needs more research, the TGA data suggest that the
amount of the reaction products increase with the increase of the Fu concentration. More
detailed mass-spectrometric investigation of this problem is a matter of further research.
Fig. 6 shows the high temperature range of DTGA curves for a PFC with the maximum
C60 content used in the study. Note that at lower C60 content the signal-to noise ratio did not
allow to extract any signal from the curves. Fig. 3 also presents DTGA curves for neat Fu.
The zero order modeling of the DTGA of neat Fu provides sublimation activation energy of ~
170 kJ/mol, which is close to the sublimation enthalpy obtained with a Knudsen cell
apparatus [34]. As seen from Fig. 3, the DTGA curves of the composites contain a peak
which position is close to the sublimation stage of neat C60. The peak intensity increases with
the increase of Fu concentration. This suggests that this stage of the DTGA curve also
corresponds to the C60 sublimation. The zero order modeling of the DTGA curves of PFCs
results in the sublimation activation energy close to that of neat Fu but with higher values of
prefactors. Therefore, the TGA analysis of model PFCs evidences the dependences of both
the thermal degradation pattern of the matrices and the sublimation behavior of Fu molecules
on the Fu concentration inside the matrix. This effect is well understood to result from the
increased dispersion of Fu molecules inside polymer matrices in comparison to that of neat
Fu. This may mean, for example, that PI has an even lower possibility to disperse the Fu
molecules, due to the lower free volume fraction in this polymer [33]. This problem is a
matter of more detailed studies.
Figure 6. Thick line presents high temperature area of DTGA spectra of polymer-fullerene composites
with the rated 12 mass. % C60 content inside dry polymer. a) PDMS-C60 composite, b) PS-C60
composite, c) PMMA-C60 composite. Thin lines – DTGA spectra of neat Fu. Dotted lines – guide for
eye showing the character of the curve.
4. Conclusion
The observations presented in this chapter indicate that the tribological properties of PI-C60
composite coatings are mainly determined by the structural transformations of the matrix,
which occur in a temperature range between 300 and 400oC, i.e. in the last imidization stages.
In presence of C60 in the PI matrix, this heat treatment results in a further decrease of the wear
rate of the composite coatings, but without appreciable changes in friction coefficients. In this
temperature range the disappearance of C60 (e.g. due to desorption and complicated chemical
transformations of C60 in the presence of PI molecules) should be considered in greater detail
e.g. using thermo mechanical analytical techniques. Thermal studies suggest that this kind of
research has to involve into consideration the free volume effects of the matrix in the
properties of the polymer-Fu composites.
Acknowledgements
A.O. Pozdnyakov expresses gratitude to the Alexander von Humboldt Foundation for support
of his research stay at IVW, Technical University of Kaiserslautern. K. Friedrich is grateful to
the Australian Research Council for his International Professorial Research Fellowship at the
AMME of the University of Sydney, Australia, in 2006/2007. Thanks are due to Dr. Hermann
Giertzsch (IVW) for taking SEM photos.
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Chapter 9
AN APPROACH FOR WELDING PARTICLE

REINFORCEMENT ALUMINUM MATRIX
COMPOSITES: TRANSIENT PULSE-IMPACT
LIQUID-PHASE WELDING
Kelvii Wei Guo1

Department of Manufacturing Engineering and Engineering Management, City
University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Kowloon, Hong Kong
Abstract
The aluminum matrix composite SiCp/ AlSi7Mg was welded by Transient Pulse-Impact
Liquid-Phase Welding (TPILPW), the effect of welding parameters on the welded joint
property was investigated, and the optimal welding parameters were put forward ultimately.
The microstructure of joint was analyzed by means of optical-microscope, scanning electron
microscope (SEM) and EPMA in order to study the relationship between the macro-properties
of joint and the microstructure. Results showed that during TPILPW: (i) the interface state
between reinforcement particle and matrix was prominently affected by the transient pulse-
impact; (ii) the initial pernicious contact-state of reinforcement particles was changed from
reinforcement (SiC)/reinforcement (SiC) to reinforcement (SiC)/matrix/reinforcement (SiC);
(iii) the harmful microstructure/brittle phase of Al4C3 was restrained from the welded joint;
(iv) the density of dislocation in the matrix neighboring to and away from the interface in the
matrix was higher than its parent composite; and (v) the intensively mutual entwisting of
dislocation was taking place. Studies illustrated that: (1) deformation was mainly occurred in
the matrix grain; and (2) in the deformation of rapid thermal pressing, the matrices around SiC
particles engendered intensive aberration offered a high density nucleus area for matrix crystal,
which was in favor of forming nano-grains and improved the properties of the successfully
welded composite joints. Such distinctly welded composite joints gave: (i) a tensile strength up
to 179MPa that was about 74.6% of the stir-cast SiCp/ AlSi7Mg; and (ii) a corresponding
radial deformation below 3% that conformed well to the deformation specification of the
welded specimens. Moreover, a prominent characteristic of TPILPW was shorter welding
time than that of the conventional welding method. By physical simulation, it showed that the
temperature in the weld would be increased sharply to some extent under the effect of
1
E-mail address: guoweichinese@yahoo.com (W. GUO). Tel.:+852-2784-4614. (Corresponding author)
350 Kelvii Wei Guo
transient pulse-impact. Furthermore, the length of solid/liquid phase state in the specimen was
ΔT
calculated, the result could be expressed as Δx = ξ L . Finally, powder
Tmax − T0
metallurgy made aluminum matrix composites, SiCp/6061Al, Al2O3p/6061Al, were welded by
TPILPW. Results showed that Transient Pulse-Impact Liquid-Phase Welding was suitable for
application in joining particle reinforcement aluminum matrix composites.
Keywords : Aluminum matrix composite, Transient Pulse-Impact Liquid-Phase Welding,

SiCp/ AlSi7Mg, SiCp/6061Al, Al2O3p/6061Al
1. Introduction
The high strength-weight ratio, good wear-ability and corrosion resistance of Aluminum
Matrix Composites (AMCs) attract substantial industrial applications [1-5]. Typically, AMCs
are currently used widely in automobile and aerospace industries, structural components, and
heat resistant-wearable parts in engines [6-8]. Due to their typical characteristics of Metal
Matrix Composites (MMCs) and their production methods, the distribution of the particles of
reinforcement elements in stir-cast of AMCs is generally inhomogeneous [3-4, 7-8].
Furthermore, the geometry of such elements may be either in form of particulates or as short
fibers and whiskers [4, 7-8]. These discontinuous natures create several problems to their
joining techniques for acquiring their high strength and good quality weld-joints. Typical
quality problems of those welding techniques currently available for joining AMCs [6-8] are
as elaborated below.
(1) The distribution of particulate reinforcements in the weld

As properties of welded joints are usually influenced directly by the distribution of
particulate reinforcements in the weld, their uniform distribution in the weld is likely to give
tensile strength higher than 80% of the parent AMCs. Conglomeration distribution or absence
(viz. no-reinforcements-zone) of the particulate reinforcements in the weld generally degrades
markedly the joint properties and subsequently resulted in the failure of welding.
(2) The interface between the particulate reinforcements and aluminum matrix
High welding temperature in the fusion welding methods (typically: TIG, Laser welding,
Electron Beam etc.) is likely to yield pernicious Al4C3 phase in the interface. Long welding
time (e.g. several days in certain occasions) in the solid-state welding methods (like:
soldering, diffusion welding, friction welding etc.) normally leads to (i) low efficiency and
(ii) formation of harmful and brittle intermetallic compounds in the interface.
To alleviate these problems incurred by the available welding processes for welding
AMCs, a Transient Pulse-Impact Liquid-Phase Welding (TPILPW) technique has been
developed. This paper aims at providing some more ground works in the welding method,
and specifically studies the influence of transient pulse-impact on the microstructures and
tensile strength of welded joints. Analysis by means of scanning electron microscope (SEM),
transmission electron microscope (TEM) and X-Ray Diffraction (XRD) allows the micro-
viewpoint of the mechanisms of TPILPW to be explored in more detail.
An Approach for Welding Particle Reinforcement Aluminum Matrix Composites 351
2. Experimental Material and Process

2.1. Experimental Material
Stir-cast SiCp/ AlSi7Mg aluminum matrix composite, reinforced with 20% volume fraction
SiC particulate of 12μm mean size, was produced. The stir-cast composites had a tensile
strength of 240MPa and solid-liquid phase transformation temperature in the range of
562.6∼578.3 ºC. Its microstructure was illustrated in Fig. 1. The stir-cast aluminum matrix
composite was then suitably machined and wire-cut to specimens of size 5mm×10mm×35mm
(Fig. 2). The chemical composition of AlSi7Mg matrix alloy was tabulated in Table 1.
Table 1. The composition of AlSi7Mg
Composition (Wt%)
Si Mg Ti Al
6.5~7.5 0.3~0.5 0.08~0.2 Bal
Figure 1. Microstructure of SiCp/ AlSi7Mg aluminum matrix composite.
Weld
5mm
10mm
35mm
Figure 2. Shape and dimension of samples.

352 Kelvii Wei Guo
2.2. Experimental Process
The quench-hardened layer and oxides, as induced by wire-cut process, on the surfaces of
aluminum matrix composite specimens were removed by careful polishing using 400# emery
cloths. The polished specimens were then properly cleaned by acetone and pure ethyl alcohol
so as to remove any contaminants off its surfaces. A DSI Gleeble-1500D thermal/mechanical
simulator with a 0.4 Pa vacuum chamber was subsequently used to perform the welding. The
Gleeble-1500D thermal/mechanical simulator is heating the specimens based on the principle
of direct resistance heating. Generally, a low voltage 50Hz AC current is applied directly
across the two ends of the specimens of which the internal resistance subsequently creates the
Joule effect to heat up themselves at their interface. The application of several thousand amps
of currents provides very fast heating rates to initiate the welding joint. The welding
temperature in the simulator is measured by means of thin wire thermocouples percussively
welded onto the surface of the specimens. The precise control of heat input is conducted by a
closed loop feedback temperature signal as sensed at any instant by these attached
thermocouples. In the process of experiments, the Gleeble-1500D simulator automatically
performed the welding after with inputting the anticipated welding parameters like (i)
welding temperature T (i.e., in range of 560˚C to 578˚C for our experiments), (ii) transient
pulse-impacting time tI (i.e., in range of 10-4s to 10-2s for our experiments), (iii) horizontal
deformation δ (i.e., in range of 0.1mm to 2mm for our experiments), (iv) welding holding
pressure P0 (i.e., in range of 2MPa to 10MPa for our experiments), and (iii) welding time t
(i.e., in range of 5s to 120s for our experiments) and so on.
Tensile test specimens (Fig. 3) of the welded joint were then specially prepared, and were
pulled with a straining velocity of 0.5mm/min using an Instron electron-mechanical universal
material testing machine. For each set of welding conditions, there were five welded joints
being pulled and their average strength was presented as the test result. The microstructures,
the interface between the reinforcement particles, and the matrix of the welded joints were
analyzed by SEM and TEM. The distribution of phases in the area of the welded joints was
investigated by XRD.
Figure 3. Size of samples for tensile test.
2.3. Operation of TPILPW
To achieve good joint, the temperature of TPILPW was selected somewhat between the solid
phase and the liquid phase of the composite materials. When the liquid matrix alloy in the
interface of jointing surfaces was at certain ratio and the jointing area was synchronously
impacted within a glimpse of time of 10-4~10-2s, SiCp/ AlSi7Mg could be successfully jointed
under the optimal operational conditions of welding temperature, welding time and holding
pressure. Fig. 4 illustrated a typical temperature and welding time cycle of a TPILPW. It
basically involved with: (i) an initially rapid increase of weld specimens, within a time of ta,
to an optimal temperature Ta at which heat was preserved constantly at Ta for a period of (tb -
ta), (ii) at time tc, a quick application of compressive force to impact the welding specimens
so as to accomplish an anticipated deformation δ within a glimpse of 10-4~10-2s, whilst the
heat preservation was still maintained at the operational temperature Ta; and (iii) a period of
natural cooling to room temperature after time tb.
Figure 4. Schematic diagram of Transient Pulse-Impact Liquid-Phase Welding.
2.4. Calculation for Volume Fraction of Liquid Phase Matrix Alloy
According to reference [4], the volume fraction of liquid phase matrix alloy is expressed as:
T1 −T
V =1−
T1 −T2 (1)
Where T1 is the temperature of the liquid phase state; T2 is the temperature of the solid
phase state.
Fig. 5 illustrated the relationship between the volume fraction of the liquid phase and
temperature.
354 Kelvii Wei Guo
Volume fraction of liquid phase

