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Corona Treatment of Polyolefin

Films — A Review
CHRISTINE (QIN) SUN, DONG ZHANG, and
LARRY C. WADSWORTH
Textiles and Nonwovens Development Center, The University of Tennessee, Knoxville, Tennessee
37996
Received: September 8, 1998
Accepted: January 7, 1999

ABSTRACT: Corona discharge introduces polar groups into the polymeric

surfaces and, as a consequence, improves the surface energy, wettability, and
adhesion characteristics. The main chemical mechanism of corona treatment is
oxidation. This article further discusses some special problems that are related
to corona treatment of polyolefin films by reviewing the recent developments in
this field, such as effect of corona treatment on adhesion, effect of resin
additives on corona treatment, insufficient treatment and over-treatment of
corona discharge, aging, and re-treatment. 䉷 1999 John Wiley & Sons, Inc.
Adv Polym Techn 18: 171 – 180, 1999

gion.7 – 9 It is now widely accepted that corona dis-

Introduction charge treatment results in an increase in surface
energy by introducing polar groups on the surface,

F or polyolefin films, surface treatments are usu-

ally necessary to improve surface wetting and
adhesion characteristics for different applications
such as adhesive bonding, printing, extrusion coat-
ings, metalized polyolefins, composites, and heat
sealing.1 Numerous methods have been developed
to modify polymer surfaces.2,3 Among them, corona
treatment is widely used in industry.
Theories proposed for the increased adhesion of
corona-treated polymer surfaces include electret
formation,4 the elimination of weak boundary lay-
ers,5 increased surface roughness due to pitting,6
and introduction of polar groups due to oxidation
and other chemical changes in the surface re-
thus improving their adhesion and wetting proper-
ties.10 –12 Oxidation plays a very important part in
corona discharge treatment under different working
gases to enhance a good adhesion and it is the main
chemical mechanism for corona treatment. In ad-
dition, corona treatment can cross-link surface
regions and increase the film’s cohesive strength.13
Since polyolefins of polyethylene (PE) and poly-
propylene (PP) are two of the three most widely
used synthetic polymers in the world,7 most of the
research on corona treatments of polyolefin films is
based on PE and PP films. Much of what we un-
derstand about the corona treatment has been gen- short
erated within the last thirty years. The purpose of standard

