Mechanism of Corona Treatment on Polyolefin Films

DONG ZHANG, QIN SUN, and LARRY C. WADSWORTH

Textiles and Nonwovens Development Center

The University of Tennessee
K n m i U e , TN37996

This paper reviews recent studies on the mechanism of corona treatment of poly-
olefin fi.lms, specifically the chemical and physical changes of this process and the
self-adhesion mechanism. Corona discharge of polymeric films introduces polar
groups into the surfaces, which increases the surface energy and, as a conse-
quence, improves substrate wettability and adhesion. The main chemical mecha-
nism of corona treatment is oxidation. In addition, corona treatment can crosslink
surface regions and increase the film cohesive strength.

INTRODUCTION as air is ordinarily a good electrical insulator, but in a

strong enough electric field it breaks down, that is, its
F or polyoleh films, surface treatments are usually
necessary to improke surface wetting and adhe-
sion characteristics in different application situations
molecules become ionized and it conducts electricity.
There is a sudden electric discharge, which usually
such as adhesive bonding, printing, extrusion coat- develops into a n arc or sparks between two electrodes.
ings, metallized polyolefins, composites, a n d heat If a solid film is placed between these electrodes and
interrupts the conductive path, instead of a hot local-
sealing (1). Numerous methods have been developed
ized arc there is a cooler, diffuse glow between the two
to modify polymer surface (2, 3).Among them, corona
treatment is widely used in industry. electrodes. This soft, bluish discharge of the air at at-
mospheric pressure is called corona.
Theories proposed foi- the increased adhesion of
The phenomenon of corona starts with a few stray
corona-treated polymer surfaces include electret for-
electrons that are present in the gas between elec-
mation (4), the eliminahon of weak boundary layers
(5), increased surface roughness due to pitting (6),
trodes because of cosmic rays or other background
and introduction of polar groups due to oxidation and radiation. If a high voltage is applied, a strong electric
other chemical changes in the surface region (7-9). I t field is created, which accelerates the electrons to-
wards the positive electrode. The electrons continually
is now widely accepted that corona discharge treatment
strike gas molecules in their path. The impacting elec-
results in an increase in surface energy by introduc-
trons may knock an orbital electron out of the mole-
tion of polar groups on the surface, thus improving
cules, leaving a positive ion and another electron that
their adhesion and wettirig properties (10, 11).
can go on to strike other molecules. Otherwise, and
Since polyoletins of polyethylene (PE) and polypro-
pylene [PP)are two of the three most widely used syn- more often, the impacting electron lifts an orbiting
electron to a n unstable, higher energy orbit, creating
thetic polymers in the world (7). most of the research
a n excited molecule. Soon the gas is full of electrons,
on corona treatments of polyolefin films is based on
PE and PP films. Much cC what we understand about positive ions, excited molecules, heat and light-in
other words, corona. The excited molecules are unsta-
the corona treatment has been generated within the
ble and decompose spontaneously into radicals, ions
last twenty-five years. The purpose of this paper is to
and photons. The dominant theory concerning corona
review the recent research on the mechanism of coro-
discharge is that polar groups are introduced into the
na treatment of polyolefin films, which may help the
polymer surfaces, which leads to higher surface ener-
industrial engineers or scientists better understand
the physical and chemical mechanisms involved and
gy and better adhesion. For example, in oxygen-con-
tained corona, a mixture of activated oxygen species is
develop the technical potential of the application of
present between the electrodes during treating, in-
corona treatment.
cluding free oxygen in its elemental form (O.), ozone
(OJ, and activated oxygen (O,*). Activated oxygen is
CORONA EFFECT
oxygen that is virbrationally and electrically excited
The term “corona”is used to describe the condition above its ground state energy (12,13). Highly reactive
of a gas, usually air between electrodes. Gases such oxygen arrangements can in turn react very rapidly

POLYMER ENGINEERING AND SCIENCE, JUNE 1998, Vol.38,No. 6 965


flLMS PFACIOS j FILM PqOXIOES
< DECOMPOSITION
I
QIOSSUNKINO
OF FILMS
. n into corona dischargefilms (1 1).