/ %
Temperature / °C
Figure 5. Volume fraction of the liquid phase as a function of temperature.
3. Results and Discussion

3.1. Influence of Welding Temperature on Properties of Welded Joints
Fig. 6 showed the relationship between the strength of welded joint and welding temperature.
It illustrated that with the temperature increasing, the strength of welded joint became higher
and higher. When the temperature was 570ºC, the strength of welded joint was up to its
maximum (179MPa), which was about 74.6% of that of SiCp/ AlSi7Mg. But, when the
temperature increased further, the ratio of liquid matrix alloy was higher (as shown in Fig. 5),
under the effect of impacting, the welding pieces slide each other, the pieces couldn’t be
jointed perfectly, and the strength of welded joint decreased.
Tensile strength of welded joints/ MPa
240
VI=560mm/s, t=30s, P0=5MPa,δ=1mm
200
160
120
80
40
0
555 560 565 570 575 580
Temperature/ ℃
Figure 6. Relationship between the tensile strength of welded joints and the welding temperature.
3.2. Selection of the Transient Pulse-Impacting Mode and Speed
Welding of aluminum matrix composites using TPILPW generally had three advantageous
characteristics. Typically, it gave: (i) low welding temperature, (ii) short welding time and
(iii) high tensile strength of the welded joints. Among these, the short welding time was the
most advantageous characteristic of TPILPW that would be superior to other welding
processes. When their composite at the interface was in certain mixing ratio of liquid and
solid phase, the welding specimens could thus be impacted fleetly to each other. Available
data showed that the welding pieces were unable to joint successfully as a result of mutually
relative sliding when the impacting time was shorter than 0.01s. For welding joint was under
impaction with impacting velocity VI: so as to cause for an overall horizontal deformation δ
within an impacting time tI, selection of any of these parameters could hence be conducted by
the relationship of VI = ( δ / tI ). Owing to the limitation of Gleeble-1500D
thermal/mechanical simulation machine, the impacting time in this study was chosen within
10-2s ~ 10-4s.
3.2.1. Testing of Three Impacting Modes
The setting parameters in transient pulse-impacting mode influence the joint quality in the
TPILPW. There were three impacting modes performed in this study for the impacting speed
constantly set at 560mm/s, and they were schematically shown in Fig. 7 Their individual
operational parameters were: (i) Mode I – the welding temperature Ta to be at 570ºC, the time
to preserve its relevant input thermal energy for maintaining at Ta (i.e. the time of heat
preservation) being below 5s, and impaction initiated immediately at tc1; (ii) Mode II – the
welding temperature Ta to be at 570ºC, the time of heat preservation being in the range of
5~10s, and impaction initiated immediately at tc2; (iii) Mode III – the welding temperature Ta
to be at 570ºC, the time of heat preservation being above 10s, and the impaction rapidly
initiated at tc3. SEM fractograph of a welded joint by Mode I (Fig. 8) gave the appearance of
some sporadic welded locations and some rather densely scattering bare reinforcement
particles. It thus suggested that the short tc1 did not allow the sufficient amount of liquid phase
to be formed when the composite matrix reached the optimal temperature of Ta. Although
some wet locations in the joint had been excellently welded, the conglomerated solid
reinforcement particles appeared to indicate that the typical transient pulse-impacting did not
weld ideally the pieces together and it consequently resulted in a lower strength joint. Under
Mode II, the relatively lengthening of heat preservation time tc2, the temperature across the
weld interface became more uniform and it simultaneously raised the amount of liquid phase
that was sufficient to wet the welding surface. Hence, it facilitated perfect weld under suitable
transient pulse-impacting speed. SEM fractograph of welded joint by Mode II (Fig. 9) showed
the disappearing of bare reinforcement particles and the appearance of changing prominently
the reinforcement/reinforcement contact to reinforcement/matrix/reinforcement one that
subsequently resulted in higher tensile strength of the joint. When the heat preservation time
was beyond 10s, i.e. for Mode III, the effective heated zone in the parent composite was
enlarged that recursively reduced its rigidity. Therefore, the application of transient pulse-
impacting would cause the relative sliding of the weldpieces that jeopardized ultimately the
formation of proper joint as seen in Fig. 10. Analysis of the microstructure of the three
356 Kelvii Wei Guo
factographs suggested that the joints performed at heat preservation time in the range of about
5~10s were relatively more superior than the other two conditions.
Figure 7. Schematic diagram of the different transient pulse-impacting modes.
Figure 8. Fractograph of welded joint by Mode I.

3.2.2. Influence of Transient Pulse-Impact on Joint Properties
Experimental results of tensile strength for the welded joints joined with different impacting
velocities were shown in Fig. 11. It illustrated that welded joints tended to give inferior
tensile strength with the impacting speeds below 70mm/s. It showed that the tensile strength
of the weld joints generally increased with increase of impacting
Figure 9. Fractograph of welded joint by Mode II.
Figure 10. Surface of welded joint by Mode III.

358 Kelvii Wei Guo
200
Tensile strength of welded joints/ MPa

T=570ºC, t=30s, P0=5MPa
180
160
140
δ=2mm
120 δ=1mm
100 δ=0.5mm
80 δ=0.1mm
60
40
20
0
0 500 1000 1500
Impacting speed/ mm/s
Figure 11. Relationship between the strength of welded joints and welding impacting speed.
Figure 12. Fractograph of welded joint at transient pulse-impact speed>700 mm/s, T=570 ˚C, t=30 s,
and P0=5 Mpa.
speeds until the latter reached a value of 560mm/s at which maximum strength of welded
joints was achieved. Beyond this value, the welded strength was reducing with increasing of
impacting speed. Basically, the initial increase of impacting speed, say in range of 0 – 560
mm/s, (i) partly reduced the amount of drifting of liquid phase composite down to bottom
region of the specimens that would prompt for non-uniform distribution of strength across the
weld, and (ii) partly decreased the uniform penetration of liquid phase composite to fill the
joint that subsequently descending its strength. Results (Fig. 11) illustrated that, for the
welding conditions herewith studied, both (i) and (ii) were optimized at impacting speed of
560 mm/s. As the impacting speed was above this particular speed, i.e. at or beyond 700
mm/s, the increase in the impacting speed resulted in more liquid matrix to be squeezed out
from the welding interface. Subsequently, there was not sufficient liquid matrix to moist
reinforcement particles and it led the reinforcement particles in forming localized
conglomeration (Fig. 12). Hence, it prompted for the descending of the strength of welded
joint.
The amount of overall horizontal deformation δ of a welded joint was normally affected
by the compression across the joining specimens, which had certain bearing in the joint
quality as well. Although its influence varies with the setting of welding parameters (Fig. 11),
the optimal deformation for the impacting speed of 560 mm/s was at δ = 1mm. Surely, the
variation of optimal deformation at different impacting speeds could be explained as the
result of (i) the uniform distribution of filtrating liquid matrix of reinforcement particles and
(ii) their amount being squeezed out from the interface. It should be particularly noted that the
strength of the individual optimal conditions could be above four folds, signifying the
importance in selecting properly the valid welding conditions when TPILPW was chosen for
joining aluminum matrix composite SiCp/ AlSi7Mg and other particles reinforcement
aluminum matrix composites.
3.3. Influence of Welding Time on Properties of the Welded Joint
Fig. 13 showed the relationship between the strength of welded joint and welding time. It
indicated that with the increment of time, the strength of welded joint became higher and
higher thanks to the depth of atom diffusion increasing. When the welding time was 30s, the
strength of welded joint was up to its maximum. But, with the welding time extending, heat
area of parent composite was increased at the same time.
240
Tensile strength of welded joints/
T=570? ,V=560mm/s, P0=5MPa,δ=1mm
200
160
MPa
120
80
40
0
0 50 100 150
Welding time/ s
Figure 13. Relationship between the strength of welded joints and the welding time.
360 Kelvii Wei Guo
Lots of liquid matrix would appear on the most surface of parent composite and form a
phenomenon of perspiration. The surplus liquid matrix would be harmful to the properties of
welded joints and parent composite itself. Consequently, the strength of welded joint would
be descended.
3.4. Influence of Holding Pressure on Properties of the Welded Joint
Fig. 14 showed the relationship between the tensile strength of welded joints and the holding
pressure. Results indicated that the initial increase in the holding pressure accompanied with
the increase in the tensile strength of welded joints until the holding pressure reached 5MPa at
which the tensile strength of welded joints was the maximum. However, further increase in
the holding pressure decreased the tensile strength of welded joints.
Tensile strength of welded joints
240 T=570? ,VI=560mm/s, t=30s,δ=1mm

200
160
/MPa
120
80
40
0
0 2 4 6 8 10 12
Holding pressure/MPa
Figure 14. Relationship between the tensile strength of welded joints and holding pressure.
3.5. Microstructure of Welded Joint
Microstructure of the welded joint with the optimal parameters (i.e., T=570˚C, VI=560mm/s,
tI=10-2~10-4s, δ=1mm, t=30s, P0=5MPa) and its corresponding fracture surface were shown in
Fig. 15. The welded joint displayed with uniformly distributing reinforcement particles and
microstructure almost similar to that of its parent composite (Fig. 1). SEM of the fracture
surface showed no sign of bare reinforcement particles, suggesting that the reinforcement
particles had been perfectly wet and the composite structure of reinforcement/reinforcement
had been changed to the state of reinforcement/matrix /reinforcement. XRD pattern of the
fracture surface (Fig. 16) did not illustrate the existence of any harmful phase or brittle phase
of Al4C3. This suggested the effective interface transfers between reinforcement particles and
matrix in the welded joint that subsequently provided favorable welding strength.
(a) Microstructure of the welded joint (b) Fractograph of the welded joint
Figure 15. SEM micrograph and fractograph of welded joint.
Figure 16. XRD pattern of the fracture surface.
3.6. Distribution of Dislocation in the Welded Joint
The distribution of dislocation in the matrix neighboring to the interface of the welded joint
by TPILPW in comparison with its parent composite was shown in Fig. 17. The clearly
distinctive interface (Fig. 17a) between SiC particle and matrix indicated that the integration
between the reinforcement particle and matrix was prominent. The effect of transient pulse-
impacting subsequently led to dislocation in the matrix lattices and showed sign of mutually
entwisting to give higher welded strength. Comparatively, its dislocation distribution in the
matrix neighboring to the interface was relatively denser than that in its parent composite (cf.
Figs 17a and 17b). Similarly, the density of dislocation and dislocation entwisting in the
matrix away from the welded interface was also higher than that of its parent composite (cf.
Figs 18a and 18b). Such favorable characteristics ultimately gave relatively superior strength
of the welded joint to that of conventional diffusion welding [9].
362 Kelvii Wei Guo
3.7. Formation of Nano-grains in the Weld
SEM micrograph (Fig. 19) of a weld by TPILPW displayed some newly-formed
Matrix
Matrix
SiC
SiC
0.25μm 0.25μm
a) welded joint b) parent composite
Figure 17. Distribution of dislocation in the matrix neighboring to the interface of the welded joint and
parent composite respectively.
a) welded joint b) parent composite
Figure 18. Distribution of dislocation in the matrix away from the interface of the welded joint and
parent composite respectively.
nano-grains in the lattices of the joint. These nano-grains would seat in the interstices of
crystal lattices and create new grain boundary in hindering the movement of neighbouring
grains and subsequently improved obviously the properties of the welded joints. The
formation of new nano-grains was the advantageous effect of transient pulse-impact in
TPILPW.
Figure 19. Nano-grains formed in the weld of SiCp/ AlSi7Mg during the TPILPW.
3.8. Physical Simulation on Effect of Transient Pulse-Impact
The results of physical simulation [4] on the effect of transient pulse-impact were as shown in
Fig. 20 to Fig. 22. It illustrated that when the welding temperature was lower than the optimal
welding temperature, and just exceeded the temperature of solid/liquid phase, under the effect
of transient pulse-impact, the temperature of weld increased slightly as shown in Fig. 20.
Temperature / °C
Time / s
Figure 20. Relationship between temperature and time simulated by Gleeble1500-D

(δ = 1mm, T =563 ˚C)
364 Kelvii Wei Guo
Temperature / °C
Time / s

(δ = 1mm T =565 ˚C)
Temperature / °C
Time / s

(δ = 1mm T =570 ˚C)
Simultaneously, it indicated that the effect of various impact speeds on the weld was nearly
same, especially when the impact speed exceeded 70 mm/s shown as magnifying area in Fig.
20. With the welding temperature increasing, the effect of impact speed would be more
obvious (cf. Fig. 21, Fig. 22 and Fig. 20). It showed that when δ = 1mm T =570 ˚C, the
temperature in the weld increased most distinctly, especially when impacting speed was 350
mm/s (Fig. 22). As a result, the atom in the weld would be diffused more effectively which
gave the higher tensile strength of welded joint as shown in Fig. 11.
3.9. Calculation on Length of Solid/Liquid Phase State
L
T0 T0 Clamp
x Δx
T T+ΔT
Specimens
Figure 23. Calculated schematic diagram of temperature distribution in heated specimens.
Supposed
Initial temperature was T0, the length of specimen was L.
Then the quantity of heat Q at the distance x in Δ t would be
∂T
Q = −αA Δt (2)
∂x
Where α was the coefficient of conduction, A was the area of cross-section.