Advances in Polymer Technology, Vol. 18, No. 2, 171– 180, 1999

䊚 1999 by John Wiley & Sons, Inc. CCC 0730-6679/99/020171-10
ADV WILEY
CORONA TREATMENT OF POLYOLEFIN FILMS
this article is to discuss some special problems on
corona treatment of polyolefin films, such as effect
of corona treatment on adhesion, effect of resin ad-
ditives, insufficient treatment and over-treatment of
corona discharge, aging, and re-treatment, which
may help the industrial engineers or scientists better
understand this complicated process and develop
new applications for this technology.
Effect of Corona Treatment on
Adhesion
The topic of “adhesion” has been studied for
hundreds of years and many definitions, terms, and
theories have been introduced to characterize this
phenomena. The following definition for adhesion
was supplied by the American Society for Testing
and Materials (ASTM): “Adhesion, is the state in
which two surfaces are held together by interfacial
forces consisting of valence forces, interlocking ac-
tion, or both.” In corona discharge treatment of
polymer films, adhesion usually refers to attractive
forces between liquid molecules (ink, adhesive, ex-
tradite) and the substrate surface molecules such as
PP, PE, and so on, or to the bonding of two substrate
surfaces. It is known that increasing the polarity of
surface molecules of substrate increases adhesion
since inks and adhesives are also polar. Corona
treatment also improves autoadhesion (film to film
adhesion).
Most converters use some types of measurement
for estimating the corona treatment level of their
films. Markgraf14 has described the “wetting tension
test” (ASTM D-2578), which is widely used to de-
termine the treatment level. The test consists of ap-
plying a mixture of formamide/cellulosic solutions
which have gradually increasing surface tensions,
in a prescribed series to the surface of a polymeric
material. The procedure is complete when the so-
lution spreads or wets the material. At this point,
the surface tension of the material is equal to the
known surface tension of the “dyne-solution,” and
one can accurately determine the surface tension of
a particular polymer material to within one dyne/
cm. There are some problems with this technique:
1. The solutions used are solvent mixtures which
vary because of contamination or evaporation.
2. The actual numbers are not meaningful when
applied to different films. For example, for
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good ink wetting and adhesion, PE or oriented
PP (OPP) surface energies need to be only 40
dynes/cm, but polyester, which is already at
47 dynes/cm, should be treated to surface en-
ergies above 50 dynes/cm.
Not only is the preceding surface measurement
technique not reliable, it often does not provide the
discrimination necessary to make decisions relative
to the printability and adhesion of the films. Contact
angle measurements are more reliable indicators of
film surface changes during corona discharge. These
methods use various liquids to probe the chemical
characteristics of the film’s surface by forming con-
tact tension boundaries which can be measured.
These liquid contact angle probes of the film’s sur-
face characteristics are more sensitive than the
“dyne liquid” methods. Blitshteyn15 examined the
theory of surface tension measurements and inves-
tigated the contact angle of water droplets as a mea-
sure of wetting surface tension. The water contact
angle test was proposed for process and quality con-
trol of corona-treated films.
The interfacial energies between a solid and a liq-
uid determine wetting characteristics. The contact
angle (␪) of a non-wetting liquid on a solid surface
is related to solid-vapor, solid-liquid, and liquid-va-
por interfacial energies (␥sv, ␥sl, ␥lv, respectively) via
Young’s equation, given by:
␥lv cos ␪ ⫽ ␥sv ⫺ ␥sl
␥lv is the liquid surface tension. ␥sv is different from
the solid surface energy, ␥s, but it is usually approx-
imately taken as equal as ␥s since the absorption of
vapor is negligible and the exact relation between
␥s and ␥sv is unknown. Therefore, the surface energy
estimated from contact angle measurements varied
depending on the probe liquids used and the model
used to analyze the data. Mangipudi et al.16 pre-
sented a direct method to measure surface energy
(␥s) of corona-treated polyethylene using the surface
forces apparatus (SFA). It was based on the follow-
ing theory.
When two smooth solid bodies are brought into
contact in the absence of any applied load, they de-
form due to the action of surface forces between
them. Further, due to the action of these attractive
forces, a finite tensile load is required to separate
the surfaces from contact. This tensile load is called
the pull-off force, Ps. This pull-off force is related to
the thermodynamic work of adhesion, W, and the short
radius of curvature of the surfaces according to the standard
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CORONA TREATMENT OF POLYOLEFIN FILMS

theoretical relations developed by Johnson, Kendall,

and Robert (JKR theory).17 The pull-off force is mea-
sured in the SFA. The basis for the JKR theory is
mechanical equilibrium between the energy re-
leased due to adhesion and the elastic energy stored
due to the deformation of the contact zone. Accord-
ing to the JKR theory the pull-off force required to
separate the surfaces from contact is given by

3␲WR
Ps ⫽
2

Where thermodynamic work of adhesion: W ⫽ 2␥s;

␥s is solid surface energy.
The extent of modification was controlled by
varying the corona energy density. The relationship
between treatment level and line speed is approxi-
mately linear. However, the relationship of the sur-
face energy of the film to power consumption is not
continuously linear.18 It has been found that this
nonlinearity is also affected by the level of slip
agents in the film.
During corona discharge, the surface compo-
nents become polarized through reaction between
the molecular oxygen and nitrogen fragments gen-
erated by the electrical discharge. The surface area
thus created is itself at a surface energy higher than
that of its surroundings. As a result, the film addi-
tives will migrate to these high-energy surfaces and
reduce the surface energy of these areas through the
slip additive’s molecular orientation at the film sur-
face.
It was proposed to separate the surface tension
into polar and nonpolar contributions.
␥s ⫽ ␥ ds ⫹ ␥ps
FIGURE 1. Surface oxygen concentration (atom %)
versus corona energy density (J/m2). Type 1 was on a
laboratory unit and type 2 was on an industrial unit. Type
2 treatment is more effective than type 1 treatment in
terms of oxygen incorporation.16
As shown in Table II, the polar component of the
surface energy is the component that significantly
changes during corona treatment of the film. The
dispersive component remains relatively un-
changed. Therefore, corona treatment increases the
polar surface energy component by introduction of
polar groups in the surface and as a consequence,
increase the substrate surface energy that leads to
improved wetting and adhesion properties. The po-
lar component of surface energy is the key to un-
derstanding the changes in adhesive behavior of the
films during corona treatment.19

