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Adhesion of polymers

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DOI: 10.1016/j.progpolymsci.2009.04.007

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Progress in Polymer Science 34 (2009) 948–968

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Adhesion of polymers
Firas Awaja a,∗ , Michael Gilbert b , Georgina Kelly a , Bronwyn Fox a , Paul J. Pigram b
a
Centre for Material and Fibre Innovation, Geelong Technology Precinct, Deakin University, Geelong, Victoria 3217, Australia
b
Centre for Materials and Surface Science and Department of Physics, La Trobe University, Victoria 3086, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Most industrially applied polymer resins and composites have low surface free energy and
Received 25 June 2008 lack polar functional groups on their surface, resulting in inherently poor adhesion proper-
Received in revised form 20 April 2009
ties. A strong research momentum to understand polymer adhesion in the last decade has
Accepted 27 April 2009
been motivated by the growing needs of the automotive and aerospace industries for better
Available online 28 May 2009
adhesion of components and surface coatings. This paper reviews the recent research efforts
on polymer adhesion with a special focus on adhesion mechanisms. It starts with an intro-
Keywords:
Adhesion duction to adhesion with explanatory notes on adhesion phenomena. Recent research on
Polymer the adhesion mechanisms of mechanical coupling, chemical bonding and thermodynamic
Thermodynamic adhesion is then discussed. The area of adhesion promoters is reviewed with the focus on
Diffusion plasma and chemical treatments, along with direct methods for adhesion measurement. The
Molecular bonding topics of polymer blends and reactive polymerization are considered and the interactions
Plasma with adhesion mechanisms are reported. The concluding section provides recommenda-
Blends tions regarding future research on the contentious aspects of currently accepted adhesion
mechanisms and on strategies for enhancing polymer adhesion strength.
© 2009 Elsevier Ltd. All rights reserved.

Contents

1. Introduction to adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 949

1.1. Adhesion phenomena . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 949
1.2. Adhesion of polymer systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 949
1.3. Surface characterization techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.1. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.2. X-ray photoelectron spectroscopy (XPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.3. Atomic force microscopy (AFM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.4. Scanning electron microscopy (SEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.5. Optical contact angle analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950
1.3.6. Attenuated total reflectance infrared spectroscopy (ATR-IR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
2. Adhesion mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
2.1. Mechanical coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
2.1.1. Support for the mechanical interlocking mechanism of adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
2.1.2. Debate opposing the mechanical interlocking mechanism of adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952
2.2. Molecular bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 952

∗ Corresponding author. Current address: School of Physics, University of Sydney, NSW 2006, Australia. Fax: +61 2 90367158.
E-mail address: firas@physics.usyd.edu.au (F. Awaja).

0079-6700/$ – see front matter © 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2009.04.007
 Author's personal copy

F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968 949

2.3. Thermodynamic mechanism of adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953

2.3.1. Surface tension theories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 954
2.3.2. Applications for the thermodynamic mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955
2.4. Other adhesion mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3. Adhesion promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3.1. Chemical treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3.2. Plasma treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957
3.3. Other treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958
4. Direct adhesion measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 959
4.1. Peel tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 959
4.2. Lap shear tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 960
4.3. Pull out test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961
4.4. Torque test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961
4.5. Scratch test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961
4.6. Stud/butt test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
5. Polymer blends and reactive polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963
5.1. Polymer blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963
5.2. Reactive polymers, adhesives and coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 963
6. Future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 964
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 965