It could be derived that the quantity of heat Q + Δ Q at the distance x + Δ x would be
⎡ ∂T ∂ ⎛ ∂T ⎞ ⎤
Q + ΔQ = −αA⎢ + ⎜ ⎟Δx ⎥ Δt (3)
⎣ ∂x ∂x ⎝ ∂x ⎠ ⎦
Suppose the per volume power was W, the heat lost of radiation and convection were
ignored, then the net quantity of heat in the unit Δ x would be
∂ 2T
ΔQ + WAΔxΔt = −α A Δx Δt (4)
∂x 2
As a result, the rate of temperature variation would be

366 Kelvii Wei Guo
∂T 1 ⎛ ∂ 2T ⎞
= ⎜⎜W + α 2 ⎟⎟ (5)
∂x ρc ⎝ ∂x ⎠
Where ρ was the density of material, c was the specific heat capacity of material.
When temperature distribution was quasi-steady state,
∂T
=0 (6)
∂x
Then the Eq. 5 would be expressed as
∂ 2T
W = −α (7)
∂x 2
Integrating Eq. 7, it gave
∂T W
= − x+b (8)
∂x α
1
When x = L,
2
∂T
=0 (9)
∂x
Then it would be obtained
WL
b= (10)
2α
Integrating Eq. 8, it gave
W 2 WL
T =− x + x + b′ (11)
2α 2α
When x = 0 , T = T0 , then
b′ = T0 (12)
Then Eq. 11 would be transformed into

W 2 WL
T =− x + x + T0 (13)
2α 2α
Or
T − T0 =
W
(L − x )x (14)
2α
1
When x = L , T = Tmax , then
2
WL2
Tmax − T0 = (15)
8α
Supposed T = Tmax − ΔT , then
(Tmax − T0 )
Tmax − ΔT − T0 = 4 (L − x )x (16)
L2
Eq. 16 could be written as
L⎡ ΔT ⎤
x= ⎢1 ± ⎥ (17)
2⎣ Tmax − T0 ⎦
The length of specimen with temperature between Tmax and Tmax − ΔT was
ΔT
Δx = L (18)
Tmax − T0
Considering the properties of particle reinforcement aluminum matrix composites, the

length of solid/liquid phase state in the specimen would be expressed as
ΔT
Δx = ξ L (19)
Tmax − T0
According to Eq. 19, the length of solid/liquid phase state in the specimen would be
calculated. With the welding temperature increasing, the length of solid/liquid phase state
would be longer, and the area of higher temperature in the weld would be increased. As a
result, the stiffness of parent material would be decreased together with the microstructure of
368 Kelvii Wei Guo
parent material became coarser accorded with Fig. 11. Under the effect of the transient pulse-
impact, the parent materials would be slid easily coincided with Fig. 10 and Fig. 12.
Moreover, it would provide a foundation of setting the optimal welding parameters (cf. Eq.
19, Fig. 5)
3.10. Mechanism of TPILPW
Owing to the existence of the high melting point and low conductivity SiC particles in the
welding interface, resistance of the TPILPW joint was higher than its parent alloy matrix. A
large amount of heat energy was released and would intensively be congregated at the joint
region. Subsequently, it led to the accumulation of sufficient amount of liquid matrix metal in
the joining interface and simultaneously there was only little annular in the interface still
entrapping the liquidus and solidus mixture. As the remaining bodies of the specimens were in
their solid state, plastic deformation and mechanical occlusion were quickly formed in the
Solid-liquid phase zone Squeezed out liquid phase
Matrix
SiC
a) b)
Squeezed out SiC particle
c)
Figure 24. Schematic representation of behaviors of reinforcements in welded zone: (a) Reinforcements
distributed in the beginning of diffusion welding; (b) Reinforcements distributed in the course of
diffusion welding; (c) Reinforcements distributed in the finish-welded joint.
uneven interfacial surface when they were under compression with high transient pulse-
impacting speed. Under the effect of such compression, deformation took place intensively in
the matrix grain and was accompanied by intensive diffusion. Simultaneously, the matrices
around SiC particles engendered intensive aberration which subsequently offered relatively
denser nucleus spots for forming nano-grains within matrix crystal (Fig. 19) and resulted in
improving distinctively the properties of welded joints. As the deformation impact energy
abruptly increased the temperature in welded zone, it was propitious to further atom diffusion
and more liquid phase forming in the welded surface which would offset the amount of liquid
phase by such additional diffusion recursively reducing. The squeezing effect would squeeze
out a little amount of liquid phase and tiny SiC particles from the joining zone shown in Fig.
24b and assist in cleaning off the remnant oxide film simultaneously and thus enhanced the
bonding effect. As flow of matrix would force SiC to flow, it promoted the more uniform
dispersion of SiC particles over the joining interface and within its vicinities. Conceptually, the
distribution of reinforcements at the incipience of diffusion welding (Fig. 24a) would spread to
that as shown in Fig. 24c within the welded joint. SEM micrograph (Fig. 25) of the
microstructure in a welded joint clearly demonstrated its conformity to the aforementioned
conception, as illustrated in Fig. 24c. Normally, transient pulse-impacting pressure on TPILPW
could rectify the interior deficiency in the composite, improve the density of composite, and
diminish the interior apertures in composite (cf. Figs 24a, 24b and 24c). Hence, it was, to certain
extent, propitious in suitably modifying the strength of the welded joint. As illustrated by the
experimental results, under certain amount of liquid phase alloy appearing in the welding
interface in TPILPW, perfect joint was achievable at the interface of matrix-reinforcement
and reinforcement-reinforcement SiCp/ AlSi7Mg provided that an impact speed was properly
selected. The short welding time of TPILPW process effectively prevented the forming of the
harmful phase in the bonded area (Fig. 16) and formed the clearly distinctive interface
between the aluminum matrix and reinforcement (Fig. 17a), and it advantageously improved
the work efficiency. In addition, the operation of TPILPW with proper transient pulse-
impacting speed was likely to prompt for high density of matrix dislocation intensively tangling
Figure 25. Microstructure of the finish-welded joint.

370 Kelvii Wei Guo
both around and far from the SiC particles (Fig. 17 and Fig. 18). The welding technique gave
the tensile strength of the joint of particle reinforcement aluminum matrix composite SiCp/
AlSi7Mg as high as 179MPa (Fig. 11) (that was about 74.6% of its as-cast parent composite)
with corresponding radial deformation below 3%.
3.11. Application of TPILPW
For validating the application of TPILPW, aluminum matrix composites, SiCp/6061Al,

Al2O3p/6061Al, made by powder metallurgy, reinforced with 15% volume fraction SiC,
Al2O3 particles of 5μm mean size, were adopted, which had the tensile strength of 360 MPa,
400MPa for SiCp/6061Al and Al2O3p/6061Al, respectively. By TPILPW, its corresponding
maximum strength of welded joints was up to 260 MPa (about 72.2 % of its parent material)
for SiCp/6061Al, 282MPa (about 70.5% of its parent material) for Al2O3p/6061Al.
Figure 26. SEM micrograph and fractograph of welded joint of SiCp /6061Al.
Figure 27. SEM micrograph and fractograph of welded joint of Al2O3p/6061Al.

Fig.26 and Fig. 27 showed the micrographs and its corresponding fractographs of welded
joints. It indicated that powder metallurgy made aluminum matrix composites could be
welded successfully by TPILPW. Consequently, as a new approach, Transient Pulse-Impact
Liquid-Phase Welding was suitable for application in particle reinforcement aluminum matrix
composites.
4. Conclusions
Results of this study on the welding of SiCp/ AlSi7Mg using Transient Pulse-Impact Liquid-
Phase Welding process allow the following particulars to be drawn.
[1] Transient pulse-impact in Transient Pulse-Impact Liquid-Phase Welding in joining