Where rs is surface tension of the film, ␥ ds is surface

tension component due to dispersive (nonpolar)
forces, and ␥ ps is surface tension component due to
polar forces. ␥s increases as the extent of surface
modification increases. The enhancement in ␥s can
be correlated to the increase in oxygen concentra-
tion on the surface. In the corona-treated samples
surface oxygen elemental concentration varied from
10 to 18% depending on the energy density level
(Fig. 1). As polar groups are introduced on the sur-
face, the surface energy of PE can increase from
about 33 to 55 mJ/m2. With an increase in the corona
treatment level, the density of polar functionalities
on the surface increases (Table I), resulting in an
enhancement in surface energy.
Effect of Resin Additives on
Corona Treatment
Polyethylene and polypropylene normally con-
tain a variety additives such as stabilizers to prevent
oxidation, retain melt index, or maintain color.
Commercially used additives include stearically
hindered phenol antioxidant, organic phosphite an-
tioxidant, silica antiblock agent, zinc stearate, alky-
dialkanolamine, and erucamide slip agent. Other
stabilizers such as metal stearates and dihydroxy short
fatty acid amines are added to control melt index standard

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TABLE I
Surface Analysis of Corona-Treated Polyethylene, XPS data16
Percentage Composition of Carbonous Functional Groups

Total O 1s
Corona Energy Concentration 9C9H 9C9O9
Density, kJ/m2 Atomic % (284.6)a (286.1) ⬎ C " O(287.6) HO 9 C " O(289.0)

Type 1 Treatment
28 10.0 86.2 9.4 2.8 1.6
54 14.3 79.6 12.4 4.9 3.1
128 14.2 81.1 11.3 4.8 2.8
Type 2 Treatment
2.5 12.7 82.4 11.1 4.3 2.2
17 17.8 77.2 13.2 5.0 4.6
a
Numbers in parentheses represent the peak position corresponding to the groups. The width at half-maximum varied from 1.3 to 1.5
eV. Type 1 treated was done on a laboratory scale unit, and type 2 was done on an industrial set up.

and color. The antioxidants normally consist of two
types: primary antioxidants which function as free
radical scavengers and secondary antioxidants
which are hydroperoxide decomposers.20 Typical
primary antioxidants are the hindered phenols (e.g.,
butylate hydroxytoluene (BHT), Irganox 1010, and
Irganox 1076). The secondary antioxidants are
typically organophosphorous compounds like tris-
nonylphenyl-phosphite (TNPP) or tetrakis [2,4-di-
tert-butylphenyl] 4,4’-biphenylylene-diphosphonite
(P-EPQ).
BHT IN LDPE
BHT in the LDPE films had no effect on corona
treatability or subsequent printability of the films.
ESCA results showed that corona-treated LDPE
films containing BHT exhibited oxygen levels com-
parable to films without BHT. In fact, oxygen levels
were slightly higher, probably due to the presence
of the oxygen containing BHT.21 Surface wetting
was identical for films with or without BHT. Ad-
hesion performance was also unaffected by the
BHT. Ink adhesion was zero for an untreated film
and 100% for a treated film, whether or not BHT
was present.
STABILIZERS IN LLDPE
Certain stabilizers used for LLDPE resins proved
to be surface active and therefore affected the results
of corona treatment of LLDPE films. XPS analysis
showed that Irganox 1010 and zinc stearate are on
the film surface, even without corona treatment.
Treatment causes TNPP, P-EPQ, and the dihydroxy
fatty amine to be detectable on the film surface. To-
tal oxygen levels measured for all treated films were
comparable to the treated film without stabilizers.

TABLE II
Surface Energy Profiles of Commercial Films18
Total Surface Energy Dispersive Component Polar Component
Films (dynes/cm) (dynes/cm) (dynes/cm)

Polyethylene (LDPE) 32 31 1
(corona treated) 43 33 10
Poly(ethylene terephthalate) 47 43 4
(corona treated) 54 41 13
Oriented Polypropylene (OPP) 30 29 1
short
(corona treated) 43 29 14
standard

174 VOL. 18, NO. 2

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Treated films containing Irganox 1010 showed stabilizers. All untreated LLDPE films showed zero
no ⬎ C " O groups. Treated films containing adhesion, and all treated LLDPE films showed 100%
P-EPQ or the fatty acid amine showed little or no ink adhesion.