1. Introduction to adhesion chemical groups at or near the interface [27]. A common

example of an adhesive system found in the automotive
1.1. Adhesion phenomena industry is the attachment of a paint coating to a poly-
mer bumper bar. Such bumper bars are frequently made
Adhesion is the interatomic and intermolecular inter- with polypropylene (PP); a material exhibiting poor sur-
action at the interface of two surfaces [1]. It is a face adhesive properties in its native state. Adhesion can
multi-disciplinary topic which includes surface chem- be improved by a number of strategies including adding an
istry, physics, rheology, polymer chemistry, stress analysis, adhesion promoter such as a chlorinated polyolefin (CPO)
polymer physics and fracture analysis. Describing the [28], flame treating the polypropylene compounds [27],
mechanism of adhesion in simple terms is difficult due to plasma treating the polypropylene to promote the creation
the complexity and evolving understanding of the subject of polar functional groups at the surface [29–34] or by
[2]. The ultimate goal is to identify a single mechanism blending in ethylene–propylene rubber (EPR) which in turn
that explains adhesion phenomena [3–10]. A range of adhe- forms a thermoplastic polyolefin (TPO) [35–38].
sion mechanisms, based variously on diffusion, mechanical, Other industries such as the building, engineering
molecular and chemical and thermodynamic adhesion and biomedical industries have also actively investigated
phenomena, are currently the subject of debate in the lit- polymer adhesion. The building industry is one of the
erature. This debate warrants their detailed explanation biggest users of polymers (for example, thermoplastic roof-
[2,6,11–15]. ing membranes and other polymer-based structures) and
Adhesion mechanisms have been known to be depen- polymer-based sealants. The major application of sealants
dant on the surface characteristics of the materials in is in circumstances where the sealing material requires
question since the early beginnings of both the aerospace the ability to withstand thermal expansion and contraction
and automobile industries. Since then, and especially in the and still bond to the substrate [26,39,40]. The engineering
last 30 years, the understanding of adhesion mechanisms industries have and are continuing to investigate polymer
has increased significantly as both industries have sought adhesion, especially with respect to polymer composites.
lighter and cheaper alternatives to metals and metal com- There have been many studies which have investigated the
ponents. This drive has been the major influence in the need surface properties of common polymers such as PP with
to understand polymer adhesion and to resolve the debate the aim of making the material more receptive to adhe-
over how the interfaces are actually adhering [11,15–19]. sives via improved wetting. One of the methods in common
use being to form a block copolymer with the non-polar
1.2. Adhesion of polymer systems substrate [41–44].
An understanding of adhesion mechanisms is of grow-
The automotive and aerospace industries have been ing importance in the biomedical field. For example, in
investigating adhesives and the associated adhesion mech- studies of the fracture of bonds between human hepatoma
anisms for more than 50 years. In recent times, the interest cell lines and polymers such as polystyrene, polymethyl-
from the sector in adhesion has been directed towards poly- methacrylate and polycarbonate [45–48]. It has been
mers and epoxy resins due to their advantageous bulk and shown that the dominant factor in cell adhesion to poly-
surface properties, low cost and good mechanical proper- mer substrates is the surface free energy of the polymer,
ties [20–26]. Adhesion between the polymer surface and irrespective of whether the surface has been covered by a
the paint substrate layer, for example, is controlled by the protein layer [48,49].
 Author's personal copy
950 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
1.3. Surface characterization techniques
Any consideration of adhesion mechanisms requires
information about the physical and chemical properties
of the adhering surfaces and the delamination surfaces in
cases where adhesion has failed in use or as a result of
mechanical testing. There are a number of surface charac-
terization techniques utilized for investigating properties
related to adhesion mechanisms and adhesion strength.
These include time-of-flight secondary ion mass spec-
trometry (ToF-SIMS), X-ray photoelectron spectroscopy
(XPS), atomic force microscopy (AFM), secondary electron
microscopy (SEM), attenuated total reflectance infrared
spectroscopy (ATR-IR) and other microscopy techniques
plus methods sensitive to surface energy such as opti-
cal contact angle analysis. There have been numerous
studies which have looked at surface properties such as
roughness, polarity, chemical composition and surface free
energy to describe and explain adhesion phenomena at
a surface or interface using the above mentioned tech-
niques [2,12,23–25,27,50–57]. Brief descriptions of these
techniques are included below.
1.3.1. Time-of-flight secondary ion mass spectrometry
(ToF-SIMS)
ToF-SIMS instruments generate surface mass spectra
under clean ultrahigh vacuum conditions. A pulsed, highly
focused primary ion beam is directed at the surface causing
the emission of secondary charged and neutral fragments
from the surface and near-surface region. The primary ion
source was formerly monoisotopic Ga but contemporary
instruments typically use Bi cluster ion sources or C60 ion
sources for superior mass range and spectral yield. Posi-
tively or negatively charged secondary ions within a narrow
energy band are extracted from the surface region and mass
analysed using a time-of-flight analyzer. The resulting mass
spectrum plots secondary ion intensity as a function of
mass/charge ratio. ToF-SIMS provides elemental, isotopic
and molecular information at extremely high surface sen-
sitivity (monolayer) [58,59]. This molecular information
provides the chemistry at the interface, allowing for molec-
ular insight into the adhesive reaction. The theory and
experimental description of the technique and examples
of data are reported elsewhere in detail [58].
1.3.2. X-ray photoelectron spectroscopy (XPS)
XPS is surface sensitive analytical technique with a
depth of analysis of the order of 5–10 nm. As with ToF-
SIMS, this surface sensitivity requires that XPS instruments
operate ideally at ultrahigh vacuum to minimize undesir-
able surface contamination. X-ray photons (generally in
range 100–2500 eV), derived from monochromated labo-
ratory X-ray sources or soft X-ray synchrotron beam lines,
irradiate the sample surface and cause the emission of
photoelectrons from the near surface region. The kinetic
energy of these electrons is determined, typically using
a hemispherical sector analyzer, and the corresponding
electron binding energy calculated. The spectra produced
show photoelectron intensity as a function of binding
energy, mapping out the electronic structure of the par-
ent atoms. Characteristic peaks in the spectra correspond
to the electronic core levels in the atoms in the near sur-
face region and can be used to identify the species present
and quantify the relative surface composition. Chemical
shifts and curve fitting of peak envelopes with multiple
contributions allows the chemical state of surface species
to be identified, for example, the oxidation state or bond-
ing environment. XPS is an information-rich technique
which provides both qualitative and quantitative elemen-
tal information for all elements apart from H and He [59].
The elemental information along with the bonding states
allow for the chemistry at the adhesive interface to be
understood. XPS also facilitates quantitative correlations
between elemental and functional groups present on the
surface and surface energy or adhesion strength. XPS oper-
ating principles are explained in detail in a variety of
published works [58–60].
1.3.3. Atomic force microscopy (AFM)
Atomic force microscopy (AFM), or more generally scan-
ning probe microscopy (SPM), is a group of contemporary
microscopy techniques that find wide application in the
physical, chemical and biological sciences. These tech-
niques are characterized by the use of a very finely pointed
probe attached to a cantilever to interrogate the sample sur-
face via raster scanning or via point-wise measurements of
probe–surface interactions, for example molecular forces
associated with chemical bonding. Scans are collected with
the probe in contact with the surface, with the probe close
proximity to but not in contact with the surface, with the
cantilever vertically at rest or oscillating at high frequency,
and with probes fabricated from a wide variety of materials,
with test molecules attached, and with insulating or met-
allised probe surface finish. AFM is widely used to generate
topographic maps of surfaces, whereby cantilever deflec-
tions arising from the interaction with surface features are
recorded as a function of raster position. AFM is able to
achieve atomic resolution in the vertical plane and 0.01 nm
spatial resolution in the horizontal plane [59]. This resolu-
tion allows for the detection of changes to topography after
surface treatment, and can be measured through roughness
values, providing valuable information on contribution of
surface roughness to adhesion strength.
1.3.4. Scanning electron microscopy (SEM)
Scanning electron microscopy (SEM) is a well known
electron beam technique in which electron scattering is
used to image the topography of the sample surface under
investigation. The electron beam is rastered across the sam-
ple surface (which must be conductive or rendered so
by coating) with the signal from the emitted secondary
electrons displayed via an electron detector. SEM has the
potential to generate images with a few nanometers spa-
tial resolution, and has a relatively large depth of field,
in some cases up to 100 times that of an optical micro-
scope [61]. This provides topographical information on the
sample surface allowing for greater understanding of the
reaction between surface treatment and substrate.
1.3.5. Optical contact angle analysis
Optical contact angle analysis (OCA) is a surface sen-
sitive technique which allows the wetting properties and
 Author's personal copy
F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
surface energy of the investigated sample to be measured.
In general, a polar and non-polar liquid are dispensed onto
the sample surface with the angle that the liquid makes
with the surface (as measured through the liquid) being
recorded. Smaller contact angles indicate a more wetting
surface with a higher surface energy and therefore a greater
work of adhesion [62]. As surface energy and wettability
are related to adhesion, OCA provides an indirect measure
of adhesion, allowing for the comparison between the work
of adhesion and direct adhesion methods.
1.3.6. Attenuated total reflectance infrared spectroscopy
(ATR-IR)
ATR-IR is conducted by passing infrared radiation into an
infrared transmitting crystal to achieve multiple reflections
between the ATR crystal and the surface under investiga-
tion. The increased spectral sensitivity and reduced depth
of analysis achieved in ATR-IR is used for surface molecular
characterization. For example, it has been used to detect
chemical bonds between proteins and nitrogen plasma
treated polypropylene (PP/N2 ). This bonding increased
adhesion between the (PP/N2 ) and the hybrid hydrogel [63].
ATR-IR has also been used to characterize improved adhe-
sion between polyethylene and a surface grafted acrylic
acid monomer (PE-g-AAc). This study concluded that cova-
lent bonds formed between carboxylic groups of grafted
polyacrylic acid and the hardener amine group improved
adhesion [64]. Similarly, after glow discharge treatment of
poly(vinylidene difluoride) ATR-IR provided information to
detect the formation of oxygen-containing species on the
polymer surface [65].
2. Adhesion mechanisms
The recent adhesion literature contains studies of three
main adhesion mechanisms: mechanical coupling, molec-
ular bonding, and thermodynamic adhesion. These are
considered in the following sections. A brief overview of the
electrical, rheological and weak boundary adhesion mech-
anisms is also presented.
2.1. Mechanical coupling
The mechanical coupling or interlocking (hook and eye)
adhesion mechanism is based on the adhesive keying into
the surface of the substrate [3,12,66]. This is similar to glue
on wood, in that the glue locks into the rough irregulari-
Fig. 1. Illustration of mechanical coupling between two substrates.
951
ties on the surface of the wood [12] Fig. 1 illustrates the
interlocking concept.
The current debate surrounding mechanical adhesion
concerns the significance of interlocking in explaining sur-
face adhesion. On one side of the argument, it is believed
that mechanical interlocking provides higher adhesion
strength. Other researchers believe that roughening of the
surface is simply increasing the surface area for more
molecular bonding interactions [54,67]. In the following
section, highlights from that debate are reported and prac-
tical examples are presented.
2.1.1. Support for the mechanical interlocking mechanism
of adhesion
A series of studies have been published discussing the
mechanical interlocking adhesion mechanism. It has been
observed, for example, that abrasive treatment of smooth
solid surfaces in the presence of an adhesive may increase
