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Handbook of Adhesive Technology

A. Pizzi, K. L. Mittal

Plasma Surface Treatment to Enhance Adhesive Bonding

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Nitu Bhatnagar
Published online on: 21 Dec 2017

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 3 Plasma Surface Treatment
to Enhance Adhesive Bonding
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Nitu Bhatnagar

CONTENTS
3.1 Introduction............................................................................................................................. 67
3.2 Adhesives................................................................................................................................. 68
3.3 Adhesion.................................................................................................................................. 70
3.3.1 Mechanism of Liquid–Solid Adhesion........................................................................ 71
3.3.2 Wetting......................................................................................................................... 72
3.3.3 Polymer–Polymer Adhesive Joint................................................................................ 73
3.4 Surface Modification of Polymers........................................................................................... 73
3.4.1 Chemical Treatment.................................................................................................... 74
3.4.2 Thermal Treatment...................................................................................................... 74
3.4.3 Mechanical Treatment................................................................................................. 75
3.4.4 Electrical Treatment.................................................................................................... 75
[Link] Electrical Treatment by Generation of Plasma............................................. 76
3.5 Effect of Plasma Treatment on Physicochemical Properties of Polymers............................... 78
3.5.1 Contact Angle Measurement and Surface Free Energy Determination..................... 78
3.5.2 X-Ray Photoelectron Spectroscopy Analysis.............................................................. 81
3.5.3 Atomic Force Microscopy Analysis............................................................................ 82
3.5.4 Adhesion Characteristics of Surface-Modified Polymers........................................... 85
3.6 Summary................................................................................................................................. 89
Acknowledgments............................................................................................................................. 89
References......................................................................................................................................... 89

3.1 INTRODUCTION
Major industrial sectors such as automotive, aerospace, and others are increasingly employing poly-
mer composites in their load-bearing structural parts, which offers benefits such as being light-
weight, good thermomechanical bulk properties, low cost, and recycling [1–4]. Apart from this, the
rationale behind the choice of polymeric composites lies in their superior physical, mechanical, and
chemical performances, along with higher resistance to corrosion and structural weakening from
radiation [5]. The use of adhesively bonded joints in these load-bearing structures is of great interest
to the aerospace and automotive industries as compared with mechanical methods (welding, rivet-
ing), which generally lead to stress and failure problems.
Structural and specialty adhesives account for about 30% of the total adhesive and sealant mar-
ket, with uses in many industries [6]. This is because of time and cost savings, high corrosion and
fatigue resistance, crack retardance, and good damping characteristics. Adhesive bonds are more
effective in assembling composite structures than other mechanical joining methods, as they pro-
vide more uniform stress distribution, lower stress concentration, and better fatigue life and corro-
sion resistance [7]. Any adhesive joint can distribute the applied load over the entire bonded area
and is suitable for joining dissimilar materials with low manufacturing cost [8].

67
 68 Handbook of Adhesive Technology, Third Edition

It has been established that for successful application of polymeric composite materials to form
structural parts using adhesive bonding, they need to have special surface properties such as polar-
ity and high surface free energy (SFE) [9]. A basic requirement for successful bonding is the spread-
ing of the adhesive on the surface of the adherend or substrate [10]. This will occur if the SFE of
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the adhesive is lower than that of the adherend, but the typical values of SFE are 30–50 mJ/m2 for
adhesives and about 12 mJ/m2 to about 70 mJ/m2 for polymers [11]. This shows that although these
polymers have found wide suitability for high-end applications, they still have some limitations in
achieving a good structural adhesive bond. Several conventional methods such as chemical treat-
ment, thermal treatment, and mechanical treatment are used to modify polymeric surfaces, but they
suffer from problems of uniformity, reproducibility, and cost-effectiveness. The need for adequate
adhesion by activating the polymeric surface without affecting the bulk properties of the polymer
has resulted in the development of plasma surface modification techniques [12], which offer a uni-
form, reproducible, economic, and environmentally friendly alternative [13]. It has been observed
that the polar component of the SFE leading to increased total SFE of the polymer increases signifi-
cantly due to generation of new functional groups as a result of surface oxidation by reactive species
in the plasma [14]. The changes in the physicochemical characteristics and surface morphology of
the polymer brought about by plasma result in strong adhesion [15].

3.2 ADHESIVES
The automotive, aerospace, building, biomedical, and other industries have been investigating the
use of various types of adhesives and sealants for numerous applications in these industries.
An adhesive or glue is a mixture in a liquid or semiliquid state that bonds items together. Adhesives
cure (harden) by either evaporating the solvent or by chemical reactions that occur between two or
more constituents [16,17]. The adhesives are classified into different types. A detailed description of
different types of adhesives is given in Table 3.1.
The choice of proper adhesive is critical to produce strong and durable bonds [24]. Unlike ther-
moplastics, thermosetting adhesives do not melt or flow on heating, but become rubbery and lose
strength. The molecular chains present in thermosetting adhesives undergo irreversible cross-link-
ing during curing [25]. The most familiar thermosetting adhesives are the family of epoxies. The
limitations of other adhesives for the joining of different materials have been solved by epoxy adhe-
sives, and presently these adhesives are widely used.
It is evident from the literature that thermoplastic resins can withstand temperatures comparable
to many aerospace graphite–epoxy prepregs (177°C). A common example of an adhesive system
found in the automotive industry is a paint coating applied to a polypropylene (PP) bumper bar.
However, it requires some pretreatments. Adhesives that have been used successfully in aerospace
are, typically, modified epoxy film adhesives with brand names such as FM300 (Cytec Industries
Inc.) for both poly(phenylene sulfide) (PPS) [26] and poly(ether ether ketone) (PEEK) [27,28], FM
377 [29], and FM 87 [30]. The building industries require such sealing materials in the form of
sealants that have the ability to withstand thermal expansion and contraction while still bonded to
the substrate [4,31,32]. Kodokian and Kinloch [33] described the use of a wide range of epoxy- and
acrylic-based adhesives for bonding applications: Hysol 9309.3, FM73M, Permabond F241, F245,
F246, and V501, and Bostik M890 and M896. An extensive review of adhesives for PEEK–graphite
composite bonding is also given in [34], and it was found that FM300 recorded a close second-highest
lap shear strength value of 23 MPa to Scotch-Weld structural adhesive film (AF-163-2K) (24.5 MPa)
when tested at 25°C. When it comes to the biomedical industry, a study of the adhesion mechanism
between human hepatoma cell lines and polymers such as polystyrene, poly(methyl methacrylate),
and polycarbonate (PC) is of much importance [35–38]. Researchers [38,39] have made an important
observation that the major factor responsible for cell adhesion to polymer substrates is the SFE of the
polymer, irrespective of whether the surface has been covered by a protein layer.
 Plasma Surface Treatment to Enhance Adhesive Bonding 69

TABLE 3.1
Classification of Adhesives
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Type Description Examples

General Classification
Thermosetting Cross-linked by strong covalent intermolecular bonds, Epoxies, polyesters, polyimides,
forming one giant molecule phenolics
Thermoplastic Molecules of most of thermoplastics combine into long Polyamides, cyanoacrylates,
polymer chains alternating with monomer units polyacrylates, poly(vinyl
acetate) (PVAc)
Elastomeric These consist of long lightly cross-linked molecules Natural rubbers, silicones,
acrylonitrile butadiene (nitrile),
neoprene, polyurethane,
styrene–butadiene

On the Basis of Function

Structural Used to bond structural materials and have the ability to Polyurethanes, polysulfides,
adhesives withstand significant loads or stresses polyesters, acrylics, special
formulations of cyanoacrylates,
anaerobics, epoxy adhesives
Nonstructural Also called holding adhesives, these are not required to Pressure-sensitive tapes,
adhesives support substantial loads but merely to hold lightweight packaging adhesives
materials in place [18]

On the Basis of Curing Method

One-Part Adhesives
Heat-activated Adhesives of this type consist of a ready mixture of two Epoxies, urethanes, polyimides
curing adhesives components and harden from melt for thermoplastics
Light/UV- Light-activated adhesives are cured under a visible or UV Acrylics, cyanoacrylates,
activated curing light of appropriate wavelength. Adhesives of this type usually urethanes
adhesives contain photoinitiators to enhance curing reaction
Moisture-activated Cured on reacting with moisture present on the substrate RTV silicones, cyanoacrylates,
curing adhesives surface or in the air urethanes
Pressure-sensitive Adhesives of this type do not cure. These materials bond to Self-stick tapes
adhesives (PSAs) adherend surfaces at room temperature as low pressure is
applied [18]

Two-Part Adhesives
A two-part adhesive is cured when its two (or more) Epoxies, urethanes, acrylics,
components are mixed. The components react chemically, silicones
forming cross-links of the polymer molecules

Description of Common Adhesives

Name Description Advantages Disadvantages
Polyurethanes Formed by cross-linking Possess low viscosity, good Pose processing problems that
highly reactive isocyanates wettability, and penetrating arise due to their reaction
with various polyols and ability—which help the adhesives with water and their gaseous
are frequently used for to spread over the substrate nature. Limited temperature
joining surface—good cohesive strength, resistance, sensitive to
and high impact resistance; good moisture in cured and
flexibility at low temperatures uncured states [19]
(Continued)
 70 Handbook of Adhesive Technology, Third Edition

TABLE 3.1 (CONTINUED)

Classification of Adhesives
Polysulfides Obtained by the reaction Adhere well to almost all Require higher humidity for
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of sodium polysulfide with adherends faster cure, show poor elastic

organic dichlorides such recovery; also result in poor
as dichlorodiethyl formal creep resistance [20]
and ethylene dichloride
Polyesters Reaction products of Often used as hot-melt adhesives, Generally have poor resistance
dibasic acids with have good resistance to water, to chemicals. Other
polyfunctional hydroxyl nuclear radiation, and undesirable properties
materials biodeterioration [20] include high flammability
and tendency to brittleness
and crazing [18]
Acrylics Synthesized from a wide Capable of adhering to most Possess poor cohesive and
selection of acrylic and metals and polymers [21]. This is shear strengths, low elevated
methacrylic ester due to their low viscosity, good temperature strength, high
monomers wettability, and penetrating ability flammability, and bad odor of
that help the liquid to spread over uncured adhesive [19]
the substrate surface
Cyanoacrylates Known as instant Very rapid curing adhesives; Bond to skin instantly, posing
adhesives or superglues, possess excellent lap shear safety risks. Unpleasant
cyanoacrylates are also strength and good shelf life [19] fumes, poor peel strength,
from the acrylic family poor resistance to impact
tree, but having a loads, limited gap cure, poor
completely different cure durability on glass, low-
system temperature resistance (lose
strength at about 85°C), and
poor solvent resistance [22]
Anaerobics Derived from Very versatile and are used in a Brittle, limited gap filling, cure
methacrylates (Plexiglas), wide variety of applications rate is surface dependent, and
the basic ingredient in very expensive [23]
anaerobic adhesives is a
special liquid of small
molecules that can
combine chemically to
form a polymer or a group
of molecules