9 O 9 C " O groups (Table III).

SLIP AGENT (ERUCAMIDE)
Clearly, the additives affect the oxidation chem-
istry of the corona treatment process. Irganox 1010 In the solvent-based ink system, the erucamide/
is classified as a free radical scavenger, while P-EPQ oligomers were evidently efficiently solved and
is a hydroperoxide decomposer.20 These results sug- good film/ink interaction was achieved. Adhesion
gest that both free radicals and peroxide species are now correlated with the surface oxygen content ob-
important in the mechanism of surface oxidation by served on the washed film samples and the presence
corona treatment, which agrees with what has been of bloomed slip agent had minimal effect. As the
proposed by others.22 Surface wetting results level of erucamide increased, it appeared to inter-
showed that only the dihydroxy fatty acid amine fere with treatment efficiency. Its presence obvi-
affected the surface wetting values. Treated films ously had a detrimental effect on film printability
containing this additive showed contact angles with water-based inks. Solvent-based inks were less
about 20 degrees lower than films without it; that affected by bloomed slip agent. In actual commer-
is, very high wetting. Tape adhesion also was af- cial applications, this effect requires a reduction of
fected only by the presence of fatty acid amine in the level of erucamide slip agent in films to obtain
treated film. This compound significantly decreased adequate printability with water-based inks. In
the force required to remove tape from the treated some cases, slip agent content should be reduced to
surface. Ink adhesion was not affected by any of the the point that other extrusion and handleability
properties of the resulting films are compromised.
HP-LDPE and LLDPE films with similar erucamide
contents, treated to equivalent surface energies,
TABLE III showed roughly equivalent ink adhesion when
Single Stabilizersin LLDPE ESCA Analysis: Curve Fit21
printed with a water-based ink.
Oxygen Species (relative %) There were two possible explanations for these
observations. Corona discharge in air was success-
ful in producing some nitrogen incorporation into
Sample, 9C9O9
the HP-LDPE films in contrast to the LLDPE sam-
Treatment Level ⬎C" 9O9C"O
ples. Alternatively, the erucamide slip agent may
Barefoot LLDPE have bloomed rapidly enough during processing
Low 57 25 19 that the surface which was actually treated was a
High 48 28 24 heavily erucamide-coated one. The discharge treat-
Irganox 1010 ment is energetic enough that erucamide on the sur-
Low 65 0 35 face could be essentially grafted to the polyethylene,
High 67 0 33 either intact or in parts, to produce bound nitrogen.
Irganox 1076 Griffin23 studied the interaction of a slip additive,
Low 58 21 21 erucamide, and corona treatment in low- and high-
High 52 26 22 density polyethylene extrusion-coated film. It
TNPP showed that the surface tension of the corona-
Low 56 29 15 treated polymer decreased with increasing slip ad-
High 45 34 21 ditive concentration and increased with increasing
P-EPQ corona treatment (Table IV). In systems containing
Low 75 25 0 no slip additive, corona treatment only slightly in-
High 77 11 9
creased the surface tension, whereas, in systems
Zinc Stearate containing slip additives, the corona treatment had
Low 59 22 19
a much more pronounced effect. Low-density poly-
High 47 28 25
ethylene showed that even at high levels of corona
Dihydroxy Fatty Acid Amine
treatment, the surface tension could be raised to the
Low 73 22 6
levels of the system containing no slip additive. short
High 77 23 0
However, it was shown that at high levels of corona standard