the strength of the adhesive joint [54,68]. However, the
destruction of the surface may allow for the formation of
macro-radicals, and hence an increase in chemical bonding
sites [54].
A common system found in the automotive industry is
the application of a paint coating to a thermoplastic poly-
olefin (TPO). Ryntz [69] demonstrated that the addition
of an adhesion promoter such as a chlorinated polyolefin
(CPO) can increase the adhesion at the paint–polymer inter-
face due to the mechanical interlocking of the substrate to
the adhesion promoter. Furthermore, Morris et al. [36,70]
investigated the distribution of CPO in a TPO system and
showed that the adhesion mechanism was due to inter-
chain entanglement and not chemical bonding. Delrio et
al. [71] considered van der Waals forces in the adhesion
between micromachined surfaces—in particular polysili-
con micromachined surfaces, but found that adhesion is
primarily dependant on the forces in the transition region
between the non-contacting areas.
The biomedical industry, and more importantly the
biomaterials sector, covers a range fields including tis-
sue engineering, biosensors and biochips and medical
implants. There has been a focus on surface engineering
of polymer materials in order to promote cell adhesion as
well as maintaining cell functionality [72–74]. This industry
has committed substantial effort to investigating polymer
adhesion and has provided support for the mechanical
adhesion theory. In recent investigations of high density
polyethylene (HDPE) composites with particulate hydrox-
yapatite (HA) it was found that adhesion is primarily due to
mechanical coupling [75]. Other work has considered the
importance of fibronectin (Fn), an adhesive protein found
in blood and cell surfaces, in tissue engineering. In a study
by Yamamoto et al. [76] it was discovered that Fn adhered
via mechanical interlocking to the substrate, thus shedding
light on the critical effect that the cell adhesive proteins
play in cell behavior. However, there is still a substantial
need, as noted by Lussi et al. [77], to understand the molec-
ular links between proteins such as fibronectin and the
cytoskeleton elements on a cellular level.
Recently, wood-fibre reinforced thermoplastic compos-
ites have been more widely used in many housing appli-
cations such as decking due to cost and weight advantages
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952 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
in comparison with conventional timber products [78]. The
main concern in a system of wood and polymer is the lack of
adhesion between the generally hydrophobic polymer and
the hydrophilic wood surfaces. Gupta et al. [79] discovered
while investigating the adhesion mechanism(s) underly-
ing wood fibre reinforced thermoplastic composites that
although polar interactions played a part in adhesion, it was
the surface roughness and in turn mechanical interlock-
ing of the substrates which allowed for the optimization
of adhesion. This was only possible through the introduc-
tion of an impact modifier at the interface of polypropylene
and the wood composite, as the introduction of wood alone
actually decreases the mechanical strength [80]. Toro et
al. [81] took this approach further in a study looking at
the effect of silica filler particles in a polypropylene-co-
polyethylene composite, reporting that not only was the
presence of a filler required for better interfacial adhesion
but the filler particle size and distribution was decisive. This
result was supported by Crespo et al. [82] who investigated
a series of natural fillers such as sawdust, rice and almond
husk with vinyl plastisols (PVC polymer matrix).
2.1.2. Debate opposing the mechanical interlocking
mechanism of adhesion
Many researchers have noted the significance of
mechanical interlocking in explaining adhesion phenom-
ena but in combination with other forces. Adhesion
between surfaces is influenced by the presence of van der
Waals forces in addition to mechanical coupling, but it was
noted that these forces are not sufficient to create the strong
interfacial bonding observed between polymers [6]. Simi-
larly, Wake [12] demonstrated in an experiment studying
the adhesion of rubber and textiles that the intrinsic adhe-
sion between fibre and rubber arises from primary forces,
chemical or van der Waals forces. In order to maximise
adhesion it was found that the fibre needed to be embedded
before the interfacial shear strength exceeded the tensile
strength [83]. In a study looking at the microstructure of
grafted polymer (polypropylene) chains Wang [84] found
that adhesion was proportional to grafting density, and
that long, less branched chains were critical in maximis-
ing adhesion. Wang and Bonfield [85] went on to study
the chemical treatment of the interface of hydroxyapatite-
high density polyethylene HA-HDPE, which resulted in
an increase in ductility, tensile strength and adhesion.
Wang [84] attributed this increase in adhesion not only to
mechanical coupling but also to the formation of chemi-
cal bonds at the interface. Tang and Martin [37] found that
adhesion between TPO and CPO was not due to inter-chain
entanglement but in fact due to diffusion of the CPO into
the TPO system.
Other school of thought suggests that the increase in
adhesive bonding is predominantly due to chemical bond-
ing and not mechanical destruction itself [54,67]. This
conclusion was reached when polymers were abrasively
treated in air and then had an adhesive coating applied
which resulted in lower adhesive strength than when the
polymers were abrasively treated in the presence of the
adhesive [54]. Vasconcelos et al. [67] studied the phase
matrix interface of aluminum-filled epoxies, showing that
the adhesion mechanism between the aluminum particles
and the epoxy matrix is dependant not only on physical and
mechanical interactions but also on chemical interactions
at the interface. Higher interfacial strength was found to
be associated with an increase in the nitrogen species from
the resin interacting with the oxidised aluminium particles
[67]. Clean surfaces are known to provide strong adhesive
bonds, whereas contaminants such as oil and greases can
form weak boundary layers at the interface causing poor
adhesion [86]. Contaminant removal as a result is impor-
tant to achieve high adhesion strength [87], although it
should be noted that acrylic adhesives are able to dissolve
oils and greases [86].
2.2. Molecular bonding
Molecular bonding is the most widely accepted mecha-
nism for explaining adhesion between two surfaces in close
contact. It entails intermolecular forces between adhesive
and substrate such as dipole-dipole interactions, van der
Waals forces and chemical interactions (that is, ionic, cova-
lent and metallic bonding). This mechanism describes the
strength of the adhesive joints by interfacial forces and also
by the presence of polar groups [83]. Molecular bonding
mechanisms require an intimate contact between the two
substrates as shown in Fig. 2. However, intimate contact
alone is often insufficient for good adhesion at the inter-
face due to the presence of defects, cracks and air bubbles
[3].
The molecular bonding mechanism is not yet fully
understood and there have been many theories proposed
to explain it. Mutsuda and Komada [88] studied poly(oxy-
2,6-dimethyl-1,4-phenylene) (PPE) bonding to rubber and
reported that the adhesion mechanism was based on
a hydrogen abstraction reaction. This occurs when the
separation between two polymer substrates becomes neg-
ligible, allowing radicals from one substrate to attack the
other causing the formation of more radicals. Recombina-
tion of these radicals with the polymer allows for chemical
bonding between substrates [88]. Further evidence for this
hypothesis was seen in the XPS and ToF-SIMS work con-
ducted by other researchers [89,90]. It was shown that
interfacial bonding was the crucial factor in the adhesion
strength between silanes and metals [3,89,90].
Another theory is discussed in the review article writ-
ten by Basin [54] which considers adhesion between solid
substrates and organic coatings. Basin [54] reported that
as the number of chemical bonds increased at the contact
zone, adhesion strength passed through a maximum value.
Once the number of chemical bonds increased past this
value, the concentration of the mechanical stresses at the
interface led to a decrease in adhesion strength due to the
excessive increases in the size of the interfacial effect. This
finding is supported by the study investigating the shear
strength of aluminium–polypropylene lap joints by Chen
et al. [91]. They found that the overriding adhesive mecha-
nism was the chemical interaction between the functional
groups at the interface and also concluded that excessive
chemical bonding at the adhesive interface could have a
negative effect on the interface strength. Adhesion strength
has been shown to depend on the thickness of the adhesive
layer for composite interfaces. Interfacial bonding strength
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Fig. 2. Schematic of the molecular bonding between substrates.
increases as the thickness of the adhesive layer is reduced
as stress is able to dissipate through the interface with
greater ease [92]. The addition of adhesion promoters such
as silane at the interface for the maleic anhydride-grafted
polypropylene system resulted in improved mechanical
properties as well as improved adhesion performance [93].
For co-polymer systems, adhesion was found to be con-
trolled in part by the architecture of the copolymer and
in part by the stresses at the interface [94]. Laurens et al.
[94] discovered for optimum adhesion strength at the inter-
face of isotactic polypropylene (iPP)-polyamide 6 (PA6), the
copolymer should have a similar molecular architecture
and high molecular weight, allowing the stress to be trans-
ported far from the interface. They found that adhesion was
governed by molecular weight, crystalline structure at the
interface, annealing conditions and the molecular architec-
ture of the polymer [94]. This research is partly supported
by the work undertaken by Toro et al. [81]. They discovered
that for polypropylene-silica and polypropylene-rice husk
systems, adhesion was largely determined by the size and
distribution of the silica which acted as the filler agent in
PP-co-PE/silica composites [81]. Zhang et al. [44] also found
that adhesion was controlled by the architecture and the
amount of copolymer found at the interface and not by the
concentration of functional groups present in a polypropy-
lene (PP)/amorphous polyamide (aPA) system.
Polar adhesives have been used previously to change
the polarity in rubber systems [92,95]. It has been shown
that there is a parallel relationship between the hydrophilic
properties of the surface and its subsequent polarity
[92,95].
Hutchinson and Iglauer [26] studied tack and peel tests
of foam and sealants used in building construction. They
found no sign of interdiffusion or electrostatic interaction at
the adhesive interface while mechanical interlocking only
had a marginal role in the adhesive strength of the system.
The primary adhesive mechanism identified was chemical
bonding of the substrates at the interface [26].
The development of surface sensitive instruments that
can provide chemical information, such as XPS and ToF-
953
SIMS, contributed significantly to the understanding of
the chemical bonding mechanism. Combining these tech-
niques with adhesion strength tests, such as peel and pull
off tests, can generate accurate correlations between the
chemical composition of the surface and the surface adhe-
sion strength.
2.3. Thermodynamic mechanism of adhesion
A significant body of research has been reported consid-
ering the thermodynamic adsorption model of adhesion;
those advocating the model argue that the other mech-
anisms discussed above have only a marginal impact
[2,8,11,17,96–100]. The advantage of the thermodynamic
mechanism over the other mechanisms is that it does not
require a molecular interaction for good adhesion, only an
equilibrium process at the interface [13]. In neutral envi-
ronments such as air, the thermodynamics of the polymer
system will attempt to minimize the surface free energy
by orientating the surface into the non-polar region of the
polymer [2]. When the polymer surface is in contact with a
polar substance such as water, good adhesion requires that
the interfacial tension be minimized [2]. Feinerman et al.
[101] showed that there are three zones for liquids inter-
acting with polymers and that the surface tension of the
solid is a function of the surface tension of the liquid. Zone
1 is the unperturbed zone; this indicates that the surface
tension of a polymer is independent of the surface tension
of the wetting liquid. There is a linear dependence between
the surface tension of the polymer and the surface tension
of the liquid in the other two zones, termed the depolar-
isation zone (polymer surface tension is lower than the
unperturbed zone), and the additional polarisation zone
(polymer surface tension is higher than in the unperturbed
zone) [101].
In 1855, Young considered a liquid of known surface
tension  L in contact with a simple solid, smooth, homoge-
neous, non-deformable and isotropic surface. The strength
of adhesion for a simple system like the one displayed in
Fig. 3 may be estimated through the work of adhesion (Wa )
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954 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968