3.3 ADHESION
Adhesion is a multidisciplinary topic that involves surface chemistry, physics, rheology, polymer
chemistry, stress analysis, polymer physics, and fracture analysis [40]. The ASTM [41] defines
adhesion as “the state in which two surfaces are held together by interfacial forces which consist
of valence forces or interlocking actions or both.” When the adhesion between two surfaces is
caused by valence forces, this is called specific adhesion, while when they are held together by
interlocking action, this is called mechanical adhesion. Both of these play important roles in
understanding the effect of surface preparation on adhesion. These various types of intrinsic
forces that may operate across the adhesive–substrate interface are referred to as the mechanisms
of adhesion [42].
 Plasma Surface Treatment to Enhance Adhesive Bonding 71

3.3.1  Mechanism of Liquid –Solid Adhesion

During liquid–solid adhesion, there are usually three interfaces involved: the solid–gas interface,
the liquid–gas interface, and the solid–liquid interface. There are two conditions that are required
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to be met when a liquid spreads over a solid surface. Firstly, the SFE of the solid–gas interface must
be greater than the combined interfacial energies of the liquid–gas and the solid–liquid interfaces.
Secondly, the interfacial free energy of the solid–gas interface must exceed the interfacial free
energy of the solid–liquid interface. The adhesion mechanisms between liquid adhesive and solid
substrate have been explained on the basis of mechanical interlocking, adsorption, diffusion, and
electrostatic theories. These mechanisms have been known to be dependent on the surface char-
acteristics of the materials being used for the automotive and aerospace industries. These theories
can be used, solely or in combination with each other, to describe almost any kind of adhesion
phenomenon [43].
The mechanical interlocking theory of adhesion essentially proposes the interlocking of the
adhesive into the irregularities of the substrate surface as the major source of intrinsic adhesion
[42]. According to this theory, good adhesion occurs only when a liquid penetrates into the pores,
holes, crevices, and other irregularities of the surface of the substrate, and locks mechanically into
the texture of the substrate [44]. Pretreatment methods applied on a surface enhance adhesion [45],
as they result in microroughness on the adherend surface, which can improve adhesion strength by
providing mechanical interlocking. Beyond mechanical interlocking, the enhancement of adhesion
strength is due to the roughening of the adherend substrate. Further, surface roughness increases
surface area, improves the kinetics of wetting, and increases plastic deformation for better adhe-
sion [46,47]. The size and shape of the special features created on the surface have an influence
on adhesion, providing a tortuous path that prevents separation of the adhesive from the adherend
[48]. However, this theory cannot explain the attainment of good adhesion strength between smooth
surfaces [42].
The diffusion theory is based on the assumption that the adhesion strength of polymers to them-
selves (autohesion) or to one another is due to mutual diffusion of macromolecules across the inter-
face, thus creating an interphase [49]. This implies that the molecular chains or chain segments
are sufficiently mobile and mutually soluble [50]. To describe the self-diffusion phenomenon of
polymers, several theories have been proposed: entanglement coupling [51], cooperativity [52], and
reptation [53]. The reptation model has been applied to study tack, green strength, healing, and
welding of polymers [54]. Some studies have shown that the interdiffusion phenomenon exists in
mobile and compatible polymers and increases intrinsic adhesion. The diffusion theory, however,
has found limited application where the polymer and adherend are not soluble or the chain move-
ment of the polymer is constrained by its highly cross-linked, crystalline structure, or when it is
below its glass transition temperature [55].
The electrostatic theory of adhesion, as primarily proposed by Deryaguin and coworkers, states
that an electron transfer mechanism between the substrate and adhesive, having different electronic
band structures, can occur to equalize the Fermi levels [56]. The result is the creation of an electri-
cal double layer (EDL) at the interface [57]. These electrostatic forces at the interface are respon-
sible for resistance to separation of the adhesive and the substrate. Thus, the adhesion depends on
the magnitude of the potential barrier at the substrate–adhesive interface [56]. However, this kind
of potential barrier does not exist in some cases [58]. This theory could not be widely accepted,
because the EDL could not be identified without separating the adhesive bond. Also, as argued by
many researchers [59,60], the effect of the EDL on the adhesive bond strength was exaggerated.
The adsorption theory states that adhesion results from intimate intermolecular contact between
two materials, and involves surface forces that develop between the atoms in the two surfaces [61].
These forces may be due to physical adsorption—mainly van der Waals forces or secondary forces.
These adhesion forces may also be due to acid–base interaction [62,63] or hydrogen bonds [64,65].
 72 Handbook of Adhesive Technology, Third Edition

To obtain good adsorption, intimate contact must be reached, so that van der Waals interaction
or acid–base interaction or both can occur; hence, good wetting is essential. Thus, criteria for good
adhesion essentially become the same criteria as for good wetting, although this is a necessary but
not sufficient condition [55].
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3.3.2  Wetting
The wetting ability of a liquid is a function of the SFEs of the solid–gas interface, the liquid–gas
interface, and the solid–liquid interface. The adhesion forces between the liquid and the second
material will compete against the cohesive forces of the liquid. Liquids with weak cohesive bonds
and a strong attraction to another material (or the desire to create adhesive bonds) will tend to spread
over the material. Interfacial interactions are an important factor in the prediction of adhesion [66].
Liquids with strong cohesive bonds and weaker adhesion forces will tend to bead up or form a
droplet when in contact with another material [67]. One way to quantify a liquid’s surface wetting
characteristic is to measure the contact angle of a drop of liquid placed on the surface of a substrate.
According to Young’s equation, the interfacial tensions (liquid–vapor: γLV, solid–liquid: γSL, and
solid–vapor: γSV) at the three-phase contact are related to the equilibrium contact angle θ through:

γ SV = γ SL + γ LV cosθ (3.1)

The contact angle (θ), as seen in Figure 3.1, is the angle at which the liquid–vapor interface
meets the solid–liquid interface. The contact angle is determined by the resultant of the adhesion
and cohesive forces.
The SFE and the dispersion ( γ SD ) and polar ( γ SP ) components for any polymer are calculated
using the equation shown:

(1 + cos θ) γ LV = 2 ( γ SD γ DLV ) 2 + 2 ( γ SP γ PLV ) 2 (3.2)

1 1

Firstly, the contact angle of deionized water θ is measured on the surface. Therefore, in this
equation, θ is the measured contact angle of deionized water where the surface tension of deionized
water γLV and its two components, the dispersion γ DLV and the polar γ PLV , are known and the two
unknowns are γ SD and γ SP for the surface. Secondly, the contact angle θ of formamide is measured
on the surface and, consequently, θ is the measured contact angle of formamide where surface ten-
sion of formamide γLV and its two components, the dispersion γ DLV and the polar γ PLV are known
and the two unknowns are γ SD and γ SP for the surface. Thus, by solving these two equations, the
unknowns γ SD and γ SP for the surface are calculated. Finally, the total SFE γS is determined by
Equation 3.3:

γ S = γ SD + γ SP (3.3)

gLV

Liquid gSL θ gSV

Solid

FIGURE 3.1  Contact angle on a solid surface. (From [Link]

With permission)
 Plasma Surface Treatment to Enhance Adhesive Bonding 73

A deeper understanding of the adhesion process is achieved by calculating the thermodynamic

solid–liquid work of adhesion (WSL) required to separate a unit area of the two phases in contact
[69]. The combination of the Dupré expression [70], which assumes that there is negligible liquid
surface area change on adhesion to a solid surface [71], and Young’s equation [72] leads to an equa-
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tion that allows prediction of the bonding characteristics of a surface through two experimentally
measurable parameters, the liquid surface tension and its contact angle on the solid surface [73]:

WSL = γ SV + γ LV − γ SL = γ LV (1 + cosθ ) (3.4)

where:
WSL is the solid–liquid work of adhesion
γLV is the surface tension or free energy of the liquid
θ is the liquid contact angle on the solid surface

One important factor that influences adhesion strength is the ability of the liquid to spread uni-
formly on the substrate [74].
For spontaneous wetting to occur:

γ SV ≥ γ SL + γ LV (3.5)

However, this is an ideal case and is not possible with all polymers.
The tendency of a drop to spread over a flat solid surface increases as the contact angle decreases.
Thus, the contact angle provides an inverse measure of wettability [75], as shown in Table 3.2.

3.3.3  Polymer–Polymer Adhesive Joint

The science of a polymeric adhesive joint is concerned with two steps: the formation of the adhesive
bond and the physical strength of the adhesive bond. As the forces of attraction between the poly-
meric chains are mainly van der Waals forces, the SFE of a polymer is low. A basic requirement
for successful bonding is the spreading of the adhesive on the surface of the adherend or substrate.
This will occur if the SFE of the adhesive is lower than that of the adherend, but the typical values
of SFE are 30–50 mJ/m2 for adhesives and about 12 mJ/m2 to about 70 mJ/m2 for polymers [11].
Since the SFE of the adhesive can hardly be altered, attempts are made to increase the SFE of the
adherend by employing different surface modification techniques. When the polymers are modified
by different treatments, polar groups are formed on the polymeric surface. The presence of polar
groups on the polymer surface bridges the forces of physical adsorption and chemical adsorption
by the formation of covalent bonds with the adhesive, where the covalent bond is the primary force
responsible for adhesion. This covalent bond plays a significant role in producing adhesive bonds
that are even stronger than the cohesive strength of polymeric materials. Thus, surface treatment is
critical in any adhesive bonding operation.

3.4  SURFACE MODIFICATION OF POLYMERS

Adhesive bonds are dependent on the chemistry of the interface, and thus control of surface chem-
istry is critical to bond quality [42,76]. Thus, the most important step in adhesive bonding is surface
modification, which not only prevents or removes contaminants that can adversely affect bonding,
but also helps in creating chemically active sites on the surface to maximize bond strength. High-
performance polymers very often do not possess the desired surface properties for strong adhesive
bonding. They are hydrophobic in nature, and in general exhibit insufficient adhesive bond strength
due to relatively low SFE [77].
 74 Handbook of Adhesive Technology, Third Edition

TABLE 3.2
Relationship of Contact Angle with Wettability
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Strength of
Contact Angle Degree of Wetting Solid–Liquid Interactions Liquid–Liquid Interactions
θ = 0 Perfect wetting Strong Weak
0 < θ < 90° High wettability Strong Strong
Weak Weak
90° ≤ θ < 180 Low wettability Weak Strong
θ = 180° Perfect nonwetting Weak Strong

Several conventional methods such as chemical treatment, thermal treatment, and mechanical
treatment have been used to modify polymeric surfaces. The different treatment methods such as
(1) chemical treatment, (2) thermal treatment, (3) mechanical treatment, and (4) electrical treatment,
along with their merits and demerits, are discussed in the following subsections.