SiCp/ AlSi7Mg resulted in higher density of dislocation in the matrix neighboring to
and away from the interface than their parent composite. Mutually and intensively
entwisting of the dislocation in the welded joint led to successful joint with higher
tensile strength.
[2] There was distinctly clear interface between SiC particle and matrix. It overcame
some diffusion problems normally encountered in conventional diffusion welding,
and prevented the formation of harmful microstructure or brittle phase in the welded
joint.
[3] The joint by TPILPW process would form nano-grains. The newly-formed nano-
grains improved the properties of welded joints that would give tensile strength of the
welded joints as high as 179MPa that was about 74.6% of its parent SiCp/ AlSi7Mg.
[4] The temperature in the weld would be increased sharply to some extent under the
effect of transient pulse-impact illustrated by physical simulation.
ΔT
[5] The length of solid/liquid phase state in the specimen was Δx = ξ L .
Tmax − T0
[6] Transient Pulse-Impact Liquid-Phase Welding was suitable for application in
particle reinforcement aluminum matrix composites conventionally made by stir-
cast and powder metallurgy.
References
[1] ‘Welding Handbook’, 1996, Miami, The American Welding Society
[2] L.M. Marzoli, A.v. Strombeck, J.F. Dos Santos, C. Gambaro and L.M. Volpone. Friction
Stir Welding of an AA6061/Al2O3/20p Reinforced Alloy. Composites Science and
Technology. 2006, 66(2): 363-371
[3] Wei Guo, Meng Hua and John Kin Lim Ho. Study on liquid-phase-impact diffusion
welding SiCp/ZL101. Composites Science and Technology. 2007, 67 (6):1041-1046
[4] Guo W. Study of new diffusion welding mechanism on particle reinforcement aluminum
matrix composites. PhD Thesis, Harbin Institute of Technology, Harbin, China, 2004,
Feb
372 Kelvii Wei Guo
[5] D. A. Porter and K. E. Easterling. Phase Transformations in Metals and Alloys, 2nd. CRC
Press, Cheltenham: Nelson Thornes. 2001
[6] Ralf Riedel. Handbook of Ceramic Hard Materials. Wiley-VCH, Weinheim, New York.
2000
[7] J.R. Davis, ASM Specialty Handbook. Aluminum and Aluminum Alloys. ASM
International, Materials Park, Ohio. 1993: 557
[8] R.K. Everett and R.J. Arsenault. Metal Matrix Composites: Mechanisms and Properties.
Boston: Academic Press, 1991
[9] Meng Hua, Wei Guo, Hang Wai Law and John Kin Lim Ho. Half-transient liquid phase
diffusion welding: An approach for diffusion welding of SiCp/A356 with Cu interlayer.
The International Journal of Advanced Manufacturing Technology. 2007
INDEX
amino acid, 299
A ammonium, 305, 306, 307
amorphous polymers, 182, 342
accelerator, 91, 165, 173
amplitude, 59, 146, 147, 153, 154, 192, 261, 262,
access, 150
270, 272, 273, 276, 287, 297, 338
accessibility, x, 315, 328
anatase, 20
accounting, 251
anisotropy, 201, 316
accuracy, ix, 176, 179, 188, 197, 198, 225, 276, 278,
annealing, 13, 14, 67
290
annihilation, 259
acetone, 20, 91, 352
APC, 27
acid, 39, 40, 63, 64, 294, 300, 309, 310, 312, 334,
aqueous solutions, 65
337
aramidic, viii, 25, 28, 31, 33, 43, 48, 59, 64, 68
acidic, 43, 47, 65
Arborite, vii
acrylate, 319
Archimedes, 181
acrylic acid, 19
aromatic polyimide, 337
activation energy, 288, 301, 344, 345
aromatic rings, 30
actuators, viii, 73, 75, 109, 134, 146, 226, 251, 252,
aspect ratio, 103, 104, 268, 296
253
Asphalt concrete, vii
additives, 296, 308, 309, 317
assessment, 71, 265
adhesion, x, 5, 38, 47, 50, 59, 63, 295, 297, 299, 300,
assignment, 327
302, 304, 308, 315, 316, 347
assumptions, 165, 167, 180
adhesion strength, 63, 304
asymmetry, 18
adhesive joints, 75, 144, 145, 147
atomic force, 9, 11, 12, 18
adhesive properties, 64
atoms, 318
adhesive strength, viii, 25
attachment, 316, 319
adhesives, 29, 65, 66, 69, 74, 75, 145, 303
attacks, 69
adsorption, 49, 276, 290, 318
attention, 10, 11, 150, 177, 178, 184, 294, 296, 304,
aerospace, vii, viii, 3, 25, 26, 66, 74, 350
308, 316
AFM, 9, 11, 12, 13, 14, 15, 16, 17
Australia, 60, 293, 333, 347
agent, 36, 40, 48, 64, 299, 300, 302, 311, 316, 325
autolysis, 309
aggregates, 19
automobiles, ix, 255, 256
aging, 33, 39, 40, 54, 63, 66, 68, 69, 150
automotive application(s), 256
Al2O3 particles, 370
availability, 5, 294, 298
algorithm, 276, 281, 290
alkaline, vii, 25, 39, 41, 42, 45, 63, 65, 69, 71
alloys, 256, 257, 265, 273 B
alternative(s), 6, 299, 308, 325
aluminum, ix, xi, 3, 4, 255, 256, 260, 262, 264, 265, band gap, 11
273, 286, 287, 288, 289, 349, 350, 351, 352, 355, beams, viii, 36, 46, 52, 55, 56, 57, 61, 67, 69, 70, 73,
359, 367, 369, 370, 371 74, 146, 153
374 Index
behavior, vii, ix, xi, 19, 20, 25, 26, 27, 28, 29, 30, 32, 158, 160, 191, 193, 194, 287, 294, 304, 316, 318,
34, 38, 39, 42, 46, 49, 52, 57, 58, 60, 62, 65, 66, 334
68, 94, 107, 146, 150, 152, 157, 158, 163, 165, carbon nanotubes, 10
167, 170, 174, 178, 179, 180, 184, 185, 191, 194, Carbon-fiber reinforced plastic (CFRP), vii, 27, 28,
225, 251, 253, 255, 262, 265, 267, 268, 270, 273, 29, 33, 37, 38, 39, 47, 51, 52, 53, 54, 55, 57, 58,
275, 276, 277, 278, 280, 282, 283, 284, 285, 286, 59, 61, 62, 63, 64, 67, 68, 69, 70
287, 288, 289, 291, 292, 293, 295, 297, 301, 308, carbonyl groups, 301
309, 311, 314, 333, 334, 336, 341, 342, 345 cast(ing), xi, 9, 11, 12, 17, 263, 273, 286, 289, 301,
bending, viii, 37, 52, 55, 56, 57, 74, 75, 78, 87, 88, 302, 305, 342, 349, 350, 351, 370, 371
89, 107, 118, 121, 125, 126, 138, 144, 145, 146, catalyst, 301
147, 217, 222, 236, 241, 244, 251, 252, 302 cation, 306
beneficial effect, 51 CCC, 66, 70
benefits, 37, 296 cell, 163, 268, 269, 270, 272, 273, 275, 276, 278,
bias, 34, 44 285, 345
binary blends, 301, 311 cellulose, vii, ix, 293, 294, 295, 296, 297, 298, 299,
biocompatibility, 300, 311 300, 301, 302, 309, 310, 311
biodegradability, 6, 294, 300, 301, 306, 308, 311, cellulose diacetate, 296
313 ceramic(s), vii, 75, 86, 103, 125, 147, 198, 206, 209,
biodegradable materials, ix, x, 293, 294, 295, 296, 210, 212, 213, 217, 222, 223, 237, 238, 241, 250,
297, 298, 299, 300, 302, 304, 305, 308, 309, 310, 251, 257, 265, 275, 288, 289, 342
311, 312, 313 chain mobility, 297
biodegradation, 301, 304, 306, 312 chemical composition, 351
biopolymer(s), 302, 309 chemical degradation, 46, 63
bisphenol, 19, 27, 47, 321 chemical interaction, 64
blends, 12, 16, 20, 299, 301, 302, 305, 308, 311 chemical kinetics, 164
blocks, 11, 12, 14, 17, 18, 29, 256, 317 chemical properties, vii, 6
bonding, 4, 29, 49, 54, 56, 74, 76, 87, 88, 89, 91, 109, chemical reactions, 46, 164, 317
144, 146, 301, 369 China, 255, 286, 293, 371
bonds, 47, 77 chitin, 294
boundary value problem, 226 chloride, 53, 55
Bragg grating, 160 chlorine, 316
branching, 162 chloroform, 302
breakdown, 47, 337 chromatography, 297, 310
buffer, 41 clean energy, 306
burning, 47 cleaning, 369
butadiene, 20 climate change, 5
clustering, 290
clusters, 21, 306
C coatings, 317, 320, 335, 337, 338, 339, 340, 341, 342,
346
C60, xi, 333, 334, 335, 337, 338, 339, 340, 341, 342,
collaboration, 188
343, 345, 346
collagen, vii
Ca2+, 305
collisions, 323
cables, 70
combined effect, 32, 52, 59, 60
calcium, 41, 42, 55
compatibility, 5, 11, 20, 270, 295, 296, 299, 300, 301,
calculus, 211, 215
304
California, 44
competition, 179, 191, 259, 307
Canada, 62, 67, 69, 70
complexity, 150, 164, 277, 344
candidates, 285
compliance, 39
capillary, 30, 308
components, vii, viii, ix, 3, 4, 5, 12, 73, 74, 164, 166,
carbon, vii, viii, 10, 25, 27, 28, 31, 32, 33, 36, 37, 38,
168, 199, 200, 201, 227, 229, 230, 234, 255, 256,
39, 42, 43, 45, 47, 48, 49, 50, 52, 53, 54, 55, 56,
265, 291, 297, 301, 302, 308, 309, 317, 321, 322,
57, 61, 63, 64, 66, 69, 70, 91, 153, 154, 155, 157,
350
Index 375
composition, 19, 301, 302, 304, 318, 351 crack, 36, 44, 55
compost(ing), 43, 306, 312 creep, 66, 256, 267
compounds, viii, 25, 297, 299, 316 critical state, 292
computation, 154, 173, 289, 291 critical value, 106
concentration, viii, 30, 41, 55, 64, 73, 74, 75, 76, 109, cross-linking reaction, 31
144, 165, 279, 280, 297, 307, 324, 345 crystalline, 13, 301, 302, 338
concrete, vii, 25, 27, 29, 36, 39, 41, 45, 46, 51, 52, crystallinity, 301, 302, 311
55, 56, 57, 58, 61, 62, 63, 64, 65, 67, 68, 69, 70, crystallization, 9, 11, 13, 14, 16, 18, 301, 302, 305,
341 307, 308, 311, 313
condensation, 337 crystallization kinetics, 301
conditioning, 40, 52, 57, 59, 65 crystals, 10, 198, 338
conduction, 3, 171, 365 curing, viii, 19, 20, 26, 27, 29, 30, 32, 34, 36, 37, 44,
conductivity, 173, 186, 188, 336, 368 46, 47, 48, 51, 52, 53, 55, 59, 64, 65, 66, 75, 146,
configuration, 47, 57, 63, 74, 335 149, 150, 151, 153, 154, 155, 157, 158, 159, 160,
confinement, 58, 70 161, 162, 163, 164, 167, 170, 172, 173, 174, 176,
conformity, 369 177, 178, 179, 180, 181, 182, 183, 184, 185, 186,
Congress, 67, 313 187, 188, 189, 190, 191, 192, 193, 194, 317, 319,
connectivity, 10 323, 324, 328
conservation, 165, 166 curing process, 29, 51, 319, 328
constant rate, 325 curing reactions, 27, 34, 44
constituent materials, vii, 27 cycles, 27, 28, 29, 36, 37, 38, 39, 52, 53, 54, 55, 56,
construction, 39, 40, 55, 150, 164, 167, 309 57, 58, 59, 63, 65, 259, 260, 262, 264, 265, 270,
consumption, 6 271, 272, 273, 274
contaminants, 352 cycling, 29, 36, 38, 39, 45, 55, 61, 63, 68, 69, 263,
continuity, ix, 80, 97, 98, 102, 118, 120, 121, 125, 265, 286, 288
136, 139, 197, 198, 204, 214, 218, 224, 225, 234,
242, 246, 247, 251
control, 11, 17, 31, 34, 37, 41, 42, 43, 46, 47, 48, 57, D
58, 61, 91, 162, 251, 252, 294, 308, 316, 333, 337,
database, 5
342, 352
decay, 47, 50, 318, 319, 322
conventional composite, 115, 304
decomposition, 64, 299, 336, 338, 344, 345
conversion, 20, 162, 164, 170, 173, 174, 175, 178,
decomposition reactions, 344, 345
183, 185, 188, 322, 344
decomposition temperature, 336
conversion rate, 162
deduction, 177
cooling, 29, 153, 155, 157, 159, 162, 163, 179, 184,
defects, 147, 152, 157, 158, 160, 164
185, 193, 301, 311, 353
defense, 3
Copenhagen, 312
deficiency, 369
copolymers, 9, 10, 11, 13, 17, 18, 19, 20, 21, 302,
definition, 110, 179, 304, 316
317
deformation, viii, ix, xi, 41, 73, 76, 108, 109, 110,
corn, 294, 296, 297, 298, 299, 309, 311
112, 144, 160, 172, 193, 226, 253, 255, 256, 257,
correction factors, 308
259, 262, 265, 267, 268, 270, 272, 273, 275, 276,
correlation(s), 66, 324, 341
277, 278, 282, 283, 284, 285, 286, 287, 288, 289,
corrosion, vii, 25, 350
291, 349, 352, 353, 355, 359, 369, 370
cost saving, 296
degradation, 27, 29, 30, 32, 33, 34, 35, 36, 39, 40, 41,
costs, 4, 150, 295
42, 43, 45, 46, 47, 48, 49, 50, 51, 52, 53, 55, 56,
cotton, ix, 293, 296
57, 58, 59, 60, 61, 62, 63, 64, 66, 67, 68, 69, 294,
coupling, ix, x, 48, 75, 76, 81, 95, 96, 103, 107, 109,
298, 299, 300, 304, 306, 308, 343, 344, 345
110, 112, 118, 136, 144, 149, 151, 157, 158, 160,
degradation mechanism, 66, 344
163, 164, 165, 167, 168, 169, 171, 172, 173, 175,
degradation process, 40, 47, 55, 62, 64
179, 180, 184, 187, 188, 190, 191, 194, 198, 299,
degradation rate, 299
300, 302, 311, 315, 316, 317, 318, 321, 325, 326,
degree of crystallinity, 301, 302
327
covering, 164
376 Index
density, xi, 10, 19, 59, 152, 165, 166, 168, 199, 207, double bonds, 47
217, 218, 227, 234, 236, 237, 244, 246, 257, 296, drug delivery, 295
328, 338, 349, 361, 366, 369, 371 drug delivery systems, 295
depolymerization, 294, 344 drugs, 303
deposition, 335 drying, 34, 44, 49, 54, 55, 57, 59
depression, 44, 301, 302 DSC, 14, 180, 182, 183, 184, 186, 187, 301, 307,
derivatives, 295, 322 323, 326, 338, 339
designers, viii, 6, 73, 75, 150, 151 ductility, 29, 39, 46, 57, 301, 302
desorption, 345, 346 durability, vii, 5, 25, 26, 27, 30, 32, 36, 39, 48, 52,
destruction, 50 53, 56, 57, 58, 60, 61, 62, 63, 65, 66, 68, 69, 70,
deviation, 39, 337 71
DGEBA, 30 duration, 57, 61, 158, 304
diamines, 299 dynamic mechanical analysis, 38, 54, 60, 302
dielectric constant, 95, 112, 199, 205, 210, 213, 238,
244
differential equations, 74, 84, 120, 121, 123, 124, E
136, 138
economics, 294
differential scanning calorimeter, 14, 180, 301, 311,
education, 286
325
egg, 297
diffusion, ix, 4, 30, 34, 39, 40, 41, 43, 55, 65, 149,
eigenvalue, 85
164, 165, 168, 169, 171, 172, 173, 174, 177, 179,
elaboration, 191
180, 297, 305, 317, 324, 336, 345, 350, 359, 361,
elasticity, 31, 43, 51, 74, 126, 171, 172, 179, 189,
368, 369, 371, 372
280, 284
diffusivity, 345
electric field, viii, 73, 76, 80, 87, 88, 89, 90, 92, 94,
dimer, 294, 344
96, 104, 105, 106, 107, 109, 112, 114, 124, 126,
discontinuity, 117, 326
127, 128, 129, 131, 132, 134, 139, 140, 141, 142,
Discontinuously reinforced metal matrix composites,
143, 144, 146
(DRMMCs), ix, 255, 256, 259, 268, 278, 284, 285
electrical properties, 11
discs, 250
electrodes, 92, 147, 252
dislocation, xi, 257, 349, 361, 362, 369, 371
electroluminescence, 333
dispersion, 4, 9, 11, 12, 14, 17, 18, 250, 252, 256,
electron, 4, 297, 334, 339, 349, 350, 352
276, 298, 299, 305, 306, 307, 314, 334, 342, 345,
electron microscopy, 297
369
elongation, 273, 302, 304, 305, 308
displacement, 84, 85, 86, 92, 94, 98, 100, 103, 110,
emission, 175, 318, 319, 322, 325, 326, 327, 328
111, 117, 119, 120, 123, 125, 132, 135, 136, 137,
endothermic, 182, 338
138, 139, 154, 173, 177, 188, 191, 198, 200, 205,
energy, 6, 47, 146, 150, 166, 168, 290, 291, 294, 296,
210, 214, 216, 217, 218, 219, 220, 221, 224, 225,
306, 318, 324, 336, 345, 368
226, 227, 230, 234, 237, 238, 241, 242, 243, 245,
energy consumption, 6, 296
247, 248, 270
energy transfer, 324
disposition, 30, 63
entropy, 168, 169
dissociation, 47
environment, vii, viii, 5, 6, 25, 29, 31, 39, 40, 41, 45,
distilled water, 31, 33, 40, 54, 65
46, 48, 51, 52, 53, 55, 56, 57, 60, 64, 66, 68, 69,
distribution, ix, 4, 58, 65, 74, 75, 82, 104, 105, 106,
71, 294
115, 121, 126, 127, 128, 139, 140, 165, 255, 256,
environmental conditions, 27, 38, 48, 52, 54, 56, 57,
268, 271, 273, 275, 276, 283, 289, 290, 298, 324,
64, 66, 67
336, 341, 344, 350, 352, 358, 359, 361, 365, 366,
environmental effects, 68
369
environmental factors, vii, 25, 69
distribution function, 283
environmental issues, 294, 308
divergence, 165
epoxy, vii, 19, 20, 27, 28, 29, 30, 31, 32, 33, 36, 37,
DMA analysis, 162
39, 40, 43, 45, 47, 48, 49, 50, 51, 52, 53, 54, 55,
DNA, 10
56, 57, 58, 59, 60, 61, 63, 66, 68, 69, 70, 91, 92,
dominance, 45
149, 151, 153, 154, 155, 156, 157, 158, 160, 161,
donors, 334
162, 163, 165, 170, 173, 174, 175, 178, 181, 182,
Index 377
183, 184, 185, 186, 187, 188, 189, 191, 194, 212, FEM, 74, 126, 149, 150, 154, 160, 167, 173, 184,
213, 317, 320, 321, 322, 323, 324, 325, 326, 327, 192, 193, 194
328 fermentation, 294
epoxy polymer, 318, 325 fiber bundles, 300
epoxy resins, 57, 183, 322, 327 fiber content, 296, 297, 298, 301, 310, 311
equilibrium, 13, 30, 43, 54, 78, 82, 96, 97, 98, 115, Fiber Reinforced Polymers (FRPs), vii, 69, 70
116, 119, 134, 135, 136, 157, 166, 238, 243, 248, fibers, vii, viii, ix, 25, 28, 30, 31, 32, 33, 35, 36, 37,
301, 302, 327, 342 38, 39, 40, 41, 42, 43, 44, 45, 46, 48, 50, 51, 52,
equipment, 47 53, 54, 55, 56, 57, 58, 60, 61, 63, 64, 65, 152, 153,
erosion, 61 157, 255, 256, 257, 262, 283, 289, 291, 293, 295,
ester(s), viii, 25, 36, 38, 39, 44, 45, 54, 55, 63, 67, 68, 296, 297, 298, 299, 300, 302, 308, 309, 310, 311,
69 334, 350
ethanol, 296, 307 filament, 112, 125
ethyl alcohol, 352 filler surface, 317
ethylene glycol, 307 fillers, ix, x, 293, 295, 297, 298, 312, 334
ethylene oxide, 9, 11, 12, 19, 20, 307 film(s), 12, 19, 20, 295, 297, 298, 301, 304, 306, 307,
Euler, 188 309, 312, 338, 339, 369
evaporation, 12, 20 financial support, 194
evidence, 28 finite element method, 74, 160, 163, 256, 283, 284,
evolution, 155, 162, 164, 165, 167, 169, 172, 175, 285
177, 178, 179, 180, 181, 182, 183, 184, 185, 186, fire resistance, 29
188, 190, 191, 268, 271, 290, 294, 297, 323, 324, flammability, 304
325 flax fiber, 297, 300, 309, 311, 312
examinations, 31, 32, 40, 46, 49 flexibility, 296
excitation, 319 flexural strength, 32, 36, 46, 49, 63, 300, 306
exciton, 11 fluctuations, 19, 291, 334
exclusion, 297, 310 fluid, 29, 40, 342
execution, 26, 66 fluorescence, x, 315, 318, 319, 322, 323, 325, 327,
exothermic, ix, 149, 150, 158, 164, 175, 178, 179, 328
180, 182, 183, 188, 190, 338, 339 fluorescent labels, x, 315, 318, 319
exothermic effects, ix, 149, 175, 183 fluorophores, 319, 328
experimental condition, 322, 340, 342, 343, 344 foams, 296, 298, 309, 310
exposure, viii, 17, 25, 26, 28, 29, 36, 37, 38, 40, 41, focusing, 26, 151, 306
42, 43, 44, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, food, 300, 303, 304, 312
57, 58, 59, 60, 61, 63, 64, 65, 66, 70, 71 Formica, vii
external environment, 26, 54, 336 fossil fuels, 47
extraction, 158 Fourier, 13, 15, 121, 305, 326, 339
extrusion, 296, 303, 304, 305, 306, 308, 313, 314 fragmentation, 38, 298
France, 66, 70, 149, 195, 196, 197, 250, 313
free energy, 167, 170
F free volume, 328, 334, 342, 345, 346
freedom, 173
fabric, 27, 28, 29, 31, 32, 33, 34, 41, 43, 44, 46, 48,
freezing, 37, 55, 67
50, 53, 55, 57, 58, 60, 61, 146, 316
friction, 333, 334, 335, 336, 341, 346, 350
fabrication, 10, 20, 26, 91
FTIR spectroscopy, 317, 323, 327, 337, 339
failure, viii, 4, 26, 28, 31, 32, 36, 37, 38, 41, 47, 48,
fullerene(s), x, xi, 333, 334, 337, 342, 343, 346, 348
49, 50, 53, 54, 56, 57, 58, 59, 61, 66, 68, 73, 74,
funding, 3
75, 76, 92, 93, 144, 150, 152, 153, 190, 191, 259,
fusion, 4, 350
262, 265, 287, 297, 309, 350
family, 10, 294
fatigue, vii, 25, 68, 74, 256, 262, 263, 265, 268, 273, G
286, 287, 289
feedback, 352 gel, 20
gelation, 162, 164, 178, 179, 182, 184, 187, 190, 191
378 Index
gene, 240 humidity, 31, 38, 52, 54, 57, 58, 59, 64, 297, 298,
generalization, 160, 249 336
generation, 152, 259, 275, 334 hybrid, vii, ix, 28, 31, 43, 48, 50, 65, 146, 197, 225,
Germany, 67, 333, 347 252, 312, 314, 341
glass, viii, 12, 14, 25, 27, 28, 29, 30, 31, 32, 33, 34, hydrochloric acid, 12, 40, 42
36, 37, 38, 39, 40, 41, 42, 43, 44, 47, 48, 49, 50, hydrogen bonds, 301, 305
51, 52, 53, 54, 55, 56, 57, 58, 60, 62, 63, 64, 65, hydrolysis, 27, 30, 34, 35, 44, 45, 46, 54, 63
66, 67, 68, 69, 70, 71, 91, 125, 157, 163, 179, 182, hydrophilic behavior, x, 293
187, 298, 302, 316, 317, 320, 321, 323, 324, 325, hydrophilicity, 296, 305
327, 328, 334, 342 hydrophobic polymer matrix, 30, 296, 299, 300
glass transition temperature, 14, 27, 32, 33, 35, 36, hydrophobic properties, 296
38, 42, 44, 49, 54, 55, 58, 60, 62, 69, 157, 163, hydroxide, 41, 42
179, 182, 187, 298, 302, 317, 325, 328 hydroxyapatite, vii
Glass-fiber reinforced plastic (GFRP), vii, 27, 29, 33, hydroxyl groups, 299, 301, 305
34, 37, 38, 39, 42, 46, 47, 51, 52, 53, 54, 55, 56, hypothesis, 154, 226, 230, 297
58, 61, 63, 65, 69, 70, 146 hysteresis loop, 267, 270, 272, 273, 275
glassy polymers, 67
glycerin, 297
glycerol, 295, 297, 303, 304, 305 I
government, 3
idealization, 269
grafting reaction, 300
identification, 168, 180
grains, xi, 283, 349, 362, 363, 369, 371
images, 12, 13, 14, 15, 289, 336, 340
graphite, 55, 66, 91
imaging, 297, 318
gravimetric analysis, 326
imidization, 338, 339, 340, 341, 346
gravity, 173
immersion, 30, 31, 32, 33, 34, 36, 38, 40, 41, 43, 44,
groups, 47, 49, 296, 299, 305, 316, 317, 318, 321,
45, 46, 48, 49, 51, 52, 53, 55, 56, 57, 59, 61, 63,
322, 324, 334, 344
64, 65, 66, 327, 328
growth, 11, 12, 36, 39, 151, 162, 163, 184, 190, 301,
impact energy, 369
302, 308, 338
impact strength, 27, 47
growth rate, 301, 302
implementation, 163, 167, 173, 273, 278, 284, 287,
guidelines, 66, 91
288
impregnation, 33, 46, 309
H in situ, 68, 264, 286, 300, 311, 322, 326
incidence, 45, 46, 47
hardener, 165, 167, 172, 173, 174, 178, 180 inclusion, 273, 278, 279, 280, 281, 283, 290, 291,
HDI, 299, 311 294, 304
heat, 3, 28, 31, 34, 35, 50, 109, 146, 163, 164, 166, inclusion bodies, 294
169, 171, 172, 173, 174, 175, 180, 182, 186, 187, indication, 64
188, 191, 257, 260, 266, 303, 306, 314, 320, 334, indicators, 66
336, 338, 340, 345, 346, 347, 350, 352, 353, 355, indices, 199, 201, 228, 279
359, 365, 368 indirect effect, 170
heat transfer, 169, 171, 172, 174, 180 induction time, 301
heating rate, 29, 91, 162, 174, 175, 178, 188, 192, industrial application, 3, 350
298, 334, 336, 338, 342, 345, 352 industry, viii, 3, 25, 26, 40, 294, 310
height, 13, 15, 44, 188, 268 inelastic, 169, 265, 278, 285, 288, 290
hemicellulose, vii inequality, 169
hemp, ix, 293, 295 inertia, 208, 235
hepatitis, 299 infinite, 155, 336
heterogeneity, 30, 47, 151, 159, 160 infrared spectroscopy, 327
Hong Kong, 3, 349 infrastructure, 26, 68, 71
hot pressing, 297 inhomogeneity, 135
HPLC, 337 initiation, 34, 47, 61
innovation, 6, 169
Index 379
inorganic fillers, 296