employs an equation of state such that surface energy may

be calculated using only one contact angle measurement
[23,105,107,108]. The following sections describe the details
of the theories and the differences between them.

2.3.1.1. Fowkes theory. This method was introduced by

Fowkes in 1962 and has been discussed widely in the lit-
erature [8,48,66,108–112]. Fowkes divided the surface free
energy into two parts, the dispersive component contain-
ing all the London forces such as dispersion (London–van
Fig. 3. Sessile drop on a surface indicating the contact angle and surface der Waals), orientation (Keesom–van der Waals), induction
tensions for the three media respectively. Reproduced with permission
from ref. [3] (Springer, 1980).
(Debye–van der Waals) and Lifshitz–van der Waals (LW)
forces, and the polar component which consists of hydro-
which is defined as gen bonding (acid/base) components.
The total surface tension is defined as
Wa = S + L − SL (1)
p
itot = id + i (4)
where  S ,  L ,  SL represent the tensions of the solid/air,
liquid/air and solid/liquid interfaces respectively. The chal- p
where (id ) is the dispersion component and (i ) is the
lenge with this equation is that only  L can be measured polar component. As Fowkes considered only the disper-
with confidence as the surface tension of the solid can only sion force interaction at the solid liquid interface, Eq. (4)
be experimentally determined against a series of known can be further developed by taking into account the geo-
liquids. metric mean of the dispersion components of both liquids,
Young [102] qualitatively described a relationship resulting in Eq. (5)
between these tensions, which may be stated algebraically 
as: SL = S + L − 2 Sd Ld (Fowkes equation) (5)
L cos  = S − SL (2)
Substituting Young’s equation, Fowke’s equation
Eq. (2) is commonly referred to as Young’s equation. In becomes
1869, Dupré [103] defined work of adhesion (Wa ) leading 
to the equation: L (1 + cos ) = 2 Sd Ld (6)
Wa = L (1 + cos ) (3)
This equation when applied to calculating surface free
Eq. (3) may be derived from Eqs. (1) and (2) by sub- energies only takes into account the dispersive interactions
stitution. Adamson outlines the origin and relationship of the system and as such is not reliable for calculations of
between these equations and comments that Eqs. (2) and complex systems. However, for simple systems its applica-
(3) are often both referred to as the Young-Dupré equation tion can provide useful approximations [48].
[95,104]. Eq. (3) provides a simple formula for Wa in terms
of the measurable contact angle and the known surface
2.3.1.2. Geometric mean theory. The geometric mean
tension of the test liquid.
approach is an extension of Fowkes’ models in that the
In a real system, however, macroscopic surface rough-
polar (hydrogen bonding) term is also considered. This
ness and surface chemical heterogeneity (non-uniform
theory is also known as OWRK after its originators Owens,
surface chemistry) may give rise to contact angle hystere-
Wendt, Rabel and Kaelble [48]. They used the geometric
sis; the advancing contact angle measured as the test fluid
mean to combine the polar and dispersive components
expands the sessile drop and advances of over new surface
together as shown in Eq. (7).
area is greater than the receding contact angle measured as
 
the sessile drop retreats. This behaviour introduces a mea- p p
SL = S + L − 2 Sd Ld − 2 S L (7)
sure of ambiguity in the determination of contact angle and
is a source of conjecture in the application of Eqs. (2) and
Combining Eq. (7) with Young’s equation generates the fol-
(3) [23,105,106]. Nevertheless, many theories have been
lowing geometric mean equation
introduced to describe and measure the surface tension
of materials with applications to polymer systems and are  
p p
described below. L (1 + cos ) = 2 Sd Ld +2 S L (8)