3.4.1 Chemical Treatment
The influence of chemical treatment on polymers includes surface alteration as well as other
morphological changes in the surface layer, such as surface roughness [78,79]. The wetting
characteristics of a polymeric surface are enhanced by the introduction of polar groups on the
surface when it is treated with a heavily oxidative liquid chemical such as chromic anhydride
with tetrachloroethane, chromic acid with acetic acid, or potassium dichromate with sulfuric
acid. The polymer surface is then rinsed clean of the etching chemicals and dried. Oxidation
may also be carried out with nitrogen oxide, cycloalkyl chromate, potassium permanganate,
and sodium hypochlorite. Chlorosulfonation and flame treatment in the presence of a halogen
could also be used. Bajpai et al. [80] have reported surface modification of the poly(methyl
methacrylate)–poly(vinylidene fluoride) (PMMA–PVDF) blend system under the chemical
environment of some organic liquids, namely, benzene, toluene, xylene, and acetone. Comyn
et al. [81] reported that although the sulfuric acid–orthophosphoric acid–water treatments were
ineffective in treating the surface of PEEK, the addition of 1% potassium permanganate, a
strong oxidizing agent, resulted in strong bonds with failure predominantly away from the
interfacial zone.
Carbon fiber (CF)-filled PEEK was chemically etched by Davies et al. [82] using a composition
of 7 g K2Cr2O7 + 12 g H2O + 150 g H2SO4. This resulted in an increase of adhesive bond strength.
Chromic acid etching increases the bondability of a plastic by introducing reactive sites, such as
hydroxyl, carbonyl, carboxylic, and −SO3H groups, to the plastic surface and forming root-like
cavities that provide sites for mechanical interlocking. The effect of this treatment varies from sub-
strate to substrate. For example, increasing the etch time and temperature increases only the etch
depth when etching PP. On the other hand, both the degree of oxidation and etch depth increase
with treatment time for polyethylene (PE). All these reactions take place in vessels under very
strict time–temperature–pressure conditions that are difficult to handle and are not feasible for use
on an industrial scale. Moreover, they require expensive waste disposal and may also pollute the
environment.

3.4.2 Thermal Treatment
Thermal treatment plays an important role in modifying the nature and concentration of sur-
face functional groups [83]. Thermal treatments have been used to produce activated car-
bons with basic character, and such carbons were effective in the treatment of some organic
 Plasma Surface Treatment to Enhance Adhesive Bonding 75

hydrocarbons [84]. Heat treatment of carbon in inert atmospheres (hydrogen, nitrogen, or argon)

could increase carbon hydrophobicity by removing hydrophilic surface functionalities, particu-
larly various acidic groups [85–88].
Thermal treatment also oxidizes the surface of polymers by introducing polar groups [89] such
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as carbonyl, carboxyl, or amide when the plastics are exposed to a blast of hot air. It also utilizes
a free radical mechanism accompanied by chain scission and some cross-linking, which helps in
improving the wettability of the surface. Ansari and Wallace [90] reported that the redox properties
of polypyrroles were improved with mild heating but were degraded at higher temperature. Lafdi
et al. [91] used heat treatment to alter the physical properties of a nanofiber-reinforced epoxy com-
posite. It was reported that heat treatment up to 1800°C resulted in improved flexural modulus and
strength of the nanocomposite, while heat treatment to higher temperatures demonstrated a slight
decrease in mechanical properties, likely due to the elimination of potential bonding sites caused by
the elimination of the truncated edges of the graphene layers.

3.4.3  Mechanical Treatment

The mechanical abrasion process has been used for surface pretreatment of polymers, because it
provides an effective and reliable way of ensuring improvement in adhesion of polymer surfaces
[92]. It serves to increase the surface area of the material by roughening the exposed areas prior
to adhesive bonding. Surface roughening increases bondability by dramatically increasing the
number of mechanical interlocking sites. Mechanical abrasion is carried out by dry blasting,
wet blasting, or hand/machine sanding. However, for low SFE plastics, the opposite effect can
occur. Silverman and Griese [27] examined a joining method using mechanical fasteners in
conjunction with FM300 adhesive for the AS4 CF–PEEK composite. Their findings revealed a
comparatively low lap shear strength value of around 17 MPa, when a chromic acid-etch surface
treatment was used prior to bonding and aluminum rivets were used to mechanically fasten the
joint.
Bhowmik et al. [93] investigated the effect of mechanical polishing prior to surface modifica-
tion of high-density polyethylene (HDPE) and PP sheets by exposure to dc glow discharge on the
SFE and their adhesive joint strength to steel. Mechanical polishing of the HDPE and PP sheets by
abrading with 800-grade emery paper prior to glow discharge treatment increased the adhesive joint
strengths over those observed in the case of unpolished polymers exposed to glow discharge only.
However, the use of prior mechanical polishing increases the joint strength only by a little more
than 10%, compared with a five-to-seven-times increase in strength observed as a consequence of
exposure to glow discharge of untreated samples. Mechanical processes are operator dependent
and labor intensive, produce dust, and are usually only employed in situations with low production
volumes. The abrasive materials that are used to remove particulates or residues are hazardous and
require disposal [94].

3.4.4 Electrical Treatment
While these traditional procedures are well tested and reliable, they are also time-consuming man-
ual processes. If not properly administered, these techniques can yield poor bond strengths, and can
even result in damage to composites that are fabricated with high-modulus fibers [95,96]. They also
suffer from problems of uniformity, reproducibility, and cost-effectiveness. The need for adequate
adhesion by activating the polymeric surface without affecting the bulk properties of the polymer
has resulted in the development of the plasma surface modification industry [12], which offers uni-
form, reproducible, economic, and environmentally friendly alternatives [13]. Electrical treatment
under atmospheric-pressure plasma (APP or normal plasma) [97] and low-pressure plasma (LPP)
(glow discharge) [98,99] are popular techniques that have been employed to modify the surfaces of
polymers.
 76 Handbook of Adhesive Technology, Third Edition

[Link]  Electrical Treatment by Generation of Plasma

Electrical treatment by generation of ionized plasma is a suitable technique that is used to modify
polymer surfaces without affecting their bulk properties. The term plasma was coined by Irving
Langmuir. A distinct fourth state of matter, it is broadly defined as partially or wholly ionized gas
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with approximately equal numbers of positively and negatively charged particles. Ionized means that
at least one electron is not bound to an atom or molecule, converting the atoms or molecules into posi-
tively charged ions. Plasma contains active species, such as electrons, ions, radicals, photons, and so
on, that initiate chemical and physical modifications on the polymer surface [100,101] by making the
surface electrically conductive and strongly responsive to electromagnetic fields. Ions and electrons
present in plasma break polymer chains due their high kinetic energy [102]. At the same time, free
radicals in plasma modify the chemical properties of polymers by introducing functional groups on
the polymer surface [103,104]. The interactions of the polymer with the plasma also alter the molecu-
lar weight of the surface layers by scissoring, branching, and cross-linking. Thus, when the material
whose surface is to be modified is placed in the plasma chamber, these energetic particles collide with
the surface of the material and cause molecular disruptions. This leads to a drastic modification of the
structure and properties of the surface [105], although this depends on the composition of the surface
and the gas used. There are mainly two types of plasmas: (1) thermal plasma and (2) cold plasma.
Thermal plasma is used to destroy solid, liquid, and gaseous toxic halogenated and hazardous
substances or to generate anticorrosion, thermal barrier, antiwear coatings, and so on. Cold plasmas
are used for surface modifications of materials, ranging from simple topographical changes to the
creation of surface chemistries and coatings that are radically different from the bulk material [106].
Cold plasmas are generated by glow discharges at reduced pressures of 0.01–10 torr, and pressure of
around 1 torr is sufficient for surface modification of polymers [107]. LPP using glow discharge and
APP using corona discharge are convenient methods for surface modification of polymers enhance
their adhesion characteristics.
[Link].1  Low-Pressure Plasma (Glow Discharge)
A glow discharge is an ionized gas consisting of equal concentrations of positive and negative charges
and a large number of neutral species. It is generated by applying a potential difference (of a few
hundred volts to a few kilovolts) between two electrodes that are inserted in a cell filled with a gas
(an inert gas or a reactive gas) at a pressure ranging from a few millitorr to 10 torr [108]. Due to the
potential difference, electrons emitted from the cathode by the cosmic radiation are accelerated away
from the cathode, and give rise to collisions with the gas atoms or molecules (excitation, ionization,
dissociation). The excitation collisions give rise to excited species, which can decay to lower levels
by the emission of light. The ionization collisions create ion–electron pairs. The ions are accelerated
toward the cathode, where they release secondary electrons. These electrons are accelerated away
from the cathode and can give rise to more ionization collisions. In its simplest form, the combination
of secondary electron emission at the cathode and ionization in the gas gives rise to self-sustained
plasma [109], as shown in Figure 3.2.
Due to the various collision processes occurring in the plasma, a large number of different
plasma species are generated: electrons, atoms, molecules, several kinds of radicals, several kinds
of (positive and negative) ions, excited species, and so on. These active species activate the surface
of the polymer and cause the surface layer to be oxidized or cross-linked, enabling it to become sig-
nificantly active for participation in adhesion. There are different variants of glow discharge plasma:

• Direct current (dc)

• Radio-frequency (RF)
• Microwave (MW)

In dc glow discharge, a continuous potential difference is applied between cathode and anode,
giving rise to a constant current. However, this setup gives problems when one of the electrodes is
 Plasma Surface Treatment to Enhance Adhesive Bonding 77

Ar0

Ar+ e–
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e– + Ar0 Ar* + e– Ar0 + e– + hv

Ar+ + 2 e– Anode
–
Ar+

M0 + e–

+ Ar*m M+ 1 M*
Cathode
+ Ar+

FIGURE 3.2  Schematic overview of the basic plasma processes in a glow discharge. When a potential dif-
ference is applied between two electrodes (target material M is the cathode and the substrate is attached to the
anode), Ar gas will break down into electrons and positive ions. The latter can cause secondary electron emis-
sion at the cathode. The emitted electrons give rise to collisions in the plasma; for example, excitation (which
is often followed by deexcitation with emission of radiation) and ionization (which creates new electrons and
ions, and therefore makes the glow discharge a self-sustaining plasma). Besides the argon ions, fast argon
atoms bombarding the cathode can also give rise to sputtering, which is important for several applications.
(From Bogaerts, A. et al., Spectrochimica Acta Part B, 57, 109–119, 2002.)

nonconducting as, due to the constant current, the electrodes become charged up, which may lead
to burnout of the glow discharge. This problem is overcome by applying an alternating voltage
between the two electrodes, as in the capacitively coupled radio-frequency (CCRF) glow discharge.
The charge accumulated during one half of the cycle is neutralized by the opposite charge accu-
mulated during the next half-cycle in the RF glow discharge. RF plasmas can be sustained at lower
gas pressure, and are characterized by higher ionization efficiency as compared with dc plasmas.
The majority of plasma processing has been carried out at low pressure in a vacuum chamber and
is viewed as a necessary processing requirement. In principle and practice, however, APPs provide a
critical advantage over widely used LPPs, as they do not require expensive and complicated vacuum
systems. Without a vacuum system, the costs of materials processing are reduced substantially and
materials issues related to vacuum compatibility are not of concern. Therefore, the use of APPs is
beginning to greatly expand the current scope of materials processing.

