CHAPTER-04

PROPERTIES OF POLYMER MATRIX NANOCOMPOSITES

This section of study will briefly discuss various properties of polymer nanocomposites

directly concerned with Aerospace applications. The properties of nanocomposites depend

on the following parameters [31]:

Process used in nanocomposite fabrication

Types of filler materials and their orientations

Degree of mixing of two phases

Type of adhesion at the matrix interface

Volume fraction of nanoparticles

Nanoparticle characteristics

Nature of the interphase developed at the matrix interface

Size and shape of nanofiller materials and

Morphology of the system

In order to achieve enhanced properties of nanocomposites, the nanosized particles

should be dispersed and distributed in the matrix material properly, otherwise there will be

agglomeration of particles and the properties of nanocomposites will deteriorate. These

aggregates will act as defects and limits the property enhancement of nanocomposite,

therefore to achieve maximum property enhancement, the nanoparticles should be

homogeneously dispersed in the matrix.

 Figure 4.1: Distribution and dispersion of nanoparticles in the matrix

Figure 4.1 shows different types of nanoparticles in the matrix material, (a) good

distribution but poor dispersion (b) poor distribution and poor dispersion, (c) poor

distribution but good dispersion, and (d) good distribution and good dispersion [20].

Impact resistance and energy absorption

Damage due to low- and high-velocity impact events weakens the structure of composite

materials due to a continuous service load. Furthermore, an impact may generate different types of

flaws before full perforation, i.e. sub-surface delamination, matrix cracks, fibre debonding or

fracture, indentation and barely visible impact damage (BVID). Over time, these effects can induce

variations in the mechanical properties of composite structures (the primary effect of a delamination

is to change the local value of the bending stiffness and the transverse-shear stiffness), leading to

possible catastrophic failure. It has been reported that the energy-absorption capability and related

properties of polymer matrices can be engineered by adding nanoscale fillers. For example, rigid

nano-sized particles such as SiO2 TiO2 , CaSiO4 , Al2O3 powder, CNTs and clay nanoplatelets can

be used.
 Figure 4.2: Damping material for an aircraft engine blade

Typical fillers for the reinforcement of polymer matrices are particles (e.g. silica or aluminium

oxide particles), tubes (e.g. nanofibres or nanotubes) and plates (e.g. nanoclay platelets). Significant

enhancement of the impact strength of polymeric nanocomposites has been achieved by adding

amino-functionalized MWCNTs or small amounts of single-walled carbon nanotube (SWCNTs).

The critical parts in aerospace vehicles depend on both the strength and toughness of the

materials they are made of, while the associated technology places strict limitations on the weight

of the different components. Notably, matrix toughening may be performed with the incorporation

of nanofillers in the polymer matrix material.

Thermal stability and fire retardancy

Due to degradation of polymer, the article becomes brittle and the life of the material becomes

limited. Thus, any polymer or its (nano)composite that is to be used in outdoor applications must be

highly resistant to all environmental conditions. Research indicates that the modified epoxy

nanocomposites possess better flame retardant properties than conventional composites. It has been

shown that carbon nanotubes can surpass nanoclays as effective flame-retardant additives if the

carbon-based nanoparticles (single- and multi-walled nanotubes as well as carbon nanofibres) form

a jammed network structure in the polymer matrix, so that the material as a whole behaves
rheologically like a gel.[76]. The thermal degradation of nanocomposites depends on clay loading,

structure and the nature of the ambient gas.

The clay acts as a heat barrier, which could enhance the overall thermal stability of the system

as well as assisting in the formation of char during thermal decomposition. Polymers that show

good fire retardancy on nanocomposite formation exhibit significant intermolecular reactions, such

as inter-chain aminolysis or acidolysis, radical recombination and hydrogen abstraction.

Figure 4.3: Barrier enhancement of nanocomposites

Clays are believed to increase the barrier properties by creating a maze or ‘tortuous path’

(Scheme 8) that retards the progress of the gas molecules through the matrix resin (Neilson, 1967).

For example, polyimide/layered silicate nanocomposites with a small fraction of O-MMT exhibited

reduction in the permeability of small gases, e.g. O2, H2O, He, CO2, and ethyl acetate vapors [Ray

and Okamoto, 2003].

Optical properties

Figure 4.4: Internal arrangement of a CNT based lighting element

The presence of reinforcement incorporation at nano-levels has been shown to have

significant effects on the transparency and haze characteristics of films. In comparison to

conventionally filled polymers, nanoclay incorporation has been shown to significantly enhance

transparency and reduce haze. With butyl rubber, polyamide and acrylic rubber based clay nano

composites, this effect has been shown to be due to modifications in the crystallization behavior

brought about by the nanoclay particles; spherullitic domain dimensions being considerably smaller.

Clays are just into thin, albeit their micro- lateral size. Thus, when single layers are dispersed in a

polymer matrix the resulting nanocomposite is optically clear in the visible region Non-linear optical

organic materials, such as porphyrins, dyes and phthalocyanines, have optical limiting properties,

which can be used to control light frequency and intensity in a predictable manner in photonic

devices. However, these are narrow-band optical materials.

The combination of the unique properties of CNTs with conducting organic polymers (e.g.,

polyaniline, polypyrrole, polythiophene, poly(3,4-ethylenedioxy thiophene), poly( p –phenylene

vinylene) and poly( m -phenylene vinylene- co -2,5-dioctoxy- p -phenylene)) makes these materials

interesting multifunctional systems with great potential in many applications such as super-
capacitors, sensors, advanced transistors, high-resolution printable conductors, electromagnetic

absorbers, photovoltaic cells, photodiodes and optical limiting devices.

Age and durability performance

The study of the degradation and stabilization of polymers is an extremely important area

from a scientific and industrial point of view and a better understanding of polymer degradation will

help to increase the life of a product. 99 Polymer degradation in broader terms includes

biodegradation, pyrolysis, oxidation, mechanical, photo- and catalytic degradation. Because of their

chemical structure, polymers are vulnerable to harmful effects in the environment. The effects of

hydrothermal aging on the thermo-mechanical properties of high- performance epoxy and its

nanocomposites have been reported in the literature.[28] It has been found that the storage modulus

and relaxation behaviour are strongly affected by water uptake, while fracture toughness and

Young’s modulus were less influenced. Becker et al. 102 found that the water uptake (in an aquatic

environment) was considerably reduced in epoxy nanocomposites with a particular clay loading

percentage. Organically modifi ed clay-reinforced PA-6 was subjected to accelerated heat aging to

estimate its long-term thermo-oxidative stability and useful lifetime compared with the virgin

material[29].