2.3.1. Surface tension theories
Consideration of the sample surface energy is a consid-
eration of sample surface tension and there are two main
approaches reported. First approach is the components
approach, whereby the surface tension is considered to be
a combination of dispersion forces (van der Waals forces)
and polar forces (hydrogen bonding). The second approach
Due to the presence of the polar term, the minimum
number of liquids required to calculate the solid surface
components is two, of known surface tension [13,23,113].
2.3.1.3. Wu harmonic mean theory. Wu started similarly to
Owens and Wendt in that he also approached Fowkes’ the-
ory and introduced the polar component; however, rather
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968 955

than a geometric mean approach he used an harmonic Based on the work of Kwok and Neumann [122], the
mean as shown in Eq. (9) [114,115]: equation of state for a solid–liquid interface may be written
p p as
4Sd Ld 4S L 
SL = S + L − − p p. (9) SL = S + L − 2 S L eˇ(S −L )
2
(16)
Sd + Ld S + L
where ˇ is a constant of the interfacial system. Combin-
Substituting with the Young equation provides the fol-
ing the above relationship with Young’s equation generates
lowing:
equation (Eq. (17)) which contains both the contact angle
p p
4Sd Ld 4S L and the interfacial tensions for both liquids and solids. This
L (1 + cos ) = + p p (10)
Sd + Ld S + L allows the constant ˇ and the surface tensions to be calcu-
lated.
The similarity between Eq. (9) and OWRK theory (Eq.  2
(10)) is that contact angle data for a minimum of two known L (1 + cos ) = 2 S L eˇ(S −L ) (17)
liquids are required to calculate the surface energies for the In recent years Kwok and Neumann [123] modified Eq.
solids, but that one liquid must be polar and the other is (17), generating a revised equation of state for solid–liquid
non-polar [48,114]. interfaces:

2.3.1.4. Acid–base theory. The acid–base theory has L (1 + cos ) = 2 S L [1 − ˇ1 (S − L )2 ] (18)
received significant support from many researchers where the solid surface free energy can be calculated using
[108,116,117]. This approach was first developed by van a contact angle measurement and the surface tension for a
Oss, Chaudhury and Good [3] as they tried to relate the sur- known liquid [48,99,105].
face tension components more closely with their chemical Comparison between the final mathematical represen-
nature. Instead of the polar component (hydrogen bond tations of each of the thermodynamic theories is presented
p
component) being described as i it was now describes in (Table 1) and briefly discussed below.
AB
as  , where AB refers to the acid–base interactions. The A major work undertaken by Della Volpe et al. [108]
non-polar (dispersion) term was described as id ; this was has compared the two main theories of thermodynamics
changed to  LW where LW describes all the London–van as they apply to surface free energy. Here they compare
der Waals forces. the Surface Tension Component acid–base (STC) with the
Thus the surface tension could be described as equation of state (EQS) theory and find that STC provides
a better understanding of the molecular interactions at
 =  LW +  AB (11) the surface [108]. Moreover their work illustrates good
As the polar term was redefined to take into account the agreement between the acid–base approach and the work
acid–base interactions, the term  AB is a combination of of adhesion data that was collected as well as correctly
contributions from electron donors ␥− and electron accep- predicting the liquid–liquid interfacial tensions. However,
tors ␥+ . The sum of the acid–base components can then be it was concluded that in many cases where the Zisman
redefined as approximation and the EQS models provide acceptable fit-
 tings they ignore contributions to surface tension, primarily
 AB = 2  + − (12) effects of spreading pressure [108,124].
The interfacial tension between the solid and liquid
interface can then be defined by: 2.3.2. Applications for the thermodynamic mechanism
   Many interesting phenomena have been revealed by
SL = S +L −2 SLW LLW − 2 S+ L− − 2 S− L+ . (13) researchers during the investigation of the thermodynamic
mechanism and theories of adhesion. In the following sec-
Combining this equation with Young’s equation gives: tion, some examples are presented. A lap shear tensile test
   was used in experimental work reported by Bhowmik et al.
L (1 + cos ) = 2 SLW LLW + 2 S+ L− + 2 S− L+ (14) [125] to measure adhesion of polymer to polymer and poly-
mer to steel systems and showed that the surface energy
As there are now three terms relating to the of the polymer increased with increasing glow discharge
solid surface, three known liquids are used for con- power. The adhesion strengths at the interface passed
tact angle measurements, two of which must be polar through a maximum value before decreasing [125]. Tavana
[8,23,48,71,118–121]. and Neumann [107] showed in an in-depth paper investi-
gating contact angles for a series of materials that as the
2.3.1.5. Equation of state. The Equation of State (EQS) for liquid surface tension increase, the predictions for contact
interfacial tensions has its origins in Young’s equation. It is angles given by the geometric mean models deviated signif-
then combined with a relation of the form icantly from the experimental results. They found that the
exponential term in the equation of state model remedied
SL = f (sv , lv ) (15)
this problem and provided a good fit to the experimental
which allows for the formation of two equations as a func- data [107]. Della Volpe et al. [108], in their investigation of
tion of the two unknowns sv (interfacial tension between polymer contact angles, showed that the results obtained
solid and vapor) and lv , (interfacial tension between the by both the equation of state and the multi-component
liquid and vapor). theory were very close [108]. Brockmann and Huther [25]
 Author's personal copy
956 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Table 1
Summary of the mathematical representations of the different thermodynamic theories on adhesion.
Theory Mathematical representation
Young  L cos  =  S –  SL

Fowkes L (1 + cos ) = 2 Sd Ld
 
Geometric mean L (1 + cos ) = 2 Sd Ld +2
p p
4 d  d 4 
Wu harmonic mean L (1 + cos ) = S L
+ p
S L
p [48,114]
 d + d  +
L
S S L
 