[Link].2  Atmospheric-Pressure Plasma

APPs [97] are gaining greater acceptance than other plasma techniques, because they are easy to
integrate into existing production lines and can treat specific parts of a substrate selectively [110,111].
Also, in contrast to most corona treatments (and dielectric barrier discharges) [112], APPs are not
limited to flat and thin substrates, but can also be used for large three-dimensional objects. APP
shows significant potential for improving interfacial adhesion. It minimizes downstream wastes
from subsequent surface preparation. Since it can be automated, it reduces process variability while
increasing reliability and processing rates [113].
APP is the name given to the special case of plasma in which the pressure approximately matches
that of the surrounding atmosphere—the so-called normal pressure. It is generated by alternat-
ing current (ac) excitation (corona discharge and plasma jets). By means of high-voltage discharge
(5–15 kV, 10–100 kHz) in the plasma jet, a pulsed electric arc is generated. A process gas, usually
oil-free compressed air flowing past this discharge section, is excited and converted to the plasma
state. This plasma then passes through a jet head to arrive on the surface of the material to be treated.
The jet head is normally at earth potential and, in this way, the potential-carrying part of the plasma
stream is largely held back [114]. In addition, it determines the geometry of the emergent beam. It is
 78 Handbook of Adhesive Technology, Third Edition

observed that during APP discharge, ion bombardment physically and chemically removes oxides
and reducible compounds from surfaces and many other contaminants are vaporized. In addition,
gas molecules are accelerated to an excited state, releasing active free radicals and ultraviolet (UV)
energy [115]. Free radicals activate chemical reactions on surfaces, inducing intermolecular cross-
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linking. When compared with corona discharges, APPs produce significantly more homogeneous
and uniform surface activation across material surfaces, and increase the microroughness of sur-
faces, with introduction of active species.

3.5 EFFECT OF PLASMA TREATMENT ON PHYSICOCHEMICAL

PROPERTIES OF POLYMERS
Many researchers have documented well that plasma treatment of polymer surfaces not only
increases the polarity of the polymer surfaces, but also results in surface roughening [116–118].
These surface properties, such as polarity and roughness, play an important role in successful appli-
cation of polymers to form structural parts using adhesive bonding [116,119].
The presence of polar groups is readily established by determining SFE through contact angle
measurements [120]. According to Williams et al. [121], adhesion is correlated with the fraction
of the polymer surface sites that are oxidized and converted into active functional groups. This
physicochemical change brought about on the polymer surface is determined by x-ray photoelec-
tron spectroscopy (XPS) and infrared (IR) spectroscopy. The change in surface morphology on the
polymer surface is measured by atomic force microscopy (AFM) analysis. Further, it is worthwhile
to note that the physicochemical change on the surface of polymers plays an important role in
contribution to adhesion strength.

3.5.1  Contact Angle Measurement and Surface Free Energy Determination

Pelagade et al. [122] studied the effect of low-energy (300 eV) argon plasma treatment on the sur-
face of PC. They observed that the SFE increased from 38.5 mJ/m2 to 74.9 mJ/m2 on increasing
the treatment time, as shown in Figure 3.3. The corresponding water contact angle decreased from
63o to 17o.
Pandiyaraj et al. [98] studied the effect of dc glow discharge air plasma on poly(ethylene tere-
phthalate) (PET) films. It was observed that the contact angle on the untreated PET surface was

80

70
Surface free energy (γs )(mJ/m2)

60

50
(SFE) γs
40
(Polar component) γ sP
30
(Dispersion component) γ sP
20

10

0
Untreated Ar (5 min) Ar (10 min) Ar (50 min)

FIGURE 3.3  Comparison of surface free energy (SFE) and its polar and dispersion components before and
after the Ar plasma treatment. (From Pelagade, S. et al., J Phys.: Conf. Ser., 208, Paper ID: 012107, 1–8, 2010.)
 Plasma Surface Treatment to Enhance Adhesive Bonding 79

86.2° for distilled water and decreased by 50% after plasma treatment. The SFE of plasma-modified
PET films increases on increasing the exposure time, as shown in Figure 3.4a. It reaches a maxi-
mum value at 15 min of exposure time, and thereafter tends to saturate. This may be due to lack of
any further change in the oxygen content incorporated onto the surface. Figure 3.4a clearly dem-
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onstrates that the total SFE of the PET film attained a higher value when the film was exposed to

75

70 280 V 350 V
300 V 400 V
65

60

55

50

45

40

35

30

25

20
0 2 4 6 8 10 15 20 25
Exposure time (min)
(a)

60
280 V 350 V
300 V 400 V
50

40

30

20

10

0
0 2 4 6 8 10 15 20 25
Exposure time (min)
(b)

FIGURE 3.4  Variation of the (a) total SFE and (b) polar component of PET film with time of exposure to
dc glow discharge plasma treatment at different discharge potentials. (From Pandiyaraj, K.N. et al., J Phys.:
Conf. Ser., 208, Paper ID: 012100, 1–7, 2010.)
 80 Handbook of Adhesive Technology, Third Edition

higher discharge potential compared with lower potentials. A similar kind of trend was observed in
the increase in polar components, as shown in Figure 3.4b.
Kitova et al. [123] studied the RF plasma treatment of PC substrates, and found that all RF
plasma treatments led to an increase in the polar component of SFE of PC. Narushima and Ikeji
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[102] used oxygen plasma to improve the adhesion strength at Cu–PEEK interfaces. It was observed
that the water contact angle on the untreated PEEK surface was 98°, which decreased to 62° and
66°, respectively, after pulsed oxygen plasma and conventional oxygen-plasma treatments. They
concluded that both pulsed oxygen plasma and conventional oxygen plasma introduced hydrophilic
oxygen functional groups that resulted in an increase in SFE of the polymer.
Iqbal et al. [124] investigated the adhesion performance of CF- and glass fiber (GF)-reinforced
PPS after surface modification with APP. It was observed that surface modification by APP resulted
in a substantial increase in the polar component of SFE of these materials, as shown in Table 3.3. In
the case of CF-reinforced PPS composite, the increase in SFE was 52% after the plasma treatment.
Lommatzsch et al. [125] used an APP jet to activate PE samples. The presence of polar func-
tional groups on the polymer surface was revealed by contact angle measurements, where it was
found that the water contact angle on an untreated PE surface was 93.3°, which decreased to 21.6°
after air-plasma treatment.
Arpagaus et al. [126] found that a plasma exposure time of 0.14 s effectively improved the wetta-
bility of HDPE and copolyamide (Co-PA) powders. The water contact angle was reduced from more
than 90° (untreated powder) down to 65° for HDPE and to 76° for Co-PA powder as a consequence
of O2–Ar-plasma treatment, indicating a more hydrophilic surface. The total SFEs increased by a
factor of 1.5, showing an increase from 31.2 mJ/m2 to 47.9 mJ/m2 for HDPE and to 44.9 mJ/m2 for
Co-PA.
Bhatnagar and coworkers [116,127] used low-pressure air–N2 plasma under RF glow discharge as
well as APP to alter wetting, chemical, and morphological characteristics of PEEK. It was observed
that the contact angles of deionized water and formamide on the PEEK surface decreased sig-
nificantly when the surface of the PEEK was modified by LPP and it decreased more with APP
treatment.
It was also interesting to note that the primarily polar component of the SFE of PEEK increased
on its exposure to both LPPs and APPs, while the change in the dispersion component of the SFE of
PEEK was relatively small. Thus, an increase in the polar component of SFE results in an increase
in the total SFE of PEEK. It was observed that the SFE of the as-received PEEK was 51.1 mJ/m2,
and increased after surface modification to the corresponding highest value of 70.7 mJ/m2 obtained
in this study when PEEK was exposed to APP for 30 s, as shown in Table 3.4. However, exposure to
LPP increased the SFE only to 60 mJ/m2 for an exposure time of 120 s.
Consequently, the increase in the total SFE of PEEK is dominated by the polar component
(Table 3.4). It is, therefore, apparent that APP is capable of increasing SFE more as compared
with LPP.

TABLE 3.3
Surface Free Energies of Substrates with Polar and Dispersion Components
before and after Plasma Treatment

Substrate Material γSP(mJ/m2) γSP(mJ/m2) γS (mJ/m2)

Untreated CF–PPS composite 24.7 22.9 47.6
Untreated GF–PPS composite 26.3 17.7 44.0
Plasma-treated CF–PPS composite 55.9 16.6 72.5
Plasma-treated GF–PPS composite 52.9 17.6 70.5
Source: Iqbal, H.M.S., et al., Polym. Eng. Sci., 50, 1505–1511, 2010 with permission.
 Plasma Surface Treatment to Enhance Adhesive Bonding 81

TABLE 3.4
Surface Free Energy Values and Its Polar and Dispersion Components of PEEK
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Sample Treatment Time (s) γSP(mJ/m2) γSD (mJ/m2) γS (mJ/m2)

Untreated PEEK 0 4.3 46.8 51.1
LPP-treated PEEK 30 24 29 53
60 30 26.2 56.2
120 36 24 60
240 34 23 57
480 31 20 51
APP-treated PEEK 30 54 16.7 70.7
60 52 16 68
Source: Jha, S. et al., J. Appl. Polym. Sci., 118, 173–179, 2010 with permission.