FYg. 1 . oxygen introductto
with polar molecules such as water, and ultimately,
oxygen-containing functional groups are introduced
into the film surface as shown in Flg. 1.
As power to the corona is increased, more ions are
formed and the average kinetic energy of the particles
is increased. The important parameter in regulating
the treatment level is the energy which the ions im-
part to the film.With an increase in relative humidity,
the discharge-energy should be increased (8). Dis-
charge treatment under high humidity conditions leads
to a proportionally higher concentration of groups
containing C-0 functionality than does treatment in
low humidity conditions. Electrons emitted by the
corona-induced photo effect were considered as the
main cause of the surface activation (14), which lead
to the surface changes both chemically and physical-
ly. Polar chemical functional groups are created on the
surface, which enhance the surface adhesion and
wettability. It is known that corona treatment can also
change the morphology of polymer films and affect
their adhesion properties. The adhesion can either in-
crease or decrease depending on the potential bond-
ing area and the presence of voids. This has been
observed by self-adhesion experiments on corona-
treated polyoleks (4, 9).
Corona discharge treatment in the presence of air
or action of oxidizing mixtures entails substantial
morphological and chemical modifications in the sur-
face region of a polymer, such as alteration of external
appearance and formation of functional groups (15,
16).Although the magnitude and the nature of these
modifications seem to depend on the treatment tech-
niques and polymers used, the overall aim of these
processes is to enhance the adhesive properties of
polymers (17). The treated surface is known to be
changed both chemically and physically by the corona
treatment (10,18).
CHEMICAL CHANGES
Corona discharge treatment results in an increase
in surface energy by introduction of polar groups on
the surface, thus improving their adhesion and wet-
ting properties. The main chemical mechanism of
corona discharge treatment is oxidation. In addition,
966
the crosslinking of the molecules on the surface takes
place which restricts mobility of the surface molecules
and results in an increase in the molecular weight.
Various analytical techniques have been used to iden-
t.@ these chemical functional groups (19,20), such as
electron spectroscopy for chemical analysis (ESCA or
XPS), second ion mass spectroscopy (SIMS), infrared
spectroscopy (IR or ATR), electron spin resonance
(ESR). Of these, XPS and IR have been most widely
used.
Oxidation
Chemical changes in polyolefins brought about by
air oxidation and photo-oxidation were detected in the
early 1950s using transmission infi-ared spectroscopy.
For example, in thermal oxidation mainly keto groups
resulted plus some aldehyde and acid groups (21). In
photo-oxidized polyethylene, similar quantities of alde-
hyde, acid and keto groups resulted. Changes have
also been detected in levels of unsaturation in both
types of oxidation leading to the postulation of the for-
mation of unstable hydroperoxide groups. Rossmann
(22) found an increased concentration of keto groups
in polyethylene.
Evidence for the existence of the hydroperoxide
intermediate, ROOH, RO,R, RO,R, -O-b=O and
> C=O, groups have been noted in the literature (13,
23-25). These polar groups provide sites for adhesion
of inks.A free oxygen atom can break a polymer mol-
ecule in two, or simply cleave a hydrogen atom. In
either case, two free radicals are formed for a net gain
of one. Free radicals in this form are very reactive
and quickly form new groups (26). Oxidation of poly-
mers by atomic oxygen occurs rapidly at the surface,
although initiation of simple thermal oxidation begins
with the relatively slow formation of hydrocarbon
radicals. The hydrocarbon radicals formed together
with alkoxy or hydroxy radicals during the initiation
stage react rapidly with oxygen atoms or molecular
oxygen. Reaction rate constants can be as high as
100,000. This translates to thousands Of chain trans-
fers in the short time that the filmis exposed to the
C O ~ ~ energy.