insertion, 304
L
insight, 303, 342
lactic acid, 294, 295, 310, 311, 312, 313
instability, 152, 154, 155, 157, 191, 193, 194, 303
lamellae, 10
Instron, 352
lamination, 107, 302
integration, 20, 94, 112, 133, 163, 209, 236, 279, 281,
language, 173
288, 291, 361
laser, 4, 153
integrity, 29, 40, 41, 75, 93, 143
lattices, 361, 362
intensity, 48, 146, 319, 322, 323, 325, 339, 343, 345
laws, 165, 167, 169, 171, 180, 187
interaction(s), viii, 12, 25, 49, 70, 157, 193, 259, 278,
leaching, 55
287, 296, 304, 307, 309, 334, 339, 342, 347
life sciences, 10
interface, x, xi, 4, 27, 28, 29, 30, 31, 32, 35, 37, 38,
lifespan, 26
39, 40, 41, 42, 46, 49, 56, 59, 60, 62, 63, 64, 77,
light scattering, 10, 19
158, 198, 228, 246, 268, 270, 273, 293, 299, 300,
lignin, vii, 296
303, 310, 317, 321, 323, 324, 325, 328, 333, 335,
lignocellulose, 297
336, 349, 350, 352, 355, 359, 360, 361, 362, 368,
limitation, 150, 152, 164, 294, 355
369, 371
linear function, 164, 170, 174, 186
interface layers, 334
linear law, 168, 169, 170
interfacial adhesion, 6, 300, 302, 308
linkage, 44
interfacial bonding, 28
liquid crystal phase, 9
interfacial properties, 320, 325
liquid crystals, 10, 19
intermetallic compounds, 4, 350
liquid monomer, 300
interphase, x, 42, 46, 49, 50, 315, 317, 318, 326, 328
liquid nitrogen, 28, 31
interpretation, 318, 319
liquid phase, xi, 350, 351, 352, 353, 354, 355, 358,
interrelations, 341
363, 367, 369, 371, 372
interval, 182, 187
literature, 26, 62, 74, 151, 179, 190, 278, 279, 294,
inversion, 284
299, 326
investment, 3
lithium, 11
ions, 40, 41, 46, 63, 306
location, 17, 77, 78, 88, 89, 321
IR spectra, 327, 335, 336
London, 68, 145, 290, 309, 312, 329
irradiation, 59
Louisiana, 73, 288
isolation, 54
low temperatures, 33, 69
isothermal, 158, 162, 181, 182, 187, 188, 189, 192,
luminescence, x
301, 307
lying, 65
isothermal crystallization, 301, 307
lysine, 299
Italy, 25, 67, 69
J M
manufacturer, 12, 91, 181