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TABLE IV
LDPE Surface Tension after Corona Treatment
(Dynes/cm)23
% Slip
Watt Density 0 0.05 0.1 0.15
(BUT/m2) Surface Tension (Dynes/cm)
1.2 56 36 35 34
3.1 58 40 36 35
6.1 62 50 50 48
treatment, the surface tension of high-density poly-
ethylene could be increased much closer to that of
the system containing no slip additive. In both low-
density polyethylene and high-density polyethyl-
ene, with 0.05% slip additive, a corona treatment
level of 10 BTU/m2 showed a greater surface ten-
sion than the system containing no slip additive at
only a watt density rating of 2 BTU/m2. As the con-
centration of erucamide increased, it appeared to in-
terfere with treatment efficiency. Its presence obvi-
ously had a detrimental effect on film printability
with water-based inks. Solvent-based inks were less
affected by bloomed slip agent. In actual commer-
cial applications, this effect usually requires a re-
duction of the level of erucamide slip agent in films
to obtain adequate printability with water-based
inks. In some cases, slip agent content should be
reduced to the point that other extrusion and ma-
terials-handling properties of the films are compro-
mised. Therefore, depending on the required end-
use properties of the polyolefin extrusion coated
substrate, a balance between percentage of slip ad-
ditive and amount of corona treatment should be
established.
Insufficient Treatment and
Overtreatment
The important parameter in regulating the treat-
ment level, as noted earlier, is the energy density
with which the polar group or ions impart to the
treated surface. Recommended treatment levels for
polyolefins are 3 – 4 watts · min/ft2, although much
higher levels are sometimes necessary for good
adhesion.18 Both insufficient treatment and over-
treatment will lead to reduced effectiveness of co-
176
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rona treatment in terms of the wettability and ad-
hesion characteristics of polyolefin films.
Insufficient treatment may result from too low
energy density level of corona or too short treatment
time so that the exposed film cannot be modified to
desired surface energy. Figure 2 shows that the co-
rona discharge time necessary to treat polypropyl-
ene film to 40 dynes/cm (the acceptable level of
treatment for printing or laminating operations) de-
pends on the relative humidity.
As the relative humidity increases, effective co-
rona treatment requires a longer discharge time. The
presence of adsorbed water appears to interfere
with the formation of the peroxide, ROOR. This sug-
gests the possibility that the initial hydrogen radical
abstraction process may be reversible in the pres-
ence of surface moisture.
Figure 3 showed that two chemical reactions take
place during the corona treatment process.23 The de-
sired process is the first reaction, which takes place
at a faster rate than the second one, at the beginning
of the reactions, forming carbonyl, carboxyl, and hy-
droxyl groups. These groups are highly polar and
thus increase the surface tension. The second reac-
tion, which occurs at a slower rate, involves the con-
version of the aforementioned carbonyl groups into
ether groups. These ether groups are nonpolar in
nature and, therefore, tend to lower the surface ten-
sion. Thus, there should be a carefully monitored
balance between having enough corona treatment
to obtain desired surface tension, but not over-
treating (i.e., excessive treating), which has also
been found to enhance the formation of nonpolar
FIGURE 2. Relative humidity effect on corona
discharge time to reach a treatment level of 40 dynes/ short
cm.18 standard
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ADV WILEY
FIGURE 3. Surface energy versus corona treatment.23
ether groups, and which detracts from adhesive
strength.
Overtreatment usually leads to occurrence of
bumps on the polyolefin surfaces and has a deteri-
orating effect on the adhesion and wettability char-
acteristics. 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 increased with a longer time
of treatment. Bump size also increased when the
temperature was raised for a constant time of treat-
ment. Bumps of about 1 ␮m in diameter were cre-
ated by 1-min treatment at 50⬚C while treatment for
15 min at 75⬚C produced 10 ␮m bumps.24
Experiments were carried out in which the flat
plane electrodes of the corona device were replaced
by two “needle” electrodes. When the PE or PP
sheet was treated in an oxygen discharge between
the electrodes, the morphological changes on the
surface were similar to those found for the flat plate
corona. However, bumps were formed only where
the discharge struck the polymer surface and the
size of the bumps decreased with increase of the
distance from the electrodes. This suggests that the
formation of bumps is in some way associated with
the corona discharge itself and is not due only to the
reaction of an active gas with the PE or PP surface.
An unexpected result was that the bumps on a
treated surface were easily removed by dipping the
sample into CCl4, ethanol, or 0.2% aqueous NaOH.
At low resolution, the solvent-dipped surface ap-
peared to be similar to the untreated surface. How-
ever, with high resolution, the treated and ethanol-
dipped surface appeared rough and textured
ADVANCES IN POLYMER TECHNOLOGY
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CORONA TREATMENT OF POLYOLEFIN FILMS
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 re-
moved.
Research has shown that polyolefin films corona-
treated for long times at elevated temperatures ex-
hibit reduced bond strength and have more loose
surface materials than films more modestly corona-
treated.24 It was speculated that these degradation
products might act as a weak boundary layer in re-
ducing self-adhesion. One could also propose that
the degradation products of such gross overtreat-
ment might mask the underlying enol groups and
prevent the close approach of the two surfaces nec-
essary for H-bond formation.
Two possible explanations of the corona-induced