M
The emission spectrum of corona discharge is quite
sensitive to the surrounding atmosphere. Small
amounts of impurities can lead to dramatic chemical
changes in the surface of the treated film (27-29). Poly-
ethylene, treated in a pure nitrogen corona, formed
basic functional groups which adsorbed acidic, but
not basic dyes. This is opposite to the dye adsorption
characteristics of polyethylene treated in air coronas
(30).
To test the oxidation hypothesis further, effects of
treating in air, 0,.N,, He, and Ar were compared. It
was concluded that it was possible to corona-treat
polymers in these gases to the same level of surface
energy, which questioned the importance of oxygen as
a factor in corona induced adhesion promotion of
polyoleh fllms. Corona treatment of polyolefln in an
POLYMER ENGINEERING AND SCIENCE, MAY 1998, Vol. 38,No. 6
 Mechanism of Corona 7keatment on Polyole@ Films
inert atmosphere should not produce oxygenated
functional groups, but studies indicated that good au-
toadhesion and ink adhesion to the film is obtained
(27, 31).Further XPS spectroscopic studies showed
that oxygen is indeed incorporated into the film sur-
face for all these gases used in discharge treatment. It
can be argued (91, therefore, that using other gases
under corona discharge may still produce free radical
sites in the film. In turn, these gases may react with
atmospheric oxygen to give a thin layer of polymer
containing ketonic functional groups. These groups
can hydrogen-bond to carbonyl groups in the poly-
meric binders of the inks or coatings, thereby increas-
ing adhesion. Previous studies (32)have supported
the hydrogen bonding theory as the primary reason of
polar groups for enhancement of film adhesion char-
acteristics through corona. The other possible sources
of oxygen in these inert atmosphere may be.
1. Owgen impurities from gases:
2. The polymer itself (containsdissolved oxygen that
may not be completely removed:
3. Apparatus often constructed of glass dielectrics,
which is a ready s c u c e of dissolved oxygen mole-
cules.
Another area in which it is believed that oxidation
plays a large part, and also helps support it, is in au-
toadhesion of polymer films-how well two similarly
treated films bond to each other. The chemical basis
for enhanced adhesion between polymer layers result-
ing from corona treatment may be due to hydrogen
bonding between the -OH of enol groups and other
oxygen containing functional groups created on the
polymer surface by the treatment. These functionali-
ties were found to result during corona discharge in
air and also when “inert” gases (nitrogen, argon) were
used. Corona discharge in hydrogen, however, pre-
vented formation of oxygen functionalities and did not
promote autoadhesion.
Increaae in Molecular ‘Weight and Crosslinking
Many researchers have noted that corona discharge
further increased the molecular weight of polymeric
materials (33-35).The free radicals introduced in-
creased molecular weight of the polymer surface
enough to give it added strength, a higher melting
point, and greater integrity. The surface oils and
waxes that made up the weak boundary layer were in-
corporated into the stronger high molecular weight
boundary layer, which w a s 0.054.1 pm thick.
Farley and Meka (33)studied the effect of corona
discharge treatment (CDT) of LLDPE with special em-
phasis on the heat-seal behavior of treated films.
Results of heat-sealing studies with electron beam ir-
radiated PE, chemically oxidized PE, and corona dis-
charged PE provided indirect evidence of the proposed
surface crosslinking mechanism.
A peroxyradical could cause either chain scission
and reduced molecular weight or chain addition and
increased molecular weipgt. Corona treatment power
POLYMER ENGINEERING AND SCIENCE, MAY 1998, Vol. 38,No. 6
levels influenced this reaction. It was reported (6)the
latter reaction was prevalent under normal treatment
conditions and the former under severe conditions of
30 minutes of high power treatment.
PHYSICAL CHANGES
It is known that corona treatment can change the
surface morphology of polyoleh films in addition to
the introduction of polar functional groups onto the
surfaces. The polar component of surface energy is
the key to understanding the changes in adhesive be-
havior of the films during corona treatment (36).
However, changes in surface morphology caused by
these processes can also affect the level of adhesion.
The surface morphology is usually studied by means
of scanning electron microscopy (SEM), atomic force
microscopy (AFM) (19, 20). This section focuses on
morphological change caused by corona treatment as
well as some other physical changes such as mechan-
ical properties.