Japan, 67, 70, 196
manufacturing, 5, 9, 11, 57, 74, 150, 256, 294, 300,
joints, viii, xi, 4, 5, 73, 74, 75, 76, 90, 91, 94, 109,
311
144, 145, 146, 349, 350, 352, 354, 355, 356, 357,
marine environment, 42, 57, 70
358, 359, 360, 362, 369, 370, 371
market(s), 4, 5, 184, 294
Jordan, 85, 86
mass loss, 338, 343, 345
material degradation, 67
K materials science, 11
matrix radius, 154
kinetic parameters, 344 MDI, 299
kinetics, 43, 161, 164, 165, 169, 170, 173, 177, 180, measurement, ix, 149, 160, 175, 193
183, 184, 187, 188, 311, 322, 323, 344 mechanical behavior, 164, 167, 168, 268, 297, 302
mechanical loadings, 103, 126
mechanical performances, ix, 255, 256
380 Index
mechanical properties, viii, ix, x, 3, 6, 25, 27, 28, 29, molecular structure, x, 47, 315, 325, 341
30, 31, 33, 40, 42, 46, 48, 50, 51, 54, 58, 60, 63, molecular weight distribution, 10, 11, 12, 14, 18, 54,
64, 65, 68, 91, 150, 151, 161, 163, 290, 293, 295, 298, 300, 303, 307
296, 297, 298, 299, 302, 304, 307, 308, 309, 310, molecules, x, 10, 298, 302, 305, 307, 315, 318, 328,
311, 312, 313, 314, 315, 316 333, 334, 339, 341, 342, 345, 346
mechanical stress, 27 monomer(s), 54, 294, 300, 317, 319, 338, 344
mechanical testing, 297, 298 Moon, 75, 146, 252
media, 54, 304, 312, 334 morphology, 9, 11, 12, 13, 15, 16, 17, 18, 19, 28, 31,
melt(s), 300, 301, 302, 303, 305, 306, 307, 313, 314 286, 301, 311, 313, 317, 339, 340, 341
melting temperature, 14, 298, 301, 302, 308, 368 motion, 166, 178, 198, 210, 214, 219, 225, 236, 333
memory, 75, 278 movement, 208, 209, 362
metallurgy, xi, 5, 350, 370, 371 multilayer films, 304, 312
metals, vii, 4, 257, 265, 273 multilayered structure, 303
methyl methacrylate, 342 multiphase materials, 290, 291
methylene, 299 multiplicity, 85
Miami, 371
Micarta, vii
micelles, 10, 21 N
Microbial, 294, 309
Na+, 305, 307
microcrystalline cellulose, 299, 310
NaCl, 39, 40, 43, 45, 53, 55
microorganisms, 43
nanocomposites, x, 3, 9, 10, 11, 17, 18, 293, 299,
microscope, xi, 12, 325, 349, 350
304, 305, 306, 307, 312, 313, 314, 334
microscopy, 9, 11, 12, 17, 18
nanometer(s), 10, 304, 317, 318, 328, 334
microstructure(s), ix, xi, 10, 163, 255, 256, 257, 271,
nanoparticles, 9, 10, 11, 12, 17, 18, 20, 308, 342
275, 285, 294, 308, 349, 350, 351, 352, 355, 360,
nanostructured materials, 9, 10, 18
367, 369, 371
nanotechnology, 10
microviscosity, 319, 322
nanowires, 20
military, vii, viii, 4, 73, 74
natural fillers, 298, 299, 302
minerals, 41
natural polymers, x, 293, 294, 295, 302, 306, 308
minority, 13
natural resources, 294
mixing, 164, 300, 308, 342, 355
nematic liquid crystal, 11, 19
MMCs, 3, 4, 5, 6, 350
Netherlands, 147, 313
model specification, 67
network, 10, 19, 20, 182
modeling, ix, 5, 126, 144, 149, 150, 151, 152, 155,
neural network(s), 334
164, 165, 167, 172, 174, 179, 180, 187, 188, 191,
New Jersey, 20
193, 194, 225, 266, 267, 278, 287, 288, 289, 290,
New Orleans, 288
291, 345
New York, 253, 312, 328, 347, 372
models, ix, 74, 151, 152, 164, 168, 180, 191, 197,
Newton, 303
198, 226, 255, 256, 265, 273, 275, 277, 278, 280,
NIR, 327
283, 284, 285, 288, 290, 308
nitrogen, 338, 342, 344
modules, 302
nodes, 173, 174, 175, 191
modulus, x, 27, 29, 31, 32, 33, 34, 35, 36, 38, 42, 43,
noise, 339, 345
45, 46, 48, 50, 51, 52, 53, 54, 55, 59, 61, 83, 97,
normal distribution, 341, 344
118, 136, 154, 162, 168, 184, 185, 190, 191, 267,
nucleating agent, 296, 307
281, 291, 293, 295, 296, 297, 298, 299, 300, 301,
nucleation, 11
302, 304, 305, 306, 307, 308
nucleus, xi, 349, 369
moieties, 334
numerical analysis, 88, 132, 163
moisture, vii, 25, 27, 30, 32, 35, 36, 38, 39, 43, 45,
46, 49, 50, 51, 52, 53, 55, 59, 60, 64, 65, 67, 296,
299, 302, 304, 308, 310 O
moisture content, 39, 43, 45, 52
mold, 33, 41, 158, 298 observations, ix, 28, 255, 256, 259, 265, 267, 341,
molecular mass, 11 344, 346
Index 381
observed behavior, 51 physical treatments, 299