3.5.2  X-Ray Photoelectron Spectroscopy Analysis

XPS analysis of O2–Ar-plasma-treated HDPE powders revealed the formation of oxygen functional
groups on the surface, such as C–O–C (alcohol or ether), O–C=O (acid or ester) and C=O (alde-
hyde or ketone). These polar groups enable interaction with water through hydrogen bonds, and are
responsible for higher powder wettability [126].
XPS analysis of untreated PET, and that treated under RF glow discharge using pulsed argon
and oxygen plasmas, shows that the C1s spectra could be decomposed into three components: C–H
at 285.0 eV, C–O at 286.5–286.8 eV, and C=O at 288.9–289.1 eV. But, the pulsed Ar and O2 plasma
treatments led to a decrease in the relative concentration of the C–H group and an increase in the
relative concentration of the C–O and C=O groups [128].
Narushima and Ikeji [102] compared the effects of pulsed oxygen plasma and conventional oxy-
gen plasma on the surface of PEEK for its surface metallization with Cu. The C1s spectrum of
PEEK film can be resolved into three main components: 285.0 eV (C–H group), 286.4 eV (C–O
group), and 287.4 eV (C=O group) [129]. The relative intensities of the C–H, C−O, and C=O com-
ponents of untreated PEEK film are 75%, 25%, and 5%, respectively. Both pulsed and conventional
oxygen-plasma treatments decrease the relative intensity of the C−H group and result in the forma-
tion of a new functional group, COO, with relative intensities of 1% and 5%, respectively, as listed
in Table 3.5. This is in accord with an increased oxygen:carbon (O:C) ratio.
Kim et al. [130] exposed a polyimide (PI) surface to Ar–N2 plasmas after KOH treatment. The
change in the surface functionalities of the PI was studied by XPS analysis. The chemical com-
position of the untreated sample was determined to be 73.1% C, 20.6% O, and 6.3% N from the
integrated peak signal intensities, as shown in Figure 3.5a. After the KOH and Ar–N2 plasma treat-
ments, the chemical composition of the PI surface changed to 62.4% C, 21.4% O, and 12.5% N
(Figure 3.5c), indicating an increase in formation of polar groups on the surface.

TABLE 3.5
Percentage Content of Each Component

Sample C–H CO C=O COO O:C ratio

Untreated PEEK 75 25 5 — 0.17
Conventional oxygen plasma-treated PEEK 68 26 6 5 0.23
Pulsed plasma-treated PEEK 69 25 6 1 0.24
 82 Handbook of Adhesive Technology, Third Edition

C1s O1s (a)

N1s
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Intensity (arb. units)

(b)
K2p K2s

(c)

N1s

200 300 400 500 600 700

Binding energy (eV)

FIGURE 3.5  The XPS survey spectra of PI at: (a) the initial state, (b) after alkaline treatment, and (c) after
Ar and N2 plasma treatment. (From Kim, C. et al., J. Korean Phys. Soc., 54, 621–627, 2009.)

Surface studies on PET film exposed to dc glow discharge air plasma indicate that polar groups
are created on the treated surface [98]. This was analyzed from the XPS C1s high-resolution spectra
for both the untreated and dc glow discharge air plasma-treated samples, as shown in Figure 3.6a
and b. The spectrum of untreated PET is composed of four main components at 285 eV (component
C1), 286.43 eV (component C2), 288.95 eV (component C3), and 291.37 eV (component C4), which
may be attributed to C–C, C–O, O=C–O, and π–π* shake-up satellite in phenyl groups, respectively
(Figure 3.6a) [117,131,132]. The spectrum of plasma-treated PET film (Figure 3.6b) also shows com-
ponents C1, C2, and C3, and additional peaks at 286.76 (component C5), 288.10 eV (component C6),
and 286.0 (component C7), which may be attributed to C–OH and/or C–O–O–H, –C=O, and C–N
groups [131].
The XPS C1s spectra (Figure 3.7) show significantly higher oxygen peaks when PEEK is exposed
to APP using air as the process gas as compared with LPP using air–N2 as the process gas, indicat-
ing extensive oxidation of the polymer surface [116]. The XPS C1s spectrum (Figure 3.7b) of LPP-
treated PEEK shows a new peak at 289.0 eV (COO group) (which is not present in the untreated
PEEK), along with peaks at 285.0 eV (C–H group), 286.5 eV (C–O group), and 287.9 eV (C=O
group). The C1s peak of APP-treated PEEK (Figure 3.7c) can also be deconvoluted into four com-
ponents: 285.0 eV (CH group), 286.5 eV (C–O group), 287.9 eV (C=O group), and 289.0 eV (COO
group), but with higher concentrations of all the three functional groups, C–O, C=O, and COO, as
is evident from Table 3.6.

3.5.3  Atomic Force Microscopy Analysis

According to some investigators [133–135], changes in surface morphology on polymer surfaces
also play an important role in improving adhesion through a process known as mechanical inter-
locking. Various researchers have studied polymer surfaces by AFM to investigate the topographi-
cal changes on the surface of polymers when they are exposed to plasma.
The variation in surface roughness after the surface treatment of PI films was determined using
AFM [130].
 Plasma Surface Treatment to Enhance Adhesive Bonding 83

10,000
C1
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8,000

6,000
CPS

C3
C2
4,000

2,000 C4

300 298 296 294 292 290 288 286 284 282 280
Binding energy (eV)
(a)

8,000

7,000 C1

6,000

5,000

4,000 C3 C2
CPS

3,000
C5 C6
2,000
C7
1,000

–1,000
302 300 298 296 294 292 290 288 286 284 282 280
Binding energy (eV)
(b)

FIGURE 3.6  XPS spectra of (a) untreated PET and (b) plasma-treated PET. (From Beamson, G., and Briggs,
D., High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database, John Wiley, Chichester,
UK, 1992.)

The untreated surface of the PI showed a root mean square surface roughness (R rms) of 1.42 nm,
as shown in Figure 3.8a. After KOH + Ar–N2 plasma treatment, root mean square surface roughness
rose to 28.52 nm, as shown in Figure 3.8b.
Pandiyaraj et al. [117] examined the topography of untreated PET films and of those exposed
to dc glow discharge air plasma by AFM. It was observed that the surface of untreated PET film
was relatively smooth (Figure 3.9a), but after plasma treatment, the surface of the PET film showed
rough morphology, as shown in Figure 3.9b.
 84 Handbook of Adhesive Technology, Third Edition

C–H C–H
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XPS intensity (a.u.)

XPS intensity (a.u.)

C–O

C–O
C=O
C=O
COO

280 282 284 286 288 290 292 294 280 282 284 286 288 290 292 294
Binding energy (eV) Binding energy (eV)
(a) (b)

C–H
XPS intensity (a.u.)

C–O

C=O
COO

280 282 284 286 288 290 292 294

Binding energy (eV)
(c)

FIGURE 3.7  XPS C1s spectra: (a) untreated PEEK, (b) low-pressure plasma (LPP) treated PEEK,
(c)  ­
atmospheric-pressure plasma (APP) treated PEEK. (From Bhatnagar, N. et al., Surf. Eng. Appl.
Electrochem., 48, 117–126, 2012.)

TABLE 3.6
Percentage Content of Each Component

Sample C–H CO C=O COO

Untreated PEEK 75 19.8 5.2 —
LPP-treated PEEK 64.2 27.0 6.5 2.3
APP-treated PEEK 59.6 27.6 7.6 5.2

When PC is exposed to low-energy Ar plasma, the roughness of the PC sample increases, as

shown in Figure 3.10b, which helps in the enhancement of its adhesion property [122].
O’Kell et al. [136] have examined by AFM the topography of untreated PE surfaces and those
exposed to RF glow discharge under air and nitrogen gases at 13 MHz. It was observed that both
plasmas caused the polymer surface to roughen, with nitrogen plasma treatment having a more pro-
nounced effect. AFM studies by Gupta et al. [132] on RF glow discharge-exposed polyester films
 Plasma Surface Treatment to Enhance Adhesive Bonding 85
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1
2
1 3
2
3 4
4

(µm)
(a)

0
1
2
1 3
2
3 4
4

(µm)
(b)

FIGURE 3.8  Variation in surface roughness of (a) bare PI films: R rms = 1.42 nm, (b) KOH + Ar 100 W + N2
60 W: R rms = 28.52 nm. (From Kim, C. et al., J. Korean Phys. Soc., 54, 621–627, 2009.)

revealed that the polymer surface became progressively rougher on exposure to glow discharge Ar
plasma followed by O2 exposure, while the virgin film had a relatively smooth surface.
Studies using AFM carried out by Bhatnagar et al. [116] also show that exposure to plasma results
in significant transformation on the polymer surface. After the LPP treatment with air–N2, the sur-
face of the PEEK showed a rough morphology, as shown in Figure 3.11b, and after APP treatment
using air, there was a further increase in surface roughness, as is evident from Figure 3.11c. This
apparent increase in surface roughness results in improvement in wettability and bond strength.