bumps on the corona-treated surface are that the po-
lyolefin possesses an inert skin on its surface which
is not much attacked by the active species in an oxy-
gen-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.25 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. It showed that friction force measurements
with AFM (Atomic Force Microscopy) on excessive
corona discharge-treated PP surfaces provided in-
formation about morphological changes. Droplet-
like protrusions were found to be physically ab-
sorbed on the polymer bulk surface. Contact angle
measurements correspond to the AFM measured
protrusion angle and hence, supported the assump-
tion of local surface melting or sublimation as a pos-
sible explanation for the formation of the protru-
sions. It was indicated from friction force
measurements that the molecules of the droplets
were chemically different and of low molecular
weight.
In the previous AFM study of Overmey et al.,26
changes in the morphology of corona-treated un-
iaxially oriented PP and biaxially oriented PP have
correlated to self-adhesive strength of the films.
Their diameters and heights of bumps increase pro-
portionally with the applied corona dose after a
threshold of about 18 J/cm2. It has been assumed short
that the loss of adhesive strength is mainly caused standard
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by (a) a reduction of the contact area and (b) the
adhesive strength of the polymer bulk surface. It has
been 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.
Aging and Re-Treatment
Once a film is corona-treated to an acceptable
level, what happens if the printing or adhesion pro-
cess does not take place immediately? It tends to
decay with time.27 Film surfaces after the treatment
are essentially dynamic rather than static. Surface
migration of additives and low molecular weight
materials will continuously change the surface until
a new equilibrium concentration is reached. This
equilibrium surface would be expected to be of
lower surface energy, which in turn, could be det-
rimental to printability, particularly with water-
based inks. Changes in surface chemistry induced
by film may stem from three phenomena:
1. Interreaction of chemical groups on the
treated surface;
2. Further oxidation and degradation with ex-
posure to air;
3. Migration of small molecules into the film or
covering of reactive sites by exudation of ad-
ditives and low molecular weight polymers to
the surface.
The amount of corona treatment decay is depen-
dent on many factors, including time, treatment
level, substrate type and amount of additives, and
handling and storage environment. The greater the
time the treated surface is left idle, the greater the
amount of decay. One study showed that between
1 and 7% of treatment was lost in 9 days, and 32 to
38% in 37 days.28 The higher the amount of initial
treatment, the greater the relative treatment loss.23
The substrate and any additives also play a sub-
stantial role in corona treatment decay. Different
polymeric materials react differently to corona treat-
ment. The tightness and handling of the roll will
also cause decay of treatment. Furthermore, the
temperature and humidity of the rolls storage en-
vironment may affect the rate of decay.
Markgraf29 reported that although treatment de-
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cay can be caused by temperature, humidity, pres-
sure, transfer, and oxygen, the greatest single cause
of surface treatment decay on polyolefins is additive
migrations, usually by fatty acids used for slip im-
provement, to the film’s surface after treatment.
These slip additives, such as erucamide and stear-
amide, seriously affect the wettability of the films.
Corona treatment has a tendency to degrade over
time, which poses a major concern to many con-
verters and their customers. Some think that this is
due to diffusion of the radicals formed during co-
rona treatment.30– 32 Many extrusion coating lines
have in-line printing and coating stations. These in-
line printing and coating stations greatly benefit
from in-line corona treatment. Immediately prior to
being printed on or coated with water or solvent-
based coatings, the substrate passes through a co-
rona treating station.
To study the effect of storing treated film and the
effectiveness of corona treatment of aged films, two
LLDPE films from each formulation were wound up
and stored for one month.33 Surface energies and ink
adhesion were measured after 7 days and again af-
ter 22 days. Surface energy measurements and
ESCA analyses were performed again after a one-
month aging period, and the films were then re-
treated with the corona discharge to a surface en-
ergy target of 45 dynes/cm. The film treated to 45
dynes for each of these three formulations.
All samples formulated with erucamide showed
increased levels of slip agent in the surface after the
aging period.33 Furthermore, the absolute amount of
erucamide observed depended on the concentration
of erucamide used in the formulation. Surface oxy-
gen contents generally increased as well, but de-
creased in the case of the additive-free films. It was
interpreted that these higher oxygen levels on for-
mulated films were due to the blooming of other
additives rather than to the continued oxidation of
the film surface. However, it was not possible from
the ESCA data to definitively identify particular ad-
ditives present. Instead, this interpretation was re-
inforced by washing the film in ether: after washing,
surface oxygen data moved toward the content ob-
served on the ether-washed samples of the same
films immediately after corona treatment.
The measured surface energy also declined
slightly with time. Printabilities, as measured by ink
adhesion, were relatively stable over the 22-day pe-
riod of the experiment. The effect of aging was most
pronounced on the samples formulated with extra
erucamide. Indeed, the only sample that exhibited short
standard
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CORONA TREATMENT OF POLYOLEFIN FILMS