occlusion, 368 physico-chemical characteristics, 318
oil, 294, 295, 298, 308 physics, 20, 164, 179, 192, 196, 333
oligomers, 307, 344 piezoelectric layers, viii, 73, 76, 87, 88, 89, 90, 108,
one dimension, 336 109, 111, 112, 114, 128, 129, 130, 131, 132, 134,
operator, 165, 168, 199, 207, 227, 234, 281, 282, 283 139, 140, 142, 143, 147, 226, 251, 252
optical fiber, 160 piezoelectricity, 197, 198
optical microscopy, 44 plane waves, 210, 247, 252
optical properties, 11 plants, 42
optimization, 150, 151, 163 plastic deformation, 260, 272, 278, 288, 290, 368
ordinary differential equations, 121, 123 plastic strain, 257, 267, 271, 273, 278, 281, 286
organ, 305, 306, 307, 308, 313, 314 plasticity, 270, 273, 275, 281, 282, 283, 287, 288,
organization, 10 289, 290, 291
orientation, 13, 57, 65, 133, 279, 283, 289, 291 plasticization, 30, 31, 33, 34, 35, 39, 44, 46, 60, 63,
oxidation, 27, 47 64, 69, 313
oxide nanoparticles, 18 plasticizer, 54, 298, 299, 302, 303, 305, 310
oxides, 316, 352 plastics, 47, 68, 294, 295, 308
platelets, 283, 305, 307
Plywood, vii
P PMDA, 337, 338, 339, 341, 342
PMMA, 342, 343, 344, 346
PAA, 334, 337, 338
polar body, 166
packaging, 13, 295, 297, 298, 299, 300, 303, 304,
polarity, x, 315, 319, 322
309, 312
polarization, 217
parameter, 130, 167, 168, 179, 182, 184, 220, 225,
poly(3-hydroxybutyrate), 311
248, 249, 322, 324
poly(vinyl chloride), 67
Paris, 194, 197, 251, 291
polybutadiene, 19
particle morphology, 289
polydispersity, 11, 298
particles, xi, 104, 262, 268, 270, 271, 272, 273, 275,
polyesters, 63, 294, 295, 298, 301, 302, 304, 305,
276, 299, 306, 316, 334, 336, 340, 341, 349, 350,
308, 310
352, 355, 359, 360, 368, 369, 370
polyethylene, vii, 298, 316
particulate reinforced metal matrix composites,
polyimide(s), xi, 29, 333, 334, 339
(PRMMCs), ix, 255, 256, 259, 262, 268
polyisoprene, 19
partition, 166
polymer(s), vii, ix, x, xi, 10, 12, 19, 21, 25, 26, 27,
passive, viii, 73
28, 29, 47, 64, 65, 66, 67, 68, 69, 70, 103, 157,
pathways, 305
160, 166, 167, 169, 172, 173, 174, 178, 196, 206,
patterning, 11
252, 275, 283, 293, 294, 295, 296, 297, 298, 299,
performance, vii, viii, ix, x, 5, 11, 25, 26, 27, 29, 39,
300, 301, 302, 303, 304, 305, 306, 307, 309, 310,
40, 43, 47, 56, 60, 62, 64, 65, 75, 91, 95, 103, 149,
311, 312, 315, 316, 317, 319, 320, 321, 325, 328,
150, 151, 153, 158, 296, 297, 299, 304, 307, 308,
333, 334, 335, 342, 343, 344, 345, 346, 347
310, 315, 341
polymer blends, 317
permeability, 304, 306, 307, 313
polymer chains, 47, 304
permeation, 307
polymer composites, vii, 25, 26, 27, 67, 68, 69, 296,
permit, 3
299, 310, 311, 325, 333, 334
peroxide, 300
polymer matrix, x, 10, 28, 283, 304, 305, 307, 311,
pesticides, 303
315, 316, 317, 320, 328, 334, 342
pH, x, 31, 34, 41, 42, 44, 45, 47, 63, 315
polymer melts, 303
phase diagram, 19, 20
polymer nanocomposites, 304, 334
PHB, 294, 301, 302
polymer structure, 169
photocatalysis, 11
polymer systems, 319
photons, 318
polymeric blends, 308
physical interaction, 302
polymeric composites, 65
physical properties, 3, 11, 20, 296, 300, 301, 313,
polymeric materials, ix, x, 293
342
382 Index
polymerization, 295, 300, 307, 311, 314, 322, 324, raw materials, x, 293
337 reactant(s), 182, 187, 337
polymerization process(es), 322 reaction rate, 165, 324
polynomial functions, 204 reading, 166
polypropylene, 298, 302 real time, 150, 155
polysaccharide, 309 reality, 68, 175
polysiloxanes, 19 recall, 205
polystyrene, 19, 20, 342 recovery, 288, 292
poor, ix, 28, 61, 167, 293, 308 recycling, 5
porosity, 158 redistribution, 37, 86, 93, 103, 106
porous materials, 291 reduction, viii, 27, 31, 32, 33, 34, 35, 36, 38, 39, 40,
Portugal, 62, 67, 68, 70 41, 42, 43, 45, 46, 49, 51, 53, 55, 56, 57, 58, 59,
potato, 305, 309 60, 64, 65, 73, 108, 131, 142, 143, 163, 302, 305,
power, 13, 15, 154, 170, 179, 365 307, 338
prediction, ix, 26, 147, 149, 153, 160, 163, 172, 188, reflection, 338
189, 190, 191, 193, 194, 255, 256, 278, 284, 285, refractive index, 10
287, 292, 336 regenerated cellulose, 295, 298
pressure, 19, 75, 91, 146, 168, 169, 172, 174, 177, regression, 342
180, 303, 335, 352, 353, 360, 369 rehabilitation, 26, 62, 69
probability, 277 reinforcement, ix, x, xi, 3, 4, 6, 34, 39, 61, 65, 66,
probe, 12, 175, 183, 322 150, 153, 191, 260, 262, 268, 272, 283, 286, 293,
product design, 6 296, 297, 298, 299, 308, 310, 315, 316, 325, 326,
product performance, 304 328, 349, 350, 352, 355, 359, 360, 361, 367, 369,
production, x, 3, 4, 5, 6, 169, 187, 293, 301, 309, 336, 370, 371
350 reinforcing fibers, 39, 63
production costs, 301 relationship(s), x, xi, 19, 82, 86, 95, 103, 111, 112,
program, 163, 187, 188, 342 119, 120, 125, 133, 139, 162, 181, 252, 294, 308,
promote, 27, 37, 62 317, 333, 336, 349, 353, 354, 355, 359, 360
propagation, 210, 238, 242, 247 relaxation, 67, 155, 157, 163, 295, 297, 327
proportionality, 267, 278 relaxation effect, 163
protective coating, 49 relaxation process(es), 295
protein, 294, 306, 313 relevance, 333, 347
protocol, 168, 175 repair, 67
pulse, xi, 58, 349, 350, 352, 355, 356, 358, 361, 362, residues, 28, 54
363, 368, 369, 371 resin molecules, 47, 64
pure water, 30, 33, 34, 35, 42, 44, 46, 50, 51, 55, 63 resins, 26, 27, 39, 46, 54, 58, 61, 62, 63, 65, 66, 150,
pyrolysis, 68 161
pyromellitic dianhydride, 337 resistance, vii, 25, 28, 37, 39, 51, 59, 63, 64, 256,
267, 272, 286, 296, 304, 305, 350, 352, 368
resolution, 179, 202, 205, 234, 339
Q resources, x, 5, 293, 299, 308, 309
retention, 35, 42, 54, 71
quaternary ammonium, 307
returns, 163, 318
rheological properties, 313
R rheology, x, 313, 333
rheometry, 307
radiation, 47, 52, 58, 59, 171, 173, 318, 365 rigidity, x, 315, 317, 319, 322, 325, 326, 355
radius, 11, 14, 15, 17, 111, 114, 117, 133, 135, 154, rods, vii, 39, 54, 69, 74
236, 241, 244, 335 room temperature, ix, 9, 11, 12, 13, 14, 15, 16, 17,
rain, 54 30, 39, 40, 54, 55, 56, 57, 59, 91, 157, 162, 186,
range, 29, 36, 39, 41, 47, 54, 57, 160, 199, 228, 260, 191, 255, 259, 266, 267, 274, 275, 287, 288, 289,
297, 300, 327, 334, 338, 341, 342, 345, 346, 351, 336, 342, 353
352, 355, 358 rotations, 83, 94, 97, 110
Index 383
roughness, 33 shear strength, 32, 34, 36, 42, 46, 50, 53, 60, 63, 92,
Royal Society, 68 94, 296
rubber, 294 shores, 44
rubbery state, 182 shortage, 294, 308
Russia, 333 sign(s), 35, 157, 159, 360, 361
signaling, 337, 341
signal-to-noise ratio, 342, 344
S silane, 48, 300, 302, 316, 317, 320, 324, 325, 327
silanol groups, 316
safety, 26, 265
silica, 17, 308, 314, 316, 317, 325, 328
salt(s), 39, 40, 41, 42, 43, 45, 46, 52, 53, 55, 56, 57,
silicon, 12, 92, 287
59, 61, 63, 64, 71
silk, 294
sample, 15, 17, 32, 33, 54, 65, 158, 161, 162, 173,
similarity, 46
182, 192, 268, 301, 326, 335, 342, 344, 345
simulation, xi, 48, 104, 151, 161, 164, 173, 174, 176,
saturation, 30, 39, 262
177, 178, 179, 183, 188, 189, 191, 192, 193, 194,
sawdust, vii
268, 269, 270, 272, 273, 275, 276, 277, 289, 290,
scaling, 337
303, 349, 355, 363, 371
scanning electron microscope (SEM), xi, 28, 31, 32,
Singapore, 58, 61, 69
40, 49, 297, 300, 302, 305, 308, 340, 347, 349,
sites, x, 315, 318, 319, 323, 325, 327, 328, 334, 344
350, 352, 355, 360, 361, 362, 369, 370
skin, 294, 303
scanning electron microscopy, 41
smart com, viii, 74, 76, 109, 110, 112, 129, 132, 133,
scatter(ing), 45, 276302, 307, 355
136, 147
school, 194
smart materials, 75
science, 20, 74, 294, 308, 334, 347
smart-structures, ix, 197
scientific community, 150
smoothing, 342
scull, vii
sodium hydroxide, 53, 296, 305
search, 342
software, 12, 125, 165, 167, 173, 188
sedimentation, 337, 342
soil, 42
seed, ix, 293
sol-gel, 9, 11, 12, 17, 18, 20
segregation, 13, 15, 18
solid phase, 352, 353, 355
selecting, 163, 359
solid state, 161, 182, 184, 185, 302, 368
self-assembly, 9, 10, 11, 14, 16, 17, 20
solidification, 18
self-organization, 10
solubility, 294, 342
semiconductor, 11
solvent(s), 9, 10, 11, 12, 14, 15, 16, 17, 303, 305,
sensing, 11, 95, 108, 112, 144
338
sensitivity, 164, 178, 302, 308, 319, 323, 325
solvent molecules, 338
sensors, viii, 73, 75, 109, 144, 146, 147, 160, 252
sorption process, 29, 30
separation, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20, 36,
Spain, 9, 70, 315
322
species, ix, 149, 165, 168, 170, 171, 172, 173, 179,
series, 29, 84, 92, 121, 198
180, 345
shape, 4, 11, 75, 153, 192, 262, 268, 272, 273, 279,
specific heat, 168, 173, 174, 175, 179, 186, 188, 366
289, 291, 300, 322, 335, 336, 340, 341, 343, 344
specific surface, 342
shape-memory, 75
specificity, 325
shear, viii, 32, 34, 35, 36, 42, 45, 46, 50, 51, 53, 57,
spectroscopy, 295, 305, 327, 338
60, 63, 73, 74, 77, 81, 82, 83, 85, 86, 87, 88, 89,
spectrum, 13, 15, 323, 339
90, 91, 92, 93, 94, 100, 103, 104, 105, 106, 107,
speed, 12, 131, 143, 294, 335, 355, 358, 359, 365,
108, 109, 110, 117, 118, 124, 125, 126, 127, 128,
369
129, 130, 131, 132, 135, 136, 138, 139, 140, 141,
spin, 9, 11, 12
142, 143, 146, 154, 162, 184, 185, 198, 199, 200,
sports, 3
210, 214, 216, 217, 218, 219, 220, 223, 225, 226,
stability, 155, 163
230, 231, 232, 234, 238, 239, 240, 242, 243, 245,
stages, 338, 346
249, 251, 262, 276, 281, 296, 298, 303, 334, 341
standards, 26, 65, 66
shear deformation, 83, 94, 110, 132, 226, 251
384 Index
starch, x, 293, 294, 295, 296, 297, 298, 299, 300, 301, systems, vii, 3, 5, 9, 11, 12, 18, 19, 20, 27, 29, 30, 31,
303, 304, 305, 308, 309, 310, 311, 312, 313, 314 32, 36, 38, 39, 40, 42, 49, 54, 57, 58, 61, 62, 65,
starch blends, 296, 299, 305, 311 66, 70, 71, 74, 75, 76, 77, 92, 100, 109, 120, 138,
state laws, 170, 171, 172 144, 151, 153, 168, 181, 182, 253, 296, 307, 317,
statistical analysis, 153 322, 323, 326, 328
steel, vii, 3, 25, 39, 52, 55, 287, 288, 290, 335, 340
storage, vii, 10, 14, 44, 294, 302, 304, 306, 337
strain, 28, 31, 33, 40, 43, 50, 54, 57, 59, 61, 62, 65, T
76, 86, 103, 111, 119, 125, 133, 139, 144, 145,
talc, 296
152, 153, 160, 163, 166, 168, 169, 173, 177, 178,
tanks, vii
179, 180, 181, 182, 188, 192, 198, 199, 201, 205,
technology, 3, 4, 5, 74, 146, 303, 306, 308, 309, 347
207, 226, 227, 258, 260, 261, 262, 263, 265, 266,
TEM, 305, 306, 350, 352
267, 268, 270, 271, 272, 273, 274, 275, 276, 277,
temperature, vii, ix, xi, 4, 11, 12, 13, 15, 16, 17, 25,
278, 279, 280, 283, 285, 286, 287, 289, 290, 302,
26, 27, 28, 29, 30, 31, 32, 35, 36, 38, 39, 40, 42,
307
43, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 59, 60,
strategies, 11, 20
62, 63, 64, 65, 66, 68, 69, 149, 157, 158, 159, 160,
strength, vii, viii, 25, 26, 27, 28, 29, 30, 31, 32, 33,
161, 162, 163, 164, 166, 167, 168, 169, 170, 172,
34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 48,
173, 174, 175, 176, 177, 178, 179, 180, 181, 182,
49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 63,
183, 185, 186, 187, 188, 189, 190, 191, 192, 194,
64, 65, 69, 73, 74, 75, 92, 93, 94, 107, 130, 132,
255, 259, 262, 265, 286, 288, 294, 297, 300, 301,
143, 144, 150, 152, 159, 256, 267, 270, 278, 286,
302, 303, 305, 306, 311, 319, 323, 324, 325, 326,
295, 296, 297, 298, 299, 300, 301, 305, 306, 350,
334, 335, 336, 338, 339, 341, 342, 343, 344, 345,
352, 354, 355, 357, 358, 359, 360, 361, 369, 370
346, 349, 350, 351, 352, 353, 354, 355, 363, 364,
stress-strain curves, 260, 261, 263, 274
365, 366, 367, 369, 371
strong interaction, 307
temperature gradient, 16, 161
structural characteristics, 78
tendons, 70
structural transformations, 346
tensile strength, xi, 4, 27, 29, 32, 33, 34, 35, 36, 38,
styrene, 9, 11, 12, 19, 20
39, 40, 41, 42, 43, 45, 46, 47, 48, 49, 51, 53, 54,
substitutes, 294
58, 59, 60, 61, 63, 64, 296, 297, 299, 300, 306,
substitution, 121
307, 309, 349, 350, 351, 354, 355, 357, 360, 365,
substrates, 63
370, 371
sugar, 294
tensile stress, 43, 48, 157, 178, 192
sulfuric acid, 47
tension, viii, 46, 50, 52, 55, 56, 57, 74, 75, 128, 133,
summer, 54, 60
134, 135, 136, 144
suppliers, 43, 50
tetrahydrofuran, 9, 11, 12
supply, 166, 303, 345
textiles, vii
supramolecular chemistry, 10
TGA, 342, 343, 344, 345
surface area, 342
theory, ix, 78, 82, 83, 85, 93, 94, 110, 132, 144, 197,
surface layer, 31
198, 200, 201, 225, 226, 250, 251, 252, 253, 270,
surface modification, x, 308, 315, 317
276, 278, 279, 284, 290, 291, 303
surface structure, 12
thermal analysis, 32, 34, 35, 38, 44, 297, 325
surface treatment, 317, 323
thermal decomposition, 335, 344
surplus, 360
thermal degradation, 303, 307, 334, 344, 345
survival, 294
thermal energy, 355
susceptibility, viii, 25, 27, 51, 308
thermal expansion, 27, 61, 62, 63, 151, 173, 174, 177,
suspensions, 342
178, 182, 186
sustainability, 308
thermal properties, ix, 293, 305, 314
swelling, 30, 44, 61, 300
thermal relaxation, 325
switching, 10, 19
thermal resistance, 297
symbols, 277
thermal stability, 306, 307
symmetry, 118, 121, 175, 205, 268
thermal treatment, 28, 29, 65, 313
synthesis, 11, 12, 17, 18, 312
thermodynamics, 166, 168
synthetic polymers, 294
thermograms, 14
Index 385
thermoplastic(s), vii, 5, 10, 19, 296, 297, 309, 310,