3.5.4  Adhesion Characteristics of Surface-Modified Polymers

The work of adhesion increases with the increase in SFE, which results in higher adhesive joint
strength [10].
Williams et al. [121] observed that the lap shear strength and crack delamination resistance of
CF–epoxy composites increased by 50% for surfaces prepared by helium–oxygen plasma activa-
tion instead of solvent wiping and abrasion. Zhang et al. [137] used air plasma to modify PPS
film to improve interfacial adhesion and mechanical properties of PPS–GF cloth composites. They
observed that tensile strength and notched impact strength of plasma-treated PPS–GF cloth (50:50)
composite increased by 11% (from 248.49 MPa to 275.70 MPa).
Iqbal et al. [124] compared the tensile lap shear strength of PPS–CF-bonded joints before and
after APP treatment with neat epoxy adhesive and nanofilled epoxy adhesive. The joint strength
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(nm)
0

5
0
500

500
1000 1000

(nm)
(a)
(nm)

0
0 100

500

500
1000
1000
(nm)
(b)

FIGURE 3.9  AFM micrographs of (a) untreated PET film and (b) plasma-treated PET film. (From Pandiyaraj,
K.N. et al., Surf. Coat. Technol. 202, 4218–4226, 2008.)

increased from 6.1 to 21.5 MPa after APP treatment, resulting in a more than three times improve-
ment in the adhesion properties of the composite joint after the plasma treatment. Analysis of
failed surfaces of untreated PPS–CF composites revealed that the failure was essentially interfacial
between composite and adhesive, but APP treatment resulted in cohesive failure of the substrate
material.
Bhatnagar and coworkers [127] observed that the tensile lap shear strength of PEEK bonded with
epoxy adhesive was significantly influenced by surface modification of PEEK under APP. The result
revealed that the tensile lap shear strength of adhesive joints increased from 0.5 MPa to 4.00 MPa
after LPP treatment using air–N2 gas and further increased to 8.00 MPa after APP treatment with
air. The fractured surfaces of untreated, LPP-treated, and APP-treated PEEK revealed that APP
treatment resulted in a shift of locus of failure from the adhesive–substrate interface to within the
adhesive or substrate material. This is in accord with the 15 times increase in the joint strength as
compared with untreated PEEK.
 Plasma Surface Treatment to Enhance Adhesive Bonding 87
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2
4
6 x 2.000 µm/div
z 200.000 nm/div
8

(a) µm

2
4
x 2.000 µm/div
6 z 200.000 nm/div
8

(b) µm

FIGURE 3.10  AFM photomicrograph of (a) untreated PC and (b) Ar plasma-treated PC. (From Pelagade, S.
et al., J Phys.: Conf. Ser. 208, Paper ID: 012107, 1–8, 2010.)
 88 Handbook of Adhesive Technology, Third Edition

nm

160
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nm
160
120 120
80
40
10
10
80 7.5
7.5
5 5
40 µm
µm
2.5
2.5
0
0 0
(a)
nm
200

160
nm
200
160
120 120
80
40
10
10
80 7.5
7.5
5 5
40
µm µm
2.5
2.5
0
0
(b) 0

nm
250

200 nm
250
200
150
150 100
50
0
10
10
100 7.5
7.5
5 5
50 µm
µm
2.5
2.5
0
0 0
(c)

FIGURE 3.11  AFM micrographs of (a) untreated PEEK, (b) low pressure plasma-treated PEEK, (c) atmo-
sphere pressure plasma treated PEEK [116].
 Plasma Surface Treatment to Enhance Adhesive Bonding 89

3.6 SUMMARY
Surface modification of polymers on exposure to plasma results in the formation of polar groups on
the polymer surfaces. This leads to an increase in the polar component of SFE, which further results
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in an increase in total SFE. As a result, the wettability of the polymer surface increases, resulting in
better spreading of the liquid resin (adhesive) and increasing work of adhesion due to polar groups,
which could form covalent bonds with the resin. The resin solidifies by cross-linking occurring due
to hardener. Also, the high temperature generated during exposure of the polymer surface to plasma
and, in particular, to APP, raises the surface temperature to a level that exceeds the glass transition
temperature (Tg) of the polymer, which could create micropits on the polymer surface and make the
surface rough. Thus, both SFE and surface roughness, which play a significant role in increasing the
joint strength, have been found to increase manifold by modifying the polymer surface on exposure
to plasma, especially APP.

ACKNOWLEDGMENTS
This book chapter is based on my PhD thesis. I am thankful to my supervisors, Prof. Sangeeta Jha
and Prof. Shantanu Bhowmik for suggesting my PhD thesis topic, guiding me to successful comple-
tion of my PhD. I am grateful to the authorities of BIT Mesra, Ranchi and SMIT, Sikkim for permit-
ting me to use their lab facilities. I am also thankful to TU Delft, the Netherlands and KAIST, South
Korea for providing analytical data used in this chapter.

REFERENCES
1. A. H. Mourad. Thermo-mechanical characteristics of thermally aged polyethylene/polypropylene
blends. Mater. Design 31, 918–929 (2010).
2. M. Friedman and G. Walsh. High performance films: Review of new materials and trends. Polym. Eng.
Sci. 42, 1756–1788 (2002).
3. J. P. Sargent. Durability studies for aerospace applications using peel and wedge tests. Int. J. Adhesion
Adhesives 25, 247–253 (2005).
4. A. R. Hutchinson and S. Iglauer. Adhesion of construction sealants to polymer foam backer rod used in
building construction. Int. J. Adhesion Adhesives, 26, 555–556 (2006).
5. H. W. Bonin, J. R. Vantine and V. T. Bui. A container based on polymer composite materials for the
ultimate disposal of spent nuclear fuel and radioactive waste. Nuclear Technol. 169, 150–179 (2010).
6. G. McGrath, Adhesives: An introduction. [Link] (2001).
7. Z. A. Aga and E. Woldesenbet. Surface preparation effect on performance of adhesively-bonded graph-
ite/epoxy composites subjected to impact. J. Adhesion Sci. Technol. 21, 51–65 (2007).
8. J. Custódio, J. Broughton and H. Cruz. A review of factors influencing the durability of structural
bonded timber joints. Int. J. Adhesion Adhesives, 29, 179–185 (2009).
9. S. Bhowmik, H. W. Bonin, V. T. Bui and R. D. Weir. Modification of high-performance polymer com-
posite through high-energy radiation and low-pressure plasma for aerospace and space applications.
J. Appl. Polym. Sci. 102, 1959–1967 (2006).
10. K. L. Mittal. The role of the interface in adhesion phenomena. Polym. Eng. Sci. 17, 467–473 (1977).
11. A. V. Pocius. Adhesives. In: Physical Properties of Polymers Handbook, Part V, J. E. Mark Ed.)
pp. 479–486, Springer, New York (2007).
12. M. Strobel, C. S. Lyons and K. L. Mittal (Eds.). Plasma Surface Modification of Polymers: Relevance
to Adhesion, CRC Press, Boca Raton, FL (1994).
13. M. Goldman, A. Goldman and R. S. Sigmond. The corona discharge, its properties and specific uses.
Pure Appl. Chem. 57, 1353–1362 (1985).
14. N. Bhatnagar, S. Jha and S. Bhowmik. Energy dispersive spectroscopy study of surface modified PEEK.
Adv. Mater. Lett. 2, 52–57, (2011).
15. N. Bhatnagar. Effect of plasma on adhesion characteristics of high performance polymers: A critical
review. Rev. Adhesion Adhesives 1, 397–412 (2013).
16. R. H. Todd, D. K. Allen and L. Alting. Manufacturing Processes Reference Guide, Industrial Press,
New York (1994).
 90 Handbook of Adhesive Technology, Third Edition

17. J. H. Lau, C. P. Wong, N. C. Lee and S. W. R. Lee. Electronics Manufacturing: With Lead-free, Halogen-
free, and Conductive-adhesive Materials, McGraw-Hill Professional, New York (2002).
18. S. Ebnesajjad and A. H. Landrock. Adhesives Technology Handbook, 2nd edn, pp. 63–135, William
Andrew, Norwich, NY (2008).
Downloaded By: [Link] At: 00:29 03 Jan 2019; For: 9781315120942, chapter3, 10.1201/9781315120942-3

19. F. C. Campbell (Ed.). Joining: Understanding the Basics, ASM International (2011).
20. A. T. Wolf. Construction sealants. In: Handbook of Sealant Technology, K. L. Mittal and A. Pizzi
(Eds.), pp. 312–388, CRC Press, Boca Raton, FL (2009).
21. A. J. Kinloch. Structural Adhesives: Developments in Resins and Primers, Elsevier Applied Science
Publishers, pp. 7–11 (1986).
22. [Link]
23. J. D. David. Adhesives and Sealants: Technology, Applications and Markets, Rapra Market Report,
Smithers Rapra Publishing, Shawbury, UK (2003).
24. R. Vodicka. Thermoplastics for Airframe Applications: A Review of the Properties and Repair Methods
for Thermoplastic Composites. A report from DSTO Aeronautical and Maritime Research Laboratory,
Melbourne, Australia (1996).
25. G. C. Mays and A. R. Hutchinson. Adhesives in Civil Engineering, p. 333, Cambridge University Press (1992).
26. B. R. Bonazza. Adhesive bonding of improved PPS thermoplastic composites. Proc. 35th International
SAMPE Symposium, pp. 859–870 (1990).
27. E. M. Silverman and R. A. Griese. Joining methods for graphite/PEEK thermoplastic composite.
SAMPE J. 25, 34–38 (1989).
28. S. Y. Wu. Adhesive bonding of thermoplastic composites. Proc. 35th International SAMPE Symposium,
846–858 (1990).
29. D. K. Kohli. Development of a high toughness heat resistant 177°C (350°F) curing 907 film adhesive
for aerospace bonding applications: FM 377 adhesive. Proc. 35th International SAMPE Symposium,
pp. 907–922 (1990).
30. J. W. Powers and W. J. Trzaskos. Recent developments in adhesives for bonding advanced thermoplastic
composite. Proc. 34th International SAMPE Symposium, 1987–1998 (1989).
31. R. Mahlberg, H. E. M. Niemi, F. Denes and R. M. Rowell. Effect of oxygen and hexamethyldisiloxane
plasma on morphology, wettability and adhesion properties of polypropylene and lignocellulosics. Int.
J. Adhesion Adhesives 18, 283–297 (1998).
32. R. M. Paroli, K. K. Y. Liu and T. R. Simmons. Thermoplastic polyolefin roofing membranes.
Construction Technology Update No. 80, Institute for Research in Construction, National Research
Council of Canada (1999).
33. G. K. A. Kodokian and A. J. Kinloch. The adhesive fracture energy of bonded thermoplastic-fibre com-
posites. J. Adhesion 29, 193–218 (1989).
34. D. C. Goeders and J. L. Perry. Adhesive bonding PEEK/IM-6 composite for cryogenic applications.
Proc. 36th International SAMPE Symposium, pp. 348–361 (1991).
35. W. Alexander and G. Eric. UV-based patterning of polymeric substrates for cell culture applications.
Biomed Microdevices 4, 33–41 (2002).
36. M. Lampin, R. Warocquier-Clérout, C. Legris, M. Degrange and M. F. Sigot-Luizard. Correlation
between substratum roughness and wettability, cell adhesion, and cell migration. J. Biomed. Mater.
Res. Part B 36, 99–108 (1997).
37. K. L. Ohashi and R. H. Dauskardt. Effects of fatigue loading and PMMA precoating on the adhesion
and subcritical debonding of prosthetic-PMMA interfaces. J. Biomed. Mater. Res., 51, 172–183 (2000).
38. Q. Zhao, Y. Liu and E. W. Abel. Effect of temperature on the surface free energy of amorphous carbon
films. J. Colloid Interface Sci. 280, 174–183 (2004).
39. J. M. Schakenraad, H. J. Busscher, C. R. Wildevuur and J. Arends. Thermodynamic aspects of cell
spreading on solid substrata. Cell Biophys. 13, 75–91 (1988).
40. F. Awaja, M. Gilbert, G. Kelly, B. Fox and P. J. Pigram. Adhesion of polymers. Prog. Polym. Sci. 34,
948–968 (2009).
41. ASTM D907. Standard Definitions of Terms Relating to Adhesives, Annual Book of ASTM Standards
Vol. 15, 06 (1984).
42. A. J. Kinloch. Adhesion and Adhesives: Science & Technology, Chapman and Hall, New York (1987).
43. A. Nihlstrand. Plasma modification of polypropylene materials for improved adhesion. Doctoral thesis,
Chalmers University of Technology, Gothenburg, Sweden (1996).
44. K. W. Allen. Theories of adhesion. In: Handbook of Adhesion, 2nd edn, D. E. Packham (Ed.), John
Wiley & Sons (2005).
 Plasma Surface Treatment to Enhance Adhesive Bonding 91