a significant difference in ink adhesion was the 45-

dyne sample formulated with extra slip agent.
The films were retreated by corona discharge to
give a surface energy of 45 dynes/cm. The re-
treated films exhibited much higher surface oxygen
contents than those observed when the samples
were treated immediately after extrusion. This was
true even on films that were previously untreated.
As a control on the corona treatment equipment
used in these experiments, freshly extruded LLDPE
films with identical formulations as the aged films
were run and treated concurrently. While these
samples did show a slightly higher level of surface
oxidation than observed previously at the 45
dynes/cm level, they were substantially lower in
surface oxygen content than the treated aged sam-
ples.
This improvement in incorporating oxygen was
also evident in the adhesion of water-based inks af- FIGURE 4. Effect of aging on the surface energy of
ter treatment. Both the additive-free film and the corona re-treated PP film.34
resin containing the standard additive package
showed better ink adhesion on the re-treated aged
samples than observed on the same films which had
been treated immediately after extrusion. indicated that the re-treatment may be an effective
Aging can affect surface energy; however, re- way to reduce the aging effect.
treatment readily restored the film’s printability. Re-
treated films appeared to give a higher surface oxy-
gen content at equivalent surface energy in
comparison to freshly treated films. In fact, both
previously treated films and aged untreated films
Summary
(not treated immediately after extrusion, etc.)
achieved much higher surface oxygen content dur- Corona discharge introduces polar groups into
ing re-treatment than those treated immediately af- the polymeric surfaces and, as a consequence, in-
ter extrusion. creases the polar component of surface energy,
Adelsky34 studied the effects of corona retreat- which is the key to understanding the improvement
ment on surface characteristics of oriented polypro- in wettability and adhesion characteristics of the
pylene films. It was pointed that the improved wet- films by corona treatment.
tability by retreatment was achieved by creation of Some resin additives such as BHT had no notable
additional polar groups on the film surface. The re- effect on corona treatability or subsequent wettabil-
treatment also “cleans” the film surface by remov- ity and adhesion of the films, but some (such as er-
ing (through oxidation, burning, or volatilization) ucamide slip agent and fatty acid amine) usually
the slip additives that have migrated to the surface. have detrimental effects on corona treatment effi-
The retreatment could be carried out in a manner ciency. The surface tension of the corona-treated po-
typical of what a printer would do before applying lyolefin films decreased with increasing concentra-
inks or coatings. tion of the additives and increased with increasing
Figure 4 showed that the re-treatment increased corona treatment.
surface energy proportionally to the power output. Sufficient treatment is necessary to modify the
The changes of dyne level upon aging were depen- exposed surface to a desired level of surface energy,
dent on the power output of corona re-treatment. but overtreatment also leads to surface polymer
The aging effect was significant when the power degradation and the occurrence of bumps on the
output was small but it became very small when the surfaces, which also has a deteriorating effect on the
power output increased up to a certain level, which adhesion and wettability characteristics. short
standard

ADVANCES IN POLYMER TECHNOLOGY 179

ADV WILEY
CORONA TREATMENT OF POLYOLEFIN FILMS
Corona treatment has a tendency to degrade over
time. The greatest cause of the aging for polyolefin
films is additive migrations, usually by fatty acids,
erucamide, and stearamide, although it depends on
many factors, such as time, treatment level, temper-
ature, humility, and pressure. Re-treatment may be
an effective way to reduce the aging effect.
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