312, 313, 316
U
thermosets, 30, 322
UK, 68, 313
thermosetting, viii, 11, 19, 20, 25, 30, 39, 46, 66, 149,
ultraviolet light, 68
150, 155, 157, 158, 159, 160, 163, 164, 165, 169,
ultraviolet radiations, vii, 25, 48
173, 175, 179, 181, 182, 183, 184, 186, 187, 191,
unconditioned, 58
193, 322
uniaxial tension, 28, 42, 48, 57
thin films, 11
uniform, 4, 17, 49, 74, 117, 120, 121, 181, 270, 279,
three-dimensional model, 200, 230, 275
280, 283, 285, 298, 303, 336, 350, 355, 358, 359,
time, ix, xi, 4, 6, 9, 11, 12, 14, 26, 27, 28, 29, 31, 32,
369
33, 34, 35, 36, 37, 41, 43, 44, 46, 49, 50, 51, 58,
users, 4, 5
59, 60, 61, 63, 66, 91, 150, 151, 153, 157, 160,
UV, 17, 47, 48, 52, 54, 58, 59, 60, 64, 69, 75, 146,
162, 163, 165, 166, 168, 173, 175, 178, 179, 180,
318
181, 182, 183, 184, 185, 187, 188, 192, 194, 197,
UV irradiation, 69
198, 199, 226, 227, 236, 255, 263, 266, 267, 268,
UV light, 52
273, 274, 278, 283, 285, 287, 288, 289, 297, 307,
UV radiation, 47, 48, 52, 54, 59, 64
317, 324, 327, 328, 336, 342, 344, 349, 350, 352,
353, 355, 359, 363, 364, 369
time factors, 266 V
time increment, 187, 188
time periods, 33, 36, 63 vacuum, 12, 33, 34, 41, 44, 47, 53, 55, 65, 199, 227,
time use, 26 352
tin, 307 validation, 76, 190, 193, 291
titania, 20, 316 validity, 164, 169, 180
titanium, 9, 12, 18, 21, 262, 290, 314 values, 28, 32, 33, 34, 43, 46, 50, 53, 59, 93, 117,
titanium isopropoxide, 314 128, 129, 155, 163, 168, 205, 211, 226, 239, 240,
Tokyo, 67, 70 301, 302, 306, 324, 336, 341, 342, 344, 345
toluene, 337, 342 vapor, 63
total energy, 166 variability, 28, 60
toxicity, 299, 308 variable(s), 53, 81, 85, 100, 110, 118, 120, 121, 123,
Toyota, 304 124, 125, 132, 138, 166, 167, 168, 181, 187, 226,
trade, 36, 52, 57 234, 239, 278, 303
transformation(s), 169, 278, 284, 339, 346, 351 variation, 43, 61, 161, 165, 168, 177, 186, 339, 359,
Transient Pulse-Impact Liquid-Phase Welding, 365
(TPILPW), xi, 349, 350, 352, 353, 355, 359, 361, vector, 85, 102, 125, 139, 192, 220, 225, 239, 243,
362, 363, 368, 369, 370, 371 248
transition(s), 10, 12, 19, 182, 295, 308, 325, 326, 328, velocity, 58, 170, 335, 352, 355
338 vibration, 225, 251, 252, 253
transition temperature, 308 vinylester, 29, 33, 34, 39, 41, 43, 44, 51, 55, 60, 68,
transmission, 145, 305, 350 70, 71
transmission electron microscopy, 305 viscoelastic properties, 334
transparency, 153 viscosity, 164, 267, 298, 299, 300, 303, 324, 342
transport, 30, 45, 169 vision, 317
transportation, 150 vulnerability, viii, 25
transverse section, 153
treatment methods, 295
trend, 34, 38, 45, 151, 163, 337 W
trial, 281
tribology, x, 333, 334 wall temperature, 301
triggers, 152 wastewater treatment, 42
trimer, 344 water absorption, 65, 300, 309, 326, 327, 328
water diffusion, 30
water sorption, 59
water vapor, 31
386 Index
wave number, 154

wave propagation, 5, 225
X
wavelengths, 47, 157
xenon, 59
weakness, 40, 152, 176
X-ray diffraction (XRD), 295, 305, 306, 350, 352,
wealth, 5
360, 361
wear, 256, 333, 334, 335, 336, 339, 340, 341, 342,
346, 350
weight loss, 300, 306, 338, 343 Y
weight ratio, vii, 25, 350
welding, xi, 4, 74, 146, 349, 350, 352, 353, 354, 355, yarn, 34, 41, 51
358, 359, 360, 361, 363, 365, 367, 368, 369, 370, yield, 4, 128, 136, 209, 213, 214, 223, 230, 237, 241,
371, 372 244, 278, 288, 318, 319, 322, 328, 350
wetting, 4, 55 yttrium, 301, 311
wheat, 296, 297, 299, 302, 304, 311, 312
windows, 10
winter, 54, 60 Z
wood, vii, 296, 297, 299, 300, 311
workers, 53, 55, 57, 60, 75, 295, 319 ZnO, 243, 244

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NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

Leading-edge composite material research / Tobias G. Wouters (editor).

Published by Nova Science Publishers, Inc. New York

Commentary: Future Prospects for MMCs 3

Communication: Meso/Nanostructured Composites Based on Self-Assembled

Research and Review Studies 23

Chapter 1 Durability Aspects of Polymer Composites Used for Restoration

Chapter 2 Smart Adhesively Bonded Composite Joints: Analysis and Design 73

Chapter 3 Thermosetting Laminates Quality: From Fiber Waviness to

Chapter 4 Modelling of Multilayered Piezoelectric Composites 197

Chapter 5 Cyclic Deformation of Discontinuously Reinforced Metal

Chapter 6 Biodegradable Polymer Composites 293

Chapter 7 Composite Materials Studied at a Molecular Scale.

Chapter 8 Thermal and Wear Studies of Polymer-Fullerene Composites 333

Chapter 9 An Approach for Welding Particle Reinforcement

FUTURE PROSPECTS FOR MMCS

Kelvii Wei Guo1

1 cheaper lower cost routes to MMCs manufacturing;

All of these are embodied in the field of:

MMCs Future Innovation

many automotive companies environmentally friendly alternatives to materials for production

MESO/NANOSTRUCTURED COMPOSITES BASED ON

A. Tercjak, J. Gutierrez, I. Garcia and I. Mondragon*

In the present study, an amphiphilic diblock copolymer of poly(styrene-block-ethylene oxide),

nematic-isotropic (TN-TI) transition at about 76 ºC and a crystal-nematic (TC-TN) transition at

The morphological behaviour of both HOBC/PSEO and TTIP/PSEO systems was

Morphologies generated in 20 wt % HOBC/PSEO mesocomposite annealed at room

Figure 3. a) TM-AFM phase image for 20 wt % HOBC/PSEO mesocomposite annealed 12 h at room

Figure 4. TM-AFM phase image for 20 wt % HOBC/PSEO mesocomposite prepared by temperature

Monitoring of the changes of the morphology generated in 20 wt % HOBC/PSEO

Morphology generated in the 20 wt % TTIP/PSEO prepared via sol-gel synthesis was

Figure 5. a) TM-AFM phase image for 20 wt % TTIP/PSEO nanocomposite annealed 12 h at room

DURABILITY ASPECTS OF POLYMER

Effect of the Temperature and Thermal Cycles

Effect of Moisture and Liquid Water

The mechanical response of ambient cured E-glass/vinylester composite immersed in

Effect of Freeze and Freeze-Thaw Cycles

Effect of Aqueous Solutions and Chemicals

The performance of FRP strengthened structures in an alkaline or acid environment depends

containing microorganisms was reproduced by exposure of laminates to compost soil with

Another environmental factor giving rise to irreversible decay of some fiber-reinforced

Effect of Combined Agents

Effect of Natural Exposure

Referring to the effect of environmental agents on performance of composites, it is noted

attributed to plasticization and hydrolysis of the matrix resin caused by immersion in a

Many of the experiments on durability aspects are conducted according to standard

The answer is obviously: no!

Guo, S; Kagawa, Y. Temperature dependence of in situ constituent properties of polymer-

Lettieri, M. Epoxy adhesives and fiber-reinforced polymer composites for restoration of

Saadatmanesh, H; Tannous, F. Durability of FRP rebars and tendons. Non-Metallic (FRP)

SMART ADHESIVELY BONDED COMPOSITE

Jinquan Cheng*, Guoqiang Li and Su-Seng Pang

induced structural deformation by inherent sensitive electro-mechanical coupling effect; when

2. Smart Adhesively Bonded Beam-Like Joint

single-strap joint with the surface /internal bonded/integrated piezoelectric patches or

Adherends Adhesive layer

(b) Smart single-strap joint with surface

(c) Smart single-strap joint with surface

(d) Smart single-strap composite joint integrated with

2.1. Smart Adhesively Bonded Single-Lap Joint