Surface Morphology
As high energy particles bombarded the film being
treated, small micropits can be formed, which are tiny
holes dug by the charges. Micropitting can lead to in-
creased adhesion through mechanical keying and a
greater potential bond area. However, alternately it
may lead to reduced adhesion because a small area of
bonding is achieved or because stress concentration
occurs due to the presence of voids. The actual effect
depends on surface energies, the viscosity of the wet-
ting liquid, and the size and shape of the irregularities.
Corona treatment in air has been shown to make
the polyolefin film surface rough (37).Surface rough-
ening is enhanced when pure oxygen or CO, was used
instead of air. Corona discharge in gases containing
no oxygen such as H,, Hr, A, or N, produced no visual
change on the surface (38).Thus, oxidation seems to
be a necessary accompaniment to the surface rough-
ening effect.
Over-treatment usually leads to occurrence of bumps
on the polyolefin surfaces and has a deteriorating ef-
fect on the adhesion and wettability characteristics.
The extreme situation is that the heat generated in
this process causes burning of the treated samples.
Surface morphology has been shown to change both
with time and temperature of treatment. At constant
temperature, the size of the bumps on PE films in-
creased with a longer time of treatment. Bump size
also increased when the temperature was raised for a
constant time of treatment. Bumps of about 1 pm in
diameter were created by 1-min treatment at 50°C
while treatment for 15 min at 75°C produced 10 pm
bumps (6). It showed that polyolefin films corona-
treated for long times at elevated temperatures exhibit
reduced bond strength and have more loose surface
materials than films more modestly corona-treated
(6).I t is speculated that these degradation products
might act as a weak boundary layer in reducing self-
adhesion. One could also propose that the degrada-
967
 Dong Zhang, Qin S u n , a n d LQny C. Wadsworth
tion products of s u c h gross over-treatment might
mask the underlying enol groups and prevent the
close approach of the two surfaces necessary for H-
bond formation. An unexpected result was that the
bumps on a treated surface were easily removed by
dipping the sample into CCl,, ethanol, or 0.2% aque-
ous NaOH. At low resolution, the solvent-dipped sur-
face appeared to be similar to the untreated surface.
However, with high resolution, the treated and ethanol-
dipped surface appeared rough and textured compared
with the original surface. Perhaps the oxygen corona
attacked the amorphous regions preferentially, thus
causing etching while becoming visible when the
degradation products were removed.
Two possible explanations of the corona-induced
bumps on the corona-treated surface are the poly-
olefin possesses an inert skin on its surface which is
not much attacked by the active species in an oxygen-
containing corona. Degradation of the polymer occurs
below this skin and a certain amount of gas is evolved.
This may cause the skin to blister and thus give rise
to the bumps observed. However, there is no apparent
reason why the skin should be removed so cleanly
when the treated surface is dipped into ethanol or other
solvents.
Overmey et aL (39) presented a study of the adhe-
sive strength to the polymer bulk surface of bumps
(termed dropletlike protrusions in their studies) of a
PP film treated with a single corona dose of 112.5
J/cm2. Bumps were found to be physically absorbed
on the polymer bulk surface. The contact angle meas-
urements supported the assumption of local surface
melting or sublimination as a possible explanation for
the formation of the bumps. It was indicated from fric-
tion force measurements that the molecules of the
bumps were chemically different and of low molecular
weight.
In the previous study of Overmey et aL (40),changes
in the morphology of corona- treated uniaxially orient-
ed PP and biaxially oriented PP have correlated to self-
adhesive strength of the films. Their diameters and
heights of bumps increase proportionally with the ap-
plied corona dose after a threshold of about 18 J/cm2.
It has been assumed that the loss of adhesive strength
is mainly caused by (a)reduction of the contact area
and (b)the adhesive strength of the polymer bulk sur-
face. It further shown that above 18 J/cm2, the molec-
ular weight of the surface molecules decreases and
oxidation takes place during all stages of the corona
treatment.