45. H. M. Clearfield, D. K. McNamara and G. D. Davis. Adherend surface preparation for structural adhe-
sive bonding. In: Adhesive Bonding, L. H. Lee (Ed.), pp. 203–235, Plenum Press, New York (1991).
46. J. R. Evans and D. E. Packham. Adhesion of polyethylene to metals: The role of surface topography.
J. Adhesion, 10, 177–191 (1979).
Downloaded By: [Link] At: 00:29 03 Jan 2019; For: 9781315120942, chapter3, 10.1201/9781315120942-3

47. C. W. Jennings. Surface roughness and bond strength of adhesives. J. Adhesion 4, 25–41 (1972).
48. L. W. Fisher. Selection of Engineering Materials and Adhesives, CRC Press, Boca Raton, FL (2005).
49. D. Tabor and R. H. S. Winterton. The direct measurement of normal and retarded van der Waals forces.
Proc. Roy. Soc. A312, 435–450 (1964).
50. S. S. Voyutskii. Autohesion and Adhesion of High Polymers, Wiley Interscience, New York (1963).
51. J. Klein. The self-diffusion of polymers. Contemp. Phys. 20, 611–629 (1979).
52. S. F. Edwards and J. W. V. Grant. The effect of entanglements on the viscosity of a polymer melt.
J. Phys. A 6, 1186–1195 (1973).
53. F. Brochard and P. G. de Gennes. Polymer-polymer interdiffusion. Europhys. Lett. 1, 221–224 (1980).
54. S. Wu, H. K. Chuang and C.D. Han. Diffuse interface between polymers: Structure & kinetics. J. Polym.
Sci. Polym. Phys. Edition 24, 143–159 (1986).
55. J. Schultz and M. Nardin. Theories and mechanisms of adhesion. In: Handbook of Adhesive Technology:
Revised and Expanded, A. Pizzi and K. L. Mittal (Eds.), pp. 53–68, Marcel Dekker, New York (2003).
56. B. V. Deryaguin, N. A. Krotova and V. P. Smilga. Adhesion of Solids, Plenum Press, New York (1978).
57. K. W. Allen. At forty cometh understanding: A review of some basics of adhesion over the past four
decades. Int. J. Adhesion Adhesives 23, 87–93 (2003).
58. J. Krupp and W. Schnabel. Light modulated electrostatic double layer adhesion. J. Adhesion 5, 269–296
(1973).
59. A. D. Roberts. Surface charge contribution in rubber adhesion and friction. J. Phys. D: Appl. Phys. 10,
1801–1819 (1977).
60. W. Possart. Experimental and theoretical description of the electrostatic component of adhesion at poly-
mer/metal contacts. Int. J. Adhesion Adhesives 8, 77–83 (1988).
61. G. Ramarathnam, M. Libertucci, M. M. Sadowski and T. H. North. Joining of polymers to metal.
Welding J. 71, 483–490 (1992).
62. K. L. Mittal and H. R. Anderson, Jr. (Eds.). Acid-Base Interactions: Relevance to Adhesion Science and
Technology, CRC Press, Boca Raton, FL (1991).
63. K. L. Mittal (Ed.). Acid-Base Interactions: Relevance to Adhesion Science and Technology, Volume 2,
CRC Press, Boca Raton, FL (2000).
64. D. L. Allara, F. M. Fowkes, J. Noolandi, G. W. Rubloff and M. V. Tirrell. Bonding and adhesion of
polymer interfaces. Mater. Sci. Eng. 83, 213–226 (1986).
65. F. M. Fowkes. Role of acid-base interfacial bonding in adhesion. J. Adhesion Sci. Technol. 1, 7–27
(1987).
66. N. Encinas, J. Abenojar and M. A. Martínez. Development of improved polypropylene adhesive bond-
ing by abrasion and atmospheric plasma surface modifications. Int. J. Adhesion Adhesives 33, 1–6
(2012).
67. S. J. Park and M. K. Seo (Eds.). Interface Science and Composites, p. 852, Elsevier, New York (2011).
68. [Link]
69. C. J. Lee, S. K. Lee, D. C. Ko, D. J. Kim and B. M. Kim. Evaluation of surface and bonding properties of
cold rolled steel sheet pretreated by Ar/O2 atmospheric pressure plasma at room temperature. J. Mater.
Process Technol. 209, 4769–4775 (2009).
70. A. W. Adamson. Physical Chemistry of Surfaces, 4th edn, Chapter 10, Wiley-Interscience, New York
(1982).
71. J. Lyklema. Fundamentals of Interface and Colloid Science, Liquid–Fluid Interfaces, Vol. 3, Academic
Press, London (2000).
72. F. W. Fowkes. Additivity of intermolecular forces at interfaces. I. Determination of the contribution to
surface and interfacial tensions of dispersion forces in various liquids. J. Phys. Chem. 67, 2538–2541
(1963).
73. W. Su. Polymer Interface and Adhesion, Marcel Dekker, New York (1982).
74. F. A. Al-Zahrani, A. A. Al-Masmoom and U. A. Khashaba. Impact of polymers and polymeric com-
posites on the development of new designs in mechanical, electrical, and civil engineering: A review.
MASAUM J. Reviews Surveys 1, 184–195 (2009).
75. E. G. Shafrin and W.A. Zisman. Constitutive relations in the wetting of low energy surfaces and the
theory of the retraction method of preparing monolayers. J. Phys. Chem. 64, 519–524 (1960).
 92 Handbook of Adhesive Technology, Third Edition

76. L. J. Hart-Smith, D. Brown and S. Wong. Surface preparations for ensuring that the glue will stick
in bonded composite structures. Paper MDC 93K0126. In: Proceedings of 10th DoD/NASA/FAA
Conference on Fibrous Composites in Structural Design (1993).
77. M. J. Shenton, M. C. Lovell-Hoare and G.C. Stevens. Adhesion enhancement of polymer surfaces by
Downloaded By: [Link] At: 00:29 03 Jan 2019; For: 9781315120942, chapter3, 10.1201/9781315120942-3

atmospheric plasma treatment. J. Phys. D: Appl. Phys. 34, 2754–2760 (2001).

78. G. L. Lashkov, A. V. Veniaminov and O. B. Ratner. Study of diffusion of anthracene structure com-
pounds in PMMA by holographic relaxometry. Polym. Sci. (USSR) 28, 487–492 (1986).
79. E. N. Krupenya, A. Yu Kagan, I. D. Simonov-Emel Yanov, V. N. Kuleznez and L. L. Mukhina, Influence
of plasticisers on the strength of multi-layer materials based on polyvinylchloride. Int. Polym. Sci.
Technol. 16, T/55–T/57 (1989).
80. R. Bajpai, V. Mishra, P. Agrawal and S. C. Datt. Surface modification on PMMA: PVDF polyblend:
Hardening under chemical environment. Bull. Mater. Sci. 25, 21–23 (2002).
81. J. Comyn, L. Mascia, B. M. Parker, S. J. Shaw and G. Xiao. Surface treatments for PEEK. In: Proceedings
of IOM Adhesives Section Meeting on Surface Preparation for Adhesive Bonding, pp. 17–26 (1997).
82. P. Davies, C. Courty, N. Xanthopoulos and H. J. Mathieu. Surface treatment for adhesive bonding of
carbon fibre-poly(etherether ketone) composites. J. Mater. Sci. Letters 10, 335–338 (1991).
83. W. Shen, Z. Li and Y. Liu. Surface chemical functional groups modification of porous carbon. Recent
Patents on Chem. Engg. 1, 27–40 (2008).
84. L. R. Radovic, I. F. Silva, J. I. Ume, J. A. Menendez, C. A. Leony Leon and A. W. Scaroni. An experimen-
tal and theoretical study of the adsorption of aromatics possessing electron-withdrawing and electron-
donating functional groups by chemically modified activated carbons. Carbon 35, 1339–1348 (1997).
85. J. A. Menendez, M. J. Illan-Gomez, C. A. Leony Leon and L. R. Radovic. On the difference between the
isoelectric point and the point of zero charge of carbons. Carbon 33, 1655–1657 (1995).
86. J. A. Menendez, J. Phillips, B. Xia and L. R. Radovic. On the modification and characterization of
chemical surface properties of activated carbon: In the search of carbons with stable basic properties.
Langmuir, 12, 4404–4410 (1996).
87. J. A. Menendez, L. R. Radovic, B. Xia and J. Phillips. Low-temperature generation of basic carbon
surfaces by hydrogen spillover. J. [Link]. 100, 17243–17248 (1996).
88. S. Shin, J. Jang, S. H. Yoon and I. Mochida. A study on the effect of heat treatment on functional groups
of pitch based activated fiber using FTIR. Carbon 35, 1739–1743 (1997).
89. T. C. Uzomah and S. C. O. Ugbolue. Time and temperature effects on the ultimate properties of ther-
mally oxidized polypropylene films. J. Appl. Polym. Sci. 66, 1217–1226 (1997).
90. R. Ansari and G. G. Wallace. Effect of thermal treatment on the electrochemical properties of conduct-
ing polypyrrole polymers. Polymer 35, 2372–2377 (1994).
91. K. Lafdi, W. Fox, M. Matzek and E. Yildiz. Effect of carbon nanofiber heat treatment on physi-
cal properties of polymeric nanocomposites: Part I. J Nanomater. Article ID 52729, [Link]
org/10.1155/2007/52729 (2007).
92. P. I. F. Niem, T. L. Lau and K. M. Kwan. The effect of surface characteristics of polymeric materials on
the strength of bonded joints. J. Adhesion Sci. Technol. 10, 361–372 (1996).
93. S. Bhowmik, P. K. Ghosh and S. Ray. Surface modification of HDPE and PP by mechanical polishing
and DC glow discharge and their adhesive joining to steel. J. Appl. Polym. Sci. 80, 1140–1149 (2001).
94. E. Finson and S. L. Kaplan. Surface treatment. [Link]
[Link] (1997).
95. R. J. Zaldivar, H. I. Kim, G. L. Steckel, J. P. Nokes and B. A. Morgan. Effect of processing parameter
changes on the adhesion of plasma-treated carbon fiber reinforced epoxy composites. J. Composite
Mater. 44, 1435–1453 (2010).
96. M. Davis and D. Bond. Principles and practices of adhesive bonded structural joints and repairs. Int.
J. Adhesion Adhesives 19, 91–105 (1999).
97. M. Thomas and K. L. Mittal (Eds.). Atmospheric Pressure Plasma Treatment of Polymers: Relevance
to Adhesion, Wiley-Scrivener, Beverly, MA (2013).
98. K. N. Pandiyaraj, V. Selvarajan and R. R. Deshmukh. Effects of operating parameters on DC glow dis-
charge plasma induced PET film surface. J. Phys.: Conf. Ser. 208, 1–7 (2010).
99. D. P. Subedi, D. K. Madhup, K. Adhikari and U. M. Joshi. Plasma treatment at low pressure for the
enhancement of wettability of polycarbonate. Indian J. Pure Appl. Phys. 46, 540–544 (2008).
100. J. Larrieu, B. Held, H. Martinez and Y. Tison. Ageing of atactic and isotactic polystyrene thin films
treated by oxygen DC pulsed plasma. Surf. Coat. Technol. 200, 2310–2316 (2005).
101. C. M. Weikart and H. K. Yasuda. Modification, degradation, and stability of polymeric surfaces treated
with reactive plasmas. J. Polym. Sci., Part B: Polym. Phys. 38, 3028–3042 (2000).
 Plasma Surface Treatment to Enhance Adhesive Bonding 93