Acid–base L (1 + cos ) = 2 SLW LLW + 2
√ 2
Equation of state L (1 + cos ) = 2 S L [1 − ˇ1 (S − L ) ]
have stated that the calculations of work of adhesion based
on surface free energies, although helpful in explaining
bond formation and adhesion strength are not applicable
to describing the durability of adhesively bonded joints.
Adhesion strength is also highly influenced by the inter-
nal stresses of the system [54]. The internal stresses are
dependent on the rate of the relaxation processes which
occur during the formation of the polymeric coatings. It
is also closely related to the rheological mechanism of
adhesion. Internal stresses are due to many factors such
as incomplete relaxation processes, unevenness of curing
in the coatings themselves due to the different rates of
polymerization, interactions with the solid surface and/or
filler, or the presence of a temperature gradient [126]. The
work carried out by Zubov et al. [54,127,128] has shown
that by using thixotropic effects during the formation of the
polymer coatings, internal stresses can be minimized caus-
ing adhesion strength to increase. In an adhesive strength
investigation of tungsten carbide–cobalt (WC–Co) inter-
faces, Watanabe et al. [129] have found that one of the key
factors for high quality adhesion was the energy dissipation
mechanism in the system.
2.4. Other adhesion mechanisms
The electrical adhesion mechanism is based on the
two materials joining at the interface having two differ-
ent band structures such that at contact there is a mutual
sharing of electrons [3]. The rheological mechanism of
adhesion has been well studied with focus primarily on
polymer–polymer systems. This theory requires that adhe-
sion occurs due to the interpenetration of substrates across
an interface. Heating the polymers above their glass tran-
sition temperatures increases the polymer chain mobility
allowing formation of a strong adhesive bond. Lenhart and
Cole studied the adhesion properties of polymer gels find-
ing that solvents in the elastomer can actually degrade
adhesion strength [130]. Hydrogen bonding structure and
the presence of entanglements at the interface also deter-
mine the stress characteristics of polymer–polymer blends
[131]. The theory of weak boundary layers is important as
it was initially thought that the interface between adhesive
and substrate would not fail, but that failure was due to the
formation of a weak boundary layer. This has been rebut-
ted vigorously as real adhesives are generally polymeric and
that the interface contains chain entanglements and cross
links, resulting in a much greater force being required for
References
[13,26,41,48,97,105,107,110,122,123,236–238]
[6,13,71,239]
p p
S L [13,23,113]
S+ L− + 2 S− L+ [8,23,48,71,118–121]
[48,99,105]
interfacial failure [3,13]. Although recently it must be noted
that surface morphology including plasma treatment can
often degrade polymeric substrates, causing the formation
of a weak boundary layer [132,133].
3. Adhesion promoters
Adhesion promoters with a variety of functional mech-
anisms have been introduced in industry and academia to
provide solutions for poor polymer adhesion. In this work,
we focus on chemical and plasma treatments of polymer
surfaces for adhesion promotion.
3.1. Chemical treatments
Chemical treatments of surfaces aim to create new
chemical/functional groups at the interface of the two
materials undergoing adhesion. Surface treatment of
polymers, especially rubber (both vulcanized and non-
vulcanized) by chemical modification with reagents such
as acids and oxidisers has been extensively investigated
and it has been shown that the treatments increase the
surface polarity. The increase in surface polarity causes an
increase in molecular forces between substrates and hence
an increase in adhesion strength [96–98,134]. Solvent-
based primers such as toluene and xylene have been
used as pretreatments to enhance adhesion of polymers,
despite the fact that the byproducts are a chemical hazard
[135,136]. Another consideration is the possibility that sol-
vents might induce molecular changes at surfaces that favor
stronger adhesion. XPS studies [137] have shown that the
surface of polyurethane undergoes rearrangements when
the surface environment is changed from air to water.
This rearrangement can be stimulated by submersing the
polyurethane in a suitable organic solvent, increasing the
mobility of the molecular chains near the surface [137].
Consequently, the formation of polar groups on the sur-
face of the polyurethane is enhanced. There have been
studies examining a range of liquids on the surface of
poly(tetrafluoroethylene) PTFE. It was concluded that there
is a complicated relationship between the surface tension
of a solid polymer to the surface tension of the wetting
liquid [101].
CPO is widely used primer in industry especially in the
manufacturing of automotive bumper bars and fascia. CPO
is formulated for application by dissolving the polymer in a
mixture of organic solvents such as toluene and xylene [34]
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
and then spray coated onto the surface of TPO to improve
the adhesive qualities of the system [36,70]. Quantitative
monitoring of CPO in terms of thickness, uniformity and
most importantly adhesion, is generally performed by dye
tagging the CPO and undertaking real time macroscopic
image analysis of the work object [28,70]. Raman chem-
ical imaging has been used as a non-invasive means of
characterizing the TPO substrate, in particular, visualiza-
tion of the bulk distribution of CPO, polypropylene and
ethylene–propylene rubber phases [36]. Lipatov [13] noted
that for adhesion and adhesion promotion between a poly-
mer and an organic surface, organosilanes were widely
employed due to their propensity to interact with hydroxyl
and other functional groups. Solvents also might provide a
cleansing effect on the treated surfaces. A film of oxide or
of organic contamination may greatly reduce the adhesion
performance of a given system [11].
In an investigation based on the controlled sur-
face modification of styrene-4-vinyl pyridene (SVP) and
ethylene-acrylic acid (EAA) with non-orientating (n-
alkane) and orientating (water) fluids, it was noticed that
few polar elements are needed to migrate into the sur-
face region to maximise bond strength. This conclusion
was based on the fact that surface reconstruction had little
effect on the adhesion properties of the non-polar sub-
strates [2].
Recently, PMMA (mixed with p-xylene) was used as a
swelling agent on ultrahigh molecular weight polyethylene
(UHMWPE) to improve its wettability. It was found that the
improvements were comparable to those reported by acid
etching and plasma treatment [138]. PMMA has also been
treated by a biomimetric process and soaked in hydrochlo-
ric acid solution which caused the formation of highly polar
carboxyl groups, resulting in an increase of a factor of two in
the adhesive strength when compared to the non-treated
samples [56]. Another study found that water modification
of PMMA substrates increased the surface polar component
more than other methods such as chemical treatment, gold
deposition and flaming [139].
Beholz et al. [5] reported that the immersion of HDPE
in sodium hypochlorite mixed with an acid increased
surface adhesiveness. They used XPS to show that chlo-
rine atoms had been added to the surface. The surface
of Poly(p-phenylene sulfide) (PPS) has been modified via
the introduction of polar groups through a combination
of chemical oxidation and plasma treatments. The surface
treatments were characterized using FTIR spectroscopy,
XPS and contact angle measurements. It was concluded
that the increase in adhesion was due to two factors, the
increased polarity due to the surface treatments and an
increase in surface roughness due to the surface modifica-
tion as measured by AFM (especially for surfaces treated
with chromosulfuric acid) [140]. Many researchers have
stated that chemical modifications of polymeric surfaces
are not suitable due to environmental and cost aspects asso-
ciated with this form of treatment [133,141,142].
3.2. Plasma treatments
Plasma treatments are a very effective way of increas-
ing the inherently poor surface properties of polymers,
957
and only short plasma treatment times are required to
increase the bond strength between two substrates. This
form of surface treatment allows for modification or tailor-
ing of surface properties without changing the overall bulk
properties of the polymer and is generally environmen-
tally friendly. Plasma treatment of surfaces often induces
the formation of oxygen-containing functional groups such
as hydroxyl groups, resulting in increased surface wet-
ting and improved adhesion [143–145]. Functional groups
reported to aid adhesion at the surface of polymers such
as PP include C O, in particular, but also CO, COO, OH and
OOH [134,146]. Uptake of environmental contaminants,
re-orientation of surface groups and further chemical reac-
tions at the surface with time, in many cases, result in an
“ageing” effect. Surface hydrophobicity is recovered with
time. This is a very serious issue in industry where sur-
face treated films may be stored prior to further coating.
Ageing effects introduce an element of uncertainty into the
long-term storage of surface treated films.
There are many plasma treatment methods and tech-
niques that have been investigated to enhance polymer
surface adhesion. Plasma treatment of the polymer sur-
face and then adjusting parameters such as gas flow, power,
pressure and treatment time allows for many refinements
to be made to the surface without changing the bulk prop-
erties [33,147]. Variables in plasma treatments such as
gas composition and plasma conditions determine how
ions, electrons, fast neutrals and radicals affect the etch-
ing, activation and cross linking between polymer surfaces
[33]. Plasma polymerization is used to create highly adher-
ent thin polymer films on the surface, allowing adhesion
between two surfaces which would not otherwise adhere
[148].
It has been shown that a short plasma pretreatment
of the surface of PP (in some cases less than 6 s) can
result in a higher bond strength than that achieved
when a primer pretreatment is used in the same cir-
cumstances [133,149]. As a result air, oxygen, nitrogen,
microwave and direct current (DC) plasma treatments are
being more widely used to increase adhesion through sur-
face oxidation [29,30,32–34,133,134,136,145,146,150–159].
Long-term plasma exposure causes formation of weak
boundary layers, causing the splitting of CH3 groups from
the tertiary C atoms, and can also cause inner chain scis-
sions, whereas short time exposure will only cause outer
chain scissions [33,133]. Non-equilibrium low-temperature
plasmas have been used to enhance the adhesive proper-
ties of the surfaces of reinforcing materials in polymers
[4].
Surface modification experiments using plasma treat-
ment require low pressures which in turn require costly
vacuum systems. New techniques involving atmospheric
pressure plasmas have been introduced to modify the sur-
faces of polymers and polymer blends. Massines et al. [160]
used atmospheric pressure glow discharge plasma success-
fully to deposit silane groups on the surface of PP films as
a method of enhancing the film surface properties. Simi-
larly, Guimond et al. [152] used atmospheric pressure glow
discharge plasmas (air corona and nitrogen) to modify the
surface properties of PP films. They found that nitrogen
increased the surface energy of the substrate to a greater
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958 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
extent due to the added presence of amine, amide and
hydroxyl functional groups.
Studies using a combination of surface analytical tech-
niques such as XPS, AFM, SIMS and optical contact angle
analysis have shown that low pressure treatment or atmo-
spheric pressure treatment results in surface properties
favoring strong adhesion [31,134,136,147,149,154]. Kwon et
al. [134] investigated plasma modified PP and found that
the maximum surface energy was achieved with a plasma
treatment time of 90 s, power of 100 W, gas flow rate of 6
LPM and ageing time of 5 min. The change in surface free
energy for the polypropylene film was affected by fast cross
linking on the surface due to the simultaneous forming
and breaking of polar groups. Kostler et al. [161] investi-
gated poly(diallylmethylammonium chloride) (PDADMAC)
and found that there were polymer chain rearrangement
processes on the sample surfaces based on the analysis of
the surface tension components by contact angle measure-
ments.
Another significant phenomenon with plasma treat-
ment of polymers is the degradation of the surface
properties through ageing. It has been suggested that this
is due to the reorientation of polar chemical groups into
the bulk of the material, which in turn reduces the sur-
face energy. Following from the thermodynamic theory on
adhesion, a reduction in the surface energy poses a prob-
lem due to the correlation between high surface energy and
good adhesion. This is shown in the study undertaken by
Dilsiz et al. [148] where carbon fibres were modified by
plasma treatment. In this study they were able to relate
adhesion strength between the surfaces to contact angle
data (surface energy calculations). Another theory on age-
ing is that polar chemical groups diffuse into the polymer
matrix, a side effect being surface degradation through
the rapid interaction of the polymer with radicals or ions
[33,153].
The type of plasma used in the surface modification
of polymers has a significant effect on the wettability
and the overall adhesion properties of the polymer. An
investigation into the characteristics of PP modified by an
Ar/O2 plasma found that although both plasma treatments
increased the surface free energy of the samples surface,
the Ar plasma treatment was more effective in improving
film wettability [154]. Plasma treatments have long been
known to increase the wettability of polymers through the
addition of polar functional groups at the polymer surface
[30,134], with the degree of crosslinking and population of
polar groups on the surface controlling surface wettability
[30]. This control of surface wettability allows for improved
adhesion at the polymer interface due to the introduction
of carbonyl and other functional groups [162].
Allylcyanide and a mixture of xylene, air and oxygen
plasmas have also been used successfully to improve the
degree of adhesion between polymers and their matrix
[148]. Oxygen plasma treatment of high-density polyethy-
lene (HDPE) with different crystalline fractions has shown
that an increased crystalline order lowers oxidation, and
hence the ageing of the polar functional groups on the
sample surface [153]. However, Hegemann et al. [33] has
shown in a series of experiments based on different surface
treatments of polymers that although oxygen containing
plasma treatments increased the wettability characteristics
of the surfaces, this could be quickly lost to the atmosphere
through ageing. They observed that N2 plasma treatments
of polycarbonate showed the lowest ageing effects but a
surface deposition of SiOx layers was the best way to main-
tain a lasting hydrophilic surface [33].
In a recent study, PP bumper bar substrates were treated
with oxygen plasma and it was found that to optimize
adhesion and wettability the plasma power was required
to be below 500 W for an exposure time of 300 s [162].
It was found that as the plasma power increased above
500 W, hydrophilic functional groups were still forming
on the surface of the polyolefins (determined through XPS
analysis), however surface roughness (AFM measurements)
began to decrease. In particular, the surface morphology
(as determined by an assembly of round grains) values
increased past this point. Oxygen plasma has also been used
to treat the surface of both polycarbonate (PC) and PMMA
to induce the deposition of diamond like carbon (DLC). It
was shown that the DLC film adhered better to PC than
to PMMA, and as a result interfacial layers were deposited
onto the surface of PMMA in order to increase its adhesion
[87].
A combination of ToF-SIMS, XPS and ATR-IR has been
used together to analyse PP films which had been treated
with an air dielectric plasma. The investigation found
that the molecular organisation at the sample surface
along with chemical conversion of the oxidised species
were responsible for the improvements in hydrophilicity
[158]. Hegemann et al. [33] identified a more permanent
hydrophilic treatment for polymer surfaces. In this study
SiOx layers were deposited onto the surface of polycarbon-
ate (PC) substrates, and were shown through contact angle
measurements to be less prone to ageing effects when com-
pared to the plasma treatments [33]. Bhowmik et al. [110]
used a combination of contact angle and XPS measure-
ments to conclude that DC glow discharge treatment of PP
increased the surface energy and also increased the surface
oxygen to carbon ratio. As surface energy is directly related
to the work of adhesion, the increase in surface energy cor-
responds to a theoretical increase in adhesion [110]. An
investigation of surface energy changes for polymethyl-
methacrylate (PMMA) demonstrated that both DC glow
discharge and microwave plasma treatments considerably
increased the surface free energy of the sample. How-
ever, only the DC glow discharge method improved coating
adhesion [156]. UV/ozone treatment is also reported by
researchers to increase the oxygen containing functional
groups on the surface [8,116].
3.3. Other treatments
A variety of surface treatment techniques for improving
adhesion other than chemical and plasma treatments have
been described. Corona discharge, as for plasma treatment,
introduces oxygen-containing polar groups to the surface
and improves the surface energy and adhesion strength
[163]. Atomic force microscopy (AFM), XPS and contact
angle measurements were used to characterize corona-
treated PP, with the surface roughness measurements
showing no significant changes to the corona-treated
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968 959