Mechanical and Rheological Properties
Dong et aL (41) studied the mechanical properties of
corona-modified cellulose/polyethylene composites. It
showed that the treatment of polyethylene and/or cel-
lulose fibers in air corona resulted in a sigmficant in-
crease in strength properties of the composite. Yield
stress increased after treatment of one or both of the
composite components. Pronounced improvement in
ductility was observed for composites containing 15%
968
to 300/0of the corona modified fiber. Yield strength and
strain, and elongation at rupture were found to be
strongly affected by corona treatments, indicating that
these composite properties were highly sensitive to
interfacial phenomena. However, initial modula and
ultimate strength of composites were generally inde-
pendent of corona treatment, which means they were
insensitive to interfacial characteristics in the com-
posites. It was concluded that the corona treatments
represent a valuable strategy for surface modification,
consistent with targeted mechanical properties of the
composites.
The same authors (42) also studied the rheological
properties of corona modified cellulose/polyethylene
composites. It showed that corona treatment for one
or both of the constituents resulted in decreased melt
viscosities relative to compounds containing untreat-
ed materials. The reduction of melt viscosity may orig-
inate from low molecular weight moieties formed on
the surfaces of both polyethylene and cellulose during
corona treatment. These may act as lubricants at in-
terfaces. Also it was found that the corona treatment
of fibers leads to higher packing volumes: this may. re-
sult from a reduction in fiber length when fibers are
processed under high shear conditions. As a result
these fibers perturb the normal flow pattern in the
melt to a lesser degree than the longer fibers of un-
treated cellulose. The rheological research by Bousmina
et aL (43) revealed that corona treatment resulted in a
decrease of dynamic shear viscosity of both PE and PS.
SELF-ADHESION MECHANISM
Early studies (6, 44-46) of corona discharge-treated
polyolebs suggested that the increased autoadhesion
was due to electret formation. The autoadhesion was
due to changes in the electrical properties of the sur-
face induced by the corona discharge. When dielectric
materials were subjected to strong electric fields, elec-
trical charges were induced in the dielectric, which
was known as the electret effect.
Surface charge due to electret formation was known
to decay with time. Also, the decay was faster at ele-
vated temperatures (47).Autoadhesion versus time of
standing was plotted in i%g.u-es 2 and 3 for treatment
in oxygen and nitrogen, respectively (6).In both cases,
there was a decrease in bonding with time of stand-
ing. The results in Figs. 2 and 3 showed that the
decay was slower after longer times and was more
rapid in nitrogen than in oxygen. If, after treatment,
the samples were stored at an elevated temperature, a
much more rapid decay in bonding was found. This
parallel between the known properties of electrets and
the adhesion behavior of corona-treated PE was fur-
ther supported for the idea that the autoadhesion and
electret formation might be related.
The results led to the suggestion that a type of elec-
tret formation was the basic reason for the increase in
the autoadhesion of PE when treated in corona dis-
charge. The industrial corona discharge treatment
showed that the printability of a PE sheet decayed
POLYMER ENGINEERING AND SCIENCE, JUNE 1998, Vol. 38, No. 6
 Mechanism of Corona Treatment on Polyolejh Films
Fg. 2. Effect o f standing on autoadhesion after nitrogen coro-
na treatment (6).
,
f the liquid is allowed to evaporate without disturbing
I 0 #)
af swans 1-1
Fg. 3. Effect of standing Ion adhesion afler air corona treat-
ment IS).
with time of standing after treatment. Although this
implies that the electret effect may be responsible
for the enhanced printxbility of PE achieved by treat-
ment in a corona discharge, ICI researchers proved
this theory is incorrect (48).
The following mechanism was proposed to account
for the enhanced self-adhesion of corona-treated poly-
olefin fim. For example of PE, in Eq I of Fig. 4, a ter-
tiary carbon atom in the PE molecule is attacked
through the mechanism of hydrogen abstraction and
hydroperoxide formation (49).The hydroperoxide de-
composes into an alko~yradical. Being unstable, the
alkoxy radical tends to undergo chain scission as Eq 2
to form a ketone and artother free radical (6).