102. K. Narushima and H. Ikeji. Plasma surface modification of poly (aryl ether ether ketone) and surface
metallization using copper metal. Sen’I Gakkaishi (translated into English) 65, 127–131 (2009).
103. K. Narushima, H. Ikeji, Y. W. Park, Y. Isono and Y. R. Islam. Plasma surface modification of aromatic
liquid crystal polymers and its resultant improvement in adhesive strength with copper thin films. Sen’I
Downloaded By: [Link] At: 00:29 03 Jan 2019; For: 9781315120942, chapter3, 10.1201/9781315120942-3

Gakkaishi (translated into English) 63, 287–294 (2007).

104. N. Inagaki. Modification of polymer surfaces by plasma. Shinku (translated into English) 43, 856–862
(2000).
105. S. L. Kaplan, E. S. Lopata and J. Smith. Plasma processes and adhesive bonding of polytetrafluoroeth-
ylene. Surf. Interf. Anal. 20, 331–336 (1993)
106. G. Bonizzoni and E. Vassallo. Plasma physics and technology: Industrial applications. Vacuum, 64,
327–336 (2002).
107. E. M. Liston, L. Martinu and M. R. Wertheimer. Plasma surface modification of polymers for improved
adhesion: A critical review. J. Adhesion Sci. Technol. 7, 1077–1089 (1993).
108. A. Sparavigna. Plasma Treatment Advantages for Textile, Cornell University Library, [Link]
ftp/arxiv/papers/0801/[Link], pp. 1–16 (2008).
109. A. Bogaerts, L. Wilken, V. Hoffmann, R. Gijbels and K. Wetzig. Comparison of modeling calculations
with experimental results for rf glow discharge optical emission spectrometry. Spectrochimica Acta
Part B 57, 109–119 (2002).
110. A. Schutze, J. Y. Jeong, S. E. Babayan, J. Park, G. S. Selwyn and R. F. Hicks. The atmospheric-pressure
plasma jet: A review and comparison to other plasma sources. IEEE Trans. Plasma Sci. 26, 1685–1694
(1998).
111. C. Tendero, C. Tixier, P. Tristant, J. Desmaison and P. Leprince. Atmospheric pressure plasmas: A
review. Spectrochimica Acta Part B, 61, 2–30 (2006).
112. H.-E. Wagner, R. Brandenburg, K. V. Kozlov, A. Sonnenfeld, P. Michel and J. F. Behnke. The barrier
discharge: Basic properties and applications to surface treatment. Vacuum 71, 417–436 (2003).
113. M. A. (Tony) Belcher, K. L. Krieg, P. J. Van Voast and K. Y. Blohowiak. Nonchemical surface treat-
ments using atmospheric plasma systems for structural adhesive bonding. In: Proc. SAMPE 2013, Long
Beach, CA (2013).
114. N. Jiang, A. Ji and Z. Cao. Atmospheric pressure plasma jets beyond ground electrode as charge over-
flow in a dielectric barrier discharge setup. J. Appl. Phys. 108, 033302 (2010).
115. R. A. Wolf. New atmospheric plasma and photografting approach for permanent surface tension and
coating adhesion. Report by Enercon Industries Corp., Milwaukee, WI (2007).
116. N. Bhatnagar, S. Jha, S. Bhowmik, G. Gupta, J. B. Moon and C. G. Kim. Physico-chemical character-
istics of high performance polymer modified by low and atmospheric pressure plasma. Surf. Eng. Appl.
Electrochem. 48, 117–126 (2012).
117. K. N. Pandiyaraj, V. Selvarajan, R. R. Deshmukh and M. Bousmina. The effect of glow discharge
plasma on the surface properties of poly (ethylene terephthalate) (PET) film. Surf. Coat. Technol. 202,
4218–4226 (2008).
118. A. Qureshi, S. Shah, S. Pelagade, N. L. Singh, S. Mukherjee, A. Tripathi, U. P. Deshpande and
T. Shripathi. Surface modification of polycarbonate by plasma treatment. J. Phys.: Conf. Ser. 208, Paper
ID: 012108, 1–6 (2010).
119. M. Noeske, J. Degenhardt, S. Strudthoff and U. Lommatzsch. Plasma jet treatment of five polymers at
atmospheric pressure: Surface modifications and the relevance for adhesion. Intl. J. Adhesion Adhesives,
24, 171–177 (2004).
120. F. M. Etzler. Determination of the surface free energy of solids: A critical review. Rev. Adhesion
Adhesives 1, 3–45 (2013).
121. T. S. Williams, H. Yu and R. F. Hicks. Atmospheric pressure plasma activation of polymers and com-
posites for adhesive bonding: A critical review. Rev. Adhesion Adhesives 1, 46–87 (2013).
122. S. Pelagade, N. L. Singh, S. Shah, A. Qureshi, R. S. Rane, S. Mukherjee, U. P. Deshpande, V. Ganesan
and T. Shripathi. Surface free energy analysis for bipolar pulsed argon plasma treated polymer films.
J Phys.: Conf. Ser. 208, Paper ID: 012107, 1–8 (2010).
123. S. Kitova, M. Minchev and G. Danev. RF plasma treatment of polycarbonate substrates. J. Optoelectron.
Adv. Mater. 7, 2607–2612 (2005).
124. H. M. S. Iqbal, S. Bhowmik, J. A. Poulis and R. Benedictus. Effect of plasma treatment and electron beam
radiations on the strength of nanofilled adhesive-bonded joints. Polym. Eng. Sci. 50, 1505–1511 (2010).
125. U. Lommatzsch, D. Pasedag, A. Baalmann, G. Ellinghorst and H. E. Wagner. Atmospheric pressure
plasma jet treatment of polyethylene surfaces for adhesion improvement. Plasma Process. Polym. 4,
S1041–S1045 (2007).
 94 Handbook of Adhesive Technology, Third Edition

126. C. Arpagaus, A. Rossi and P. R. von Rohr. Short-time plasma surface modification of polymer powders
in a downflowing tube reactor. Surf. Coat. Technol. 200, 525–528 (2005).
127. S. Jha, S. Bhowmik, N. Bhatnagar, N. K. Bhattacharya, U. Deka, H. M. S. Iqbal and R. Benedictus.
Experimental investigation into the effect of adhesion properties of PEEK modified by atmospheric
Downloaded By: [Link] At: 00:29 03 Jan 2019; For: 9781315120942, chapter3, 10.1201/9781315120942-3

pressure plasma and low pressure plasma. J. Appl. Polym. Sci. 118, 173–179 (2010).
128. N. Inagaki, S. Tasaka, K. Narushima and H. Kobayashi. Surface modification of PET films by pulsed
argon plasma. J. Appl. Polym. Sci. 85, 2845–2852 (2002).
129. K. Narushima, S. Tasaka and N. Inagaki. Surface modification of poly(aryl ether ether ketone) by pulsed
oxygen plasma. Jpn. J Appl. Phys 41, 6506–6516 (2002).
130. C. Kim, D. Jeong, J. Hwang and H. Chae. Argon and nitrogen plasma surface treatments of polyimide
films for electroless copper plating. J. Korean Phys. Soc. 54, 621–627 (2009).
131. G. Beamson and D. Briggs. High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database,
John Wiley, Chichester, UK (1992).
132. B. Gupta, J. Hilborn, C. Hollenstein, C. J. G. Plummer, R. Houriet and N. Xanthopoulos. Surface modi-
fication of polyester films by RF plasma. J. Appl. Polym. Sci. 78, 1083–1091 (2000).
133. A. N. Gent and C. W. Lin. Model studies of the effect of surface-roughness and mechanical interlocking
on adhesion. J. Adhesion 32, 113–125 (1990).
134. R. J. Zaldivar, H. I. Kim, G. L. Steckel, D. Patel, B. A. Morgan and J. P. Nokes. Surface preparation for
adhesive bonding of polycyanurate-based fiber-reinforced composites using atmospheric plasma treat-
ment. J. Appl. Polym. Sci. 120, 921–931 (2010).
135. W. S. Kim, I. H. Yun and J. J. Lee. Evaluation of mechanical interlock effect on adhesion strength of
polymer-metal interfaces using micro-patterned surface topography. Intl. J. Adhesion Adhesives 30,
408–417 (2010).
136. S. O’Kell, T. Henshaw, G. Farrow, M. Aindow and C. Jones. Effects of low-power plasma treatment on
polyethylene surfaces. Surf. Interface Anal. 23, 319–327 (1995).
137. S. Zhang, G. Huang, X. Wang, Y. Huang, J. Yang and G. Li. Effect of air plasma treatment on the
mechanical properties of polyphenylene sulfide/glass fiber cloth composites. J. Reinforced Plast.
Composites 32, 786–793 (2013).