samples, while the XPS and contact angle values showed mechanical characteristics of polymer–wood composites
the O/C ratio decreased with ageing [144]. (PWC), primarily PP and sawdust [80].
Rubbers such as styrene–butadiene rubber (SBR) have
been chemically treated to increase adhesive properties. 4. Direct adhesion measurements
Trichloroisocyanuric acid (TCI) increased adhesion strength
of SBR [164]. This method is environmentally hazardous Direct adhesion measurements such as pull off tests,
and as such chloramine T (CT) (N-chloro-sodium-p- peel tests, lap and shear tests, and scratch tests are destruc-
tolue-nsulphenamide) was used as the chlorinating agent tive methods that measure the force required to break, tear
in another study. It was shown that CT/H2 O solution and delaminate surfaces at the interface. Understanding the
acidified with sulfuric acid was a suitable alterna- locus of failure for any system is of high importance. When
tive to TCI treatment [142]. Surface treatments for MAPP was pre-blended with PP and formed a copolymer
ethylene–propylene-diene rubber (EPDM) include treat- with Ny6 the locus of failure was found to be dependant
ing with maleic anhydride grafted rubber, which increased not only on bonding temperature but also bonding time
adhesion strength between the two compounds [165]. [173]. Similarly, when the pull off test method was used to
Ground rubber tire (GRT) was shown to substitute for analyse microwave irradiated PP, it was found that the locus
EPDM successfully in dynamically vulcanized EPDM/acrylic of failure changed from adhesive to cohesive failure along
modified HDPE blends without the loss of thermoplastic the bond for good adhesion values [174].
behaviour at a 60:40 rubber/plastic ratio [166]. While many direct measurements of adhesion strength
Irradiation treatments are used to increase the wet- provide qualitative data, tests such as peel and pull up
tability of polymer surfaces, which result in an increase tests provide a quantitative measure of adhesion. How-
of adhesion characteristics of biomaterial surfaces. PMMA ever, many tests are required to provide consistent results.
has been treated with a CO2 , Nd:YAG (Neodyium-doped Further, direct methods do not provide physical interpreta-
yttrium aluminium garnet) laser, an excimer laser and tions of different adhesion measurements. A combination
a high power diode laser (HDPL). It was found that the of direct adhesion measurement and surface characteriza-
Nd:YAG and HDPL interaction with the surface of PMMA tion using techniques such as XPS, ToF-SIMS and contact
did not effect the wettability characteristics at all, although angle measurements is an optimum way of investigating
the surface treatment with excimer laser radiation did polymer adhesion. This section deals primarily with the
improve the wettability of PMMA [167]. The impact of role of direct adhesion measurement.
hard X-ray exposure of PMMA has been examined with
Gas Chromatography–Mass Spectrometry (GC–MS), result- 4.1. Peel tests
ing in finding trapped volatiles at the surface including
the MMA monomer [168]. Deep UV irradiation of PMMA The peel test is an excellent example of an adhesion test
characterized by XPS has found carboxyl groups amongst whose values are only useful in a relative sense. Adhesive
others on the surface of the treated sample. This treatment tape is placed and pressed on the surface of the sample
provided a simple and fast route for cell adhesion with to be tested, for example, an ink/paint layer on a substrate.
enhanced adhesion results and the elimination of chemical Pressure is applied by a rubber cylinder with a defined force
treatments [4,45] and in a repeatable manner (Fig. 4). The tape is detached
Adhesion strength is also increased when block (or graft)
polymers are added to the interface, working like a molec-
ular bridge between the two homopolymers [169,170].
For instance, when the coupling agent maleic anhydride
grafted PP was used to reinforce the interface between PP
and amorphous anhydride a dramatic adhesion enhance-
ment was observed [44]. Similarly, graft copolymers were
introduced to the PP/poly(vinylidene fluoride) (PVDF)
interface where it was observed that adhesion strength
increased by a factor of 15 [171]. Styrene maleic anhydride
random copolymer (SMA-8 wt.% MA) and poly(methylene
(phenylene isocyanate)) (PMPI), dual compatibilizers, were
demonstrated to bridge the interface of PET forming
PET-co-PMPI-co-SMA allowing for improved mechanical
properties [172]. Fracture toughness also increased at the
interface between nylon 6 (Ny6) and PP with the introduc-
tion of maleic anhydride grafted polypropylene (MAPP);
fracture toughness increased as the intermolecular reac-
tions between MAPP and Ny6 increased [173]. MAPP has
also been used with silane coupling agent to increase
the interfacial strength of polypropylene–mica (PP-mica)
composites. Again it was found that an increase in MAPP
Fig. 4. Schematic of peel test. P, h and ā represent the applied shear force,
improved the adhesion strength between the mica filler beam depth and beam length respectively. Image reproduced with per-
and the PP [93]. MAPP has also successfully improved the mission from ref. [234] (Elsevier, 2005).
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960 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Fig. 5. Schematic of the twist peel test [180] (John Wiley & Sons, Inc., 2003).
quickly from the inked surface and the percentage of ink
remaining on the substrate can be visually evaluated as a
percentage of the original layer.
T-peel tests have been used to delaminate samples of
polypropylene and polyethylene bonded with a Ziegler-
Natta catalysed ethylene copolymer (ZNPE). In this study,
the delamination was propagated by a constant force in
the steady-state region, allowing for the calculation of the
delamination toughness G
2F
G= (19)
W
where F is the average peel force and W the width of the
sample. The problem encountered in this study was the
contribution of plastic deformation to the overall G value.
While it has been reported previously that reducing the
peel rate can reduce the contribution due to deformation
[175], other studies did not confirm this finding [176].
T-Peel tests were also used by Bhat and Upadhyay [177]
in their investigation of plasma induced surface modifica-
tion of PP. In this study, the delamination toughness G value
was not calculated but adhesion strength was measured
using an Instron tensile tester. It was reported that when the
polymer was plasma treated for a short length of time (less
than 1 min) adhesion strength decreased, before increas-
ing with time. Machine marks and contaminants are often
found in commercial manufacturing processes, so when
samples are plasma treated for short lengths of time the
surface is actually “cleaned” by the plasma, explaining the
adhesion trend.
Different findings using oxygen plasma treated PP and
lignocellulosics were reported by Mahlberg et al. [178]. In
their study they measured adhesion using a 90◦ peel test
and found that the highest adhesion values were observed
for the shortest treatment time. They also found that adhe-
sion is improved when both the film and the substrate are
treated [178].
Other derivatives of peel tests have been used to inves-
tigate adhesion on polymer surfaces. Carrino et al. [179]
showed via dry (without primer) and wet (with primer)
peel tests that cold plasma surface modification does
increase the adhesive strength of paint coatings on PP. Peel
tests have also been used to measure adhesive strength as a
function of thickness, molecular mass and amount of filler
in a study which used a poly(methyl acrylate) PMA and
glass slide system. This study found that there was a linear
association between adhesive force and the peel velocity
[112].
Peel tests have been used in the investigation of nitric
and sulfuric acid treatments of PP by Vasconcellos et al.
[109]. While the delamination constant G was not cal-
culated in this study, the authors were able to measure
quantitatively the adhesive strength between the PP and
leather substrate. They concluded that mechanical cou-
pling rather than the chemical treatments was the main
reason for improved adhesion strength to PP [109].
Boullanger et al. [180] used the twist peel test (Fig. 5)
in order to conserve the geometry of the poly(vinyl aceto-
formal) PVF enameled wire. The peel test and fibre pull out
tests would have destroyed both the geometry and the wire,
whereas the twist peel test does not and is also commonly
used in the wire winding industry. Although the twist peel
test is purely qualitative it did allow for sample compar-
isons to take place and hence a measure of the relative
adhesive strength [180].
4.2. Lap shear tests
Lap shear tests are similar to peel tests although this
method of adhesion measurement is more commonly
quantitative in nature. Fig. 6 shows a typical test config-
uration in which two PMMA sheets bonded in the center
using a two part toughened acrylic and, once cured, a load
from the tensile tester is applied at a rate of 1 mm/min [55].
A lap shear study of surface fluorination of PP with
polyester adhesive showed an increase of adhesive strength
up to a fluorination time of 20 min, although there was a
decrease in strength after this time [181]. This phenomenon
was also seen by Court et al. [55] in a study of ageing
on adhesion strength in a PMMA system. It was demon-
strated that adhesion strength decreased as a function of
ageing time. Cherain and Lehman [182] have also used lap
shear tests to measure adhesion strength for adhesively
bonded polystyrene (PS) and high-density polyethylene
(HDPE) and blends. They found that adhesive strength
increased with increasing PS content. Sturiale et al. [183]
showed through lap shear tests and FTIR analysis, con-
sistent with the work of Cherain and Lehman, that the
presence resole-type phenolic resins enhances adhesion at
the epoxy–amine interface [183].
A more comprehensive way of exploring and measur-
ing adhesion phenomena is through a combination of both
direct and indirect measurements. In the study under-
taken by Muhlhan et al. [133], lap shear tests were used
to measure the mechanical strength of overlapped plasma-
treated PP samples in conjunction with XPS measurements.
XPS data revealed the concentration of functional groups
at the surface increasing with plasma treatment time, as
expected, and yet this did not correlate to higher adhesive
strength determined in the lap shear tests [133].
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Fig. 6. Schematic of tensile lap shear test reproduced from ref. [55] (Else-
vier, 2001).
Ochi et al. [184] investigated the mechanism of adhesion
in epoxy and silica hybrid systems. Their results indicated
that adhesion strength increased with curing temperature
and they were able to demonstrate that unmodified epoxy
resin had a very low bonding strength when compared to
the modified resin [184].
4.3. Pull out test
A schematic of the pull out test is shown in Fig. 7.
The metallic block is restrained in place while the sample
shim is pulled out at a constant speed. Such tests are com-
monly used in combination with other adhesion testing
approaches.
Fibre bundle pullout tests were used by Jana et al. [185],
to evaluate adhesion between ultrahigh-molecular-weight
polyethylene (UHMWPE) fibres and nano-epoxy matri-
ces, concluding that reactive graphitic nanofibres (r-GNFs)
improved fibre-matrix adhesion.
Earlier it was reported that Ochi et al. [184] used a
lap shear test to demonstrate increasing adhesion strength
with surface treatment time. Mirabedini et al. [174] tested
PP treated with microwave irradiation, and found through
the use of a pull off test that when the tensile force was
applied normally to the sample surface, adhesion strength
increased as a function of treatment time with no initial
decrease [174].
In a similar study of ozone treatments of poly(ethylene
terephthalate) and poly(hydroxyethyl methacrylate), a
961
Fig. 7. Schematic of pull out test, reproduced from ref. [235] (National
Physical Laboratory, 2004).
combination of SEM, XPS and contact angle measurements
was used to investigate the surface chemistry of the treated
polymer surfaces. Pull out tests were then used to measure
the interfacial bond strength between the polymer fibres,
and hence give an estimation of adhesion. Results indicated
that ozone treatment increased the carboxylic, anhydride
and hydroxyl group surface concentration in comparison to
the untreated samples, with the pull out tests also indicat-
ing that adhesion strength increased with ozone treatment
[186].
4.4. Torque test
Torque tests provide good quality quantitative adhe-
sive information. One such test was used to investigate
the adhesive force at a hexamethyldisiloxane (HMDSO) gas
modified polypropylene substrate. A hydrophobic polymer
veneer was formed on the surface as a result of the treat-
ment. A slotted steel stud was attached to the surface with
cyanoacrylate adhesive and a torque wench used to deter-
mine torque at failure. Shear stress (T) was calculated using
the relationship,
165I
T= (20)
d3
where I is the measured torque and d the diameter of the
stud [39]. No great difference in adhesion strength was
found as a function of treatment time and the failure types
observed were not statistically significant [39].
4.5. Scratch test
The scratch test is closely related to the nanoindentation
test, and for simplicity, the two will be considered together.
In both cases adhesion is assessed using a fine tip that is
dragged across the samples surface under an increasing
load, resulting in an indentation (shown schematically in
Fig. 8). Indentation and scratch tests are well suited to the
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962 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Fig. 8. Schematic of scratch test reproduced from ref. [203] (National
Physical Laboratory, 2004).
investigation of thin films and coatings, generally produc-
ing definitive results [187].
Nanoindentation has been used to investigate surface
properties such as hardness and coating delamination force
for polymers. In the exploratory work by Beake et al. [188],
nanoindentation was applied to thermoplastic materials
(for example plasma-polymerized hexane films) which
were, in general, harder and stiffer than general thermo-
plastics [188].
Failure mechanisms for polymer systems have also used
in scratch tests to explain surface condition. In a study
between a gelatin coating and nitrogen plasma-treated
PET surface, it was found that the failure mechanism was
dependant on a series of interactions between the indenter
and the coating. The study also supplemented the previ-
ous work carried out by Ochi et al. [184] and others in that
they found that the critical load increased as a function of
nitrogen plasma time [189].
The outcomes from indentation tests are sometimes
dependant on the interactions between the indenter and
the coating. Finite Element Analysis (FEA) has been used
to normalise the effect the geometry of the tip has on the
results by only considering the stress and not the load
applied to the coatings [190,191]. One such study using FEA
was the investigation of acrylic polymers coated on steel
substrates. In this study it was concluded that the scratch
behavior of coatings can be evaluated in a manner similar
to bulk polymers [192].
Jardet and Morel [191] analyzed scratch parameters
that relate to mechanical properties. They reported a cor-
relation between the tensile stress-strain behaviour and
scratch fracture toughness for poly(methylmethaacrylate)
(PMMA). Modifying the scratch test to measure not only
the normal force range but also the tangential forces
simultaneously allows for a complete tribological approach
to surface characterization, in as much that the energy
which is dissipated in the scratching process can also be