Equation
3 shows the tautomerization of the ketone to the enol
form. The weakly acidic hydrogen of the enol can then
H bond with a carbonyl in an adjacent surface as
shown in Eq 4 . There are numberous pathways of ke-
tone formation in the corona activated oxidation of PE
and this one is typical.
The immediate failure of joints to which H-bonding
POLYMER ENGINEERINGAND SCIENCE, JUNE 1998, Vol. 38,No. 6
4.
Q.4. Formntion of ketones in PE by corona treatment (491.
liquids have been applied is apparently due to the
ability of these liquids to disrupt the enolcarbonyl H
bond because of their stronger H-bonding tendency.
This argument was strengthened by the reversibility
of the effect. The enolcarbonyl H-bonds reform when
the joint. The failure of solvents of strong acids and
bases to affect the adherability of corona-treated film
can be explained by assuming that at least one end of
the molecular bearing the enol group is still attached
to the film surface by carbon-carbon bonds.
Discharge treatment of polyolefins in almost all
gases leads to the incorporation of oxygen functions
into the surface. However, hydrogen is unique, which
prevents formation of oxygen functionalities and does
not promote self-adhesion. It indicates that film auto
adhesion increases with an increase in surface oxida-
tion. The chemical basis for enhanced adhesion be-
tween polyolefin films resulting from corona treatment
may be due to hydrogen bonding between the -OH
of enol groups and other oxygen containing groups
created in the polymer surface by the treatment. This
H-bonding theory of auto-adhesion enhancement of
corona treated polyolefin films is consistent with the
above-mentioned oxidation mechanism of corona
treatment.
SUMMARY
Corona discharge of polymeric films introduces
polar groups into the surfaces resulting in increases
in the surface energy and, as a consequence, im-
proved substrate wettability and adhesion character-
istics. The main chemical mechanism of corona
treatment is oxidation. In addition, corona treatment
can crosslink surface regions and increase the film
cohesive strength.
The formation of polar functional groups and reac-
tive species appears to be the mechanism through
which improved surface characteristics are imparted
to the films. Some of these species are:
969
 Dong Zhang, QinSun, and Larry C. Wadsworth
Peroxides and ozanides: RO,R, ROOH, RO,R
Ions: NO^,
R-C=O
?-
Neutral functional groups:
> C=O, -&OH,
1 H d = O , RO-b=O, -NO,
Ozone
Film surface crosslinking
Corona treatment under many other gases also can
enhance the surface adhesion and wettability charac-
teristics, which indicated that using other gases under
corona discharge may still produce reactive species
and polar functional groups. XF'S spectroscopic stud-
ies showed that oxygen is indeed incorporated into the
film surface for all these gases used in discharge
treatment. Therefore, oxidation plays a very important
part in corona discharge treatment under different
working gases to enhance a good adhesion.
The chemical constituents formed on the film sur-
face by corona discharge are largely controlled by the
composition of the gas between the electrodes as well
as the f ilm and its additives. The effectiveness of coro-
M treatment on polymeric films depends on the rela-
tive humidity during discharge. The hgher the surface
moisture concentration, the longer is the required time
of corona discharge. This suggests the possibility that
the initial hydrogen abstraction process may be re-
versible in the presence of surface moisture. Corona
treatment discharge can change the morphology of
polymer films and affect their adhesive properties. The
increased surface roughness can lead to either in-
creased or decreased adhesion, depending on surface
energies, potential bonding and presence of voids.
Excessive treatment hal l y leads to an over-treatment
situation, which can result in occurrence of bumps on
the polyolefh surfaces and causes a deteriorating effect
on the adhesion and wettability characteristics. The
heat generated in this process also marginally helps
to b u m off or evaporate very low molecular weight
fractions that may have migrated to the surface since
extrusion.
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Received M a y 30,1997
Revised actober 1997
POLYMER ENGINEERINGAND SCIENCE, JUNE 1998. Vol. 38,No. 6