measured [193,194]. One such approach was undertaken
by Wang and Lim [195], who found that in a tungsten
carbide (WC) particle and polymer system the coatings
containing the WC showed greater hardness and scratch
resistance when compared to the pure polymer coating
values [195].
4.6. Stud/butt test
Pull off tests, commonly known as a stud or butt test,
are used to measure adhesion between a substrate and an
Fig. 9. Schematic of tensile butt/stud adhesion test, reproduced from ref.
[235] (National Physical Laboratory, 2004).
ink or paint coating. An adhesive is applied to the paint
coating and a metallic stud (aluminium) is glued onto the
surface. A force is then applied perpendicular to the sur-
face of the substrate at a constant rate. Fig. 9 illustrates
the test schematically. The pull off test provides a superior
adhesion measurement for systems such as polymer–metal
interfaces [196].
The pull off test is not limited to the automotive and
polymer sectors. It has been applied to integrated cir-
cuits. In the work by Chiang and Hsieh [197], it was found
that the pull off test was able to show that the adhe-
sion strength of a resin decreased with an increase of
the inorganic filler (hexagonal boron nitride hBN). The
pull off test has been used directly to assess the adhe-
sive bond strength at metal and polymer interfaces, for
example in printed circuit boards. Turunen et al. [198]
showed using pull off testing that an adhesion promoter
substantially increased the durability at coating/copper
interfaces.
In the development of high speed broadband services,
there has been a growing interest in metal/smooth polymer
composites especially the need for an improvement in their
adhesive properties [199,200]. An investigation of telecom-
munications materials by Liu et al. [201] which looked at
144 I/O Film-BGA integrated circuit substrates found that
adhesion strength could be characterized using a combi-
nation of XPS and stud pull off test experiments. In model
studies of epoxy/electroless copper systems, it was found
that the pull off test values based on the schematic in Fig. 9
correlated well with the contact angle results (in particular
the polar component of the surface free energies) and XPS
results [200,202,203].
The pull off test in conjunction with contact angle anal-
ysis and XPS has also been used in the investigation of
the interface of polypropylene and spherical glass parti-
cles. It was found that adhesion strength was greater when
the polypropylene surface was treated with hydrocar-
bon functional groups as opposed to fluorocarbon groups
[204].
A combination of direct and indirect techniques for
investigating adhesion may be used to provide further
information about adhesion strength and phenomena, as
summarized in (Table 2).
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Table 2
Combination of direct and indirect techniques used by researchers for the adhesion investigations.
Direct technique Indirect technique
Lap Shear test XPS
FTIR
EDS, Contact Angle
SEM, XPS
XPS, Contact Angle
Pull out test SEM, XPS, Contact Angle
Pull off/Stud test XPS
XPS, SEM
XPS, Contact Angle
XPS, SEM
Nanoindentation/Scratch test XPS, Contact Angle
SEM, Contact Angle, Raman Spectroscopy
Peel test FTIR-ATR
5. Polymer blends and reactive polymers
5.1. Polymer blends
Adhesion performance of various polymer types may
be improved significantly by blending with other poly-
mers [27,34–37,69,70,116,205–209]. The preceding sections
included many examples of the relationships between
adhesion strength and polymer blends. The key topic of
stress at the polymer interface and its role in adhesion will
be considered in this section.
This process is especially important when related to
the interface of a polyolefin and a paint surface as the
integrity of the composite is determined by how well stress
is transferred from the interface to the substrate [96]. In an
experiment employing deuterated aromatic thermosetting
copolyester (ATSP) and poly(4,4 -diphenylether pyromel-
litimide) (PMDA-ODA), Xu et al. [210] found that by partially
curing both polyimides, the interface was increased allow-
ing for the easy transportation of stress from the interface,
increasing adhesion. In a similar study, the interfacial
shear strength of composite systems of polymer coatings
incorporating both carbon fibre and vinyl ester were inves-
tigated. Greater diffusion was shown to lead to greater
interfacial shear strength as both SEM micrographs and
adhesive strength values showed greater diffusion for poly-
mer coating to carbon fibre than the coating to the vinyl
ester [211].
A combination of tensile cracking tests, optical
microscopy, SEM and transmission electron microscopy
(TEM) were used to demonstrate that in a CPO/TPO system,
while the diffusion of the CPO is important in adhe-
sion strength, the diffusion of the rubber phase is of
equal importance to overall strength [37]. Karmaker and
Youngquist [212] found that employing maleic anhydride
grafted polypropylene as a coupling agent in jute fibre–
polypropylene composites resulted in enhanced adhesion
between the fibres and the polymer matrix. The increase
in adhesion offset the adhesion strength loss associated
with fibre attrition from the injection molding stage [212].
963
Polymer system Reference
Plasma treated PP system [133]
Epoxy–amine system, Polyimide (PI) films [183,240,125]
DC glow discharge treated HDPE [91]
Maleic anhydride-grafted pp in PP [116]
PE, PEEK
Ozone treatment of PET and poly(hydroxyethyl [186]
methacrylate
144 I/O Film-BGA [201]
Copper metallised glass fibre reinforced epoxy [198]
Flame treated PP [236]
PP–copper compound [241]
Plasma polymerized hexane films [188]
Plasma treated PET [189]
Acrylic coated polymers [192]
Ion implanted PC surface [206]
Oxygen and pulse plasma of polypropylene and [242]
poly(tetrafluoroethylene)
Similarly, adhesion strength was found to be dependent on
the process of combining polymer blends together. Maleic
anhydride grafted polypropylene (MA-g-PP) was used as
a coupling agent in a sisal fibre–polypropylene composite.
By blending the materials in a two stage process, breakage
of the sisal fibre at the injection step is avoided to a high
degree resulting in improved mechanical properties [213].
The addition of styrene–butadiene (SB) block copoly-
mers (BCs) to polystyrene–polybutadiene (PS/PB) blends
was investigated with small angle X-Ray scattering method
(SAXS), SEM and image analysis (IA). It was shown that
this addition substantially increased the toughness of the
PS/PB blends [214]. Polymer blends of polypropylene (PP)
and polystyrene (PS) were investigated with FTIR, SEM, DSC
and tensile tests after first being functionalized through
the addition of maleic anhydride grafted PP (PP-g-MA)
and styrene maleic anhydride random copolymer (SMA)
compatibilisers respectively. It was concluded that the
mechanical properties (adhesion strength) increased due
to the compatibilisers abilities to lower interfacial tension
at the interface causing a more efficient transfer of stress
under load.
Manufacturers of next generation electronic circuits are
also beginning to investigate polymer composite materials.
Raballand and coworkers [215] investigated the properties
of ethyl-polyhedral oligomeric silsequioxane (ethyl-POSS)
finding that when exposed to oxygen plasma a protective
silicon oxide layer formed increasing etch times and mak-
ing it a useful material for bilayer lithography [215].
5.2. Reactive polymers, adhesives and coatings
Increasing attention has been paid by researchers to the
use of reactive polymerization and reactive substances and
surfaces in the application of adhesion. In this article, brief
examples are given of graft polymerization, hot melt reac-
tive adhesives, reactive coatings and reactive surfactant.
Polymer surfaces that have intelligent functionalities which
respond to the environment or to an external stimuli are
discussed in a review by Luzinov et al. [216].
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964 F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
Plasma graft polymerization has been used signifi-
cantly by researchers to improve adhesion of polymer
systems [217–220]. Yamada et al. [219] described a proce-
dure for plasma graft polymerization of vinyl monomers
with reactive groups onto the surface of poly(p-phenylene
terephthalamide) fibre. The reactive groups were reacted
with the resin/hardener matrix to form covalent bonds. The
pull out testing was used then to examine the increase of
adhesion strength between the fiber and the resin matrix
as a result of grafting. Gupta et al. [217] showed that an
increase of surface roughness and decrease in contact angle
measurements were observed in PET films after plasma
induced grafting with acrylic acid. Peel strength improve-
ment of expanded poly(tetrafluoroethylene) (ePTFE) film
by O2 RF plasma treatment and grafting polymerization
with hydrophilic monomers of acrylamide (AAm), glycidyl
methacrylate (GMA) and 2-hydroxyethyl methacrylate
(HEMA) were conducted by Li et al. [220]. They reported
a significant increase in peel strength as a result of plasma
graft polymerization at specific conditions.
An investigation into the effect that shear flow per-
pendicular to the interface was curried out on interfacial
morphologies for reactive polymer blends of polystyrene
modified with carboxylic acid (PS-mCOOH) blended
with poly(methyl methacrylate-ran-glycidyl methacrylate)
(PMMA-GMA). Here, the reaction between the carboxylic
acid in PS-mCOOH and PMMA-GMA occurred easily at high
temperatures to form an in situ copolymer PMMA-graft-PS.
It was found that the in situ graft copolymer stabilized the
interfacial morphology and did not increase the interfacial
roughness [221].
p-Nitrophenyl methacrylate (NPMA) and diethoxy-
propyl methacrylate (DEPMA) were polymerized using
a chain transfer agent cumyl dithiobenzoate (CDB) with
azobisisobutyronitrile (AIBN) to increase conversion by
reversible addition-fragmentation chain transfer (RAFT)
polymerization to investigate the possibility of NPMA and
DEPMA being used to prepare drug carriers. In the study
it was concluded that not only could pNPMA and pDEPMA
be used to prepare drug carriers but that up to 86% of the
side chains of pNPMA were successfully substituted with
glycine methyl ester (amino acid) [222].
Hot melt reactive adhesives have been used by
researchers due to their excellent physical proper-
ties [223–226]. An example of hot melt adhesives is
the Isocyanate-functionalized polyurethane pre-polymer
[226]. The permeation of the water from the environment
into the pre-polymer triggers the reaction with the iso-
cyanate functional groups to establish the curing reaction
[227]. The mechanism of moisture-cure isocyanate reac-
tive hot melt adhesive has been reported by Comyn et al.
[224]. They discovered that water permeability is the main
parameter that affects curing rate. Duffy et al. [228] exam-
ined a ternary reactive blend of polyether, polyester and
acrylic to model a polyurethane based hot melt reactive
adhesive. They described the effect of blending param-
eters such as the functionality and molecular weight of
the polyether and the polyester on the blend miscibil-
ity behavior. They also explained that urethane groups
improve the compatibility of the blend at low degree of
polymerization. Cui et al. [223] examined the crystalline
structure in isocyanate reactive hot melt adhesives. They
reported that crystalline structure was found in the fully
cured polyurethane–urea crosslinked matrix even though
it is said to diminish with the moisture cure. They also
concluded that while the crystalline structure delays cur-
ing reaction in the early stage, it reinforces the cohesive
strength of the fully cured polymer matrix. The descrip-
tion, developments and applications of high performance
polyurethane and its subclass coatings are reported thor-
oughly by Chattopadhyay and Raju [229]
Reactive coating [230] is used in many systems in which
a good adhesion is reported between the coating and
the substrate. Further, new class of adhesives based on
poly(acrylate/siloxane) hybrids has been reported recently
to bond polymer substrates with low surface energy [231].
Sonnenschein et al. [231] showed that these adhesives are
produced from the independent polymerization of the sili-
con oilgomers and acrylic monomers. Recent studies [232]
showed that the addition of reactive surfactant during
the polymerization process of acrylic, vinylic and styrenic
monomers improves the end product adhesion strength.
6. Future perspective
Adhesion is impacted by many phenomena. The diver-
sity and inter-disciplinary nature of these phenomena
made it difficult to produce a single theory or mechanism
that explains the chemical and physical manifestations of
the adhesion. There is considerable debate in the literature
regarding each of the adhesion mechanisms. For example,
within the thermodynamic theory of adhesion, it is not set-
tled which theory is best to describe the surface free energy
of solids—whether it be an equation of state theory or an
acid–base approach. One should understand, however, that
the diversity of polymer systems implies that all mecha-
nisms and theories of adhesion should be embraced in the
research in combination to explain adhesion strength or the
lack of.
Although, the chemical and physical composition of
the first few atomic layers determines adhesion and other
properties of the polymer, it is the layer underneath, the
subsurface, which in part controls the outer layers. The
crosslinking and double bonds restrict the mobility in the
subsurface, resulting in the stabilization of the functional
groups on the surface. Further research is needed to exam-
ine the polymer sub-surface layers and explain their effect
on surface properties.
Investigation is also needed to improve the quantita-
tive measures of adhesion. Amongst the myriad of methods
reviewed in this article there seems to be no strong evi-
dence as to which method is best equipped to provide an
outright value for adhesion. This is in part due to the major-
ity of adhesion tests being qualitative, reporting results
relative to a given set of samples.
Polymer products manufacturers and parts produc-
ers should take advantage of the surface segregation
effect to produce polymer products with improved surface
properties. Consequently, researchers should improve the
knowledge on polymer additives that promote adhesion
and their interaction with the segregation phenomena. This
knowledge will assist manufacturers to eliminate the need
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F. Awaja et al. / Progress in Polymer Science 34 (2009) 948–968
for expensive and often environmentally hazardous surface
treatments for finished parts.
Non-destructive analysis such as X-ray tomography of
the surface needs to be developed further to provide struc-
tural information. Surface structural information has the
potential to provide correlations with surface adhesion
strength or surface energy. The non-destructive nature of
the test will allow more accurate examination of surface
polymers. These techniques are mostly valuable in the
study of the quality of adhesive joints and bonds in polymer
structures [233].
Finally, the advances that have been made in the recent
years in the accurate analysis of the surface chemical com-
positions using instruments such as XPS and ToF-SIMS have
the potential for advancing the theoretical and practical
aspects of polymer adhesion significantly. Better knowl-
edge of the chemical composition of the polymer surfaces
in comparative studies with adhesion strength tests will
accurately illuminate correlations between the chemical
bonding mechanism and adhesion. Further, polymers with
tailored adhesion strength could be produced through the
changes in surface chemical structures.
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