CMYK

C TECHNOLOGY
OVER STORY

Adhesion
Promotion
by Surface
Bhupendra Singh
Product Manager
Bloom Packaging Pvt. Ltd.,
Mumbai

Modification of
Polymer
Introduction
Polyolefin’s constitute the most often surface
treated materials. The good chemical resis-
tance and the non-polar nature of the
polyolefin’s surface prevent a good adhesion
of the printing ink as well as labels. Amongst
polyolefin’s polyethylene has the lowest sur-
face free energy of 31 dynes/cm @20°C. Ma-
terials with surface energy below 33 dynes/
cm require pre-treatment and above 36-38
dynes/cm may usually be directly printed. Use
of corona, flame and other methods increases
the surface energy level in excess of 42 dynes/
cm. Ideally, the surface energy of the plastic
should be 7 to 10 dynes/cm higher than the
surface tension of the solvent or liquid. For
example, a printing ink having a surface ten-
sion of 30 dynes/cm would not wet to a ma-
terial having a surface energy less than 37-39
dynes/cm. Hence polyolefin’s are frequently
subjected to surface treatment to improve
their bonding characteristics.
Need for Printing on Plastics
• One important reason is to produce a
greater range of multicolor decoration
where single color moulding is more eco-
nomic.
• Printing of plastics offers greater scope
to the designer in selective decoration, as
The most often used methods are solvent cleaning
and etching, corona discharge for films, flame
treatments for moulded articles, plasma treatment
and UV treatment method.
more then a single color may be used.
• Printing can be used to alter the surface
appearance giving a less plastic image
by reducing the gloss.
• Certain decorative effects can be con-
ferred which are difficult to produce by
moulding in colours, such as polychro-
matic, wood grained and pearl finish.
• Light colored finishes are obtained from
dark colored resin such as phenolics.
• Plastics are painted for covering the de-
fects such as flow lines, glass fibers in re-
inforced plastics.
• Self-coloured mouldings are more expen-
sive if a range of colors is necessary. Main-
taining the continuity in the color and
low gloss is difficult.
• It also permits the use of mixed residues
of regenerated plastics of various colors.
• It adds eye appeal to the articles.
• Printing reduces the electrostatic charge
and hence dusts attraction on the surface.

THE ECONOMIC TIMES POLYMERS • FEBRUARY - MARCH, 2008 37

CMYK
Polyolefin's constitute
the most often surface
treated materials. The
good chemical
resistance and the
non-polar nature of the
polyolefin's surface
prevent a good
adhesion of the
printing ink as well as
labels.
38 THE ECONOMIC TIMES POLYMERS
• Ultra violet resistance of the plastics can
be improved for exterior applications.
Methods for Surface Modifications
Various methods are used for the surface
modification such as
• Solvent cleaning and etching
• Mechanical abrasion
• Chemical etching
• Additives
• Flame treatment
• Corona discharge
• Plasma treatment
• Ultra violet irradiation
The most often used methods are sol-
vent cleaning and etching, corona discharge
for films, flame treatments for moulded ar-
ticles, plasma treatment and UV treatment
method.
Solvent Cleaning and Etching
Solvent cleaning and etching is one of the
most common techniques of surface treat-
ment. The surface of plastic is normally con-
taminated with grease and dust which comes
from various sources such as mold release
agent, rust preventives, lubricants, dust etc. It
is because of these foreign matters, adhe-
sion of paint, ink or adhesive to the plastic
surface becomes very difficult.
To improve the adhesion of the paint, ink
or adhesive, the surface of the substrate is
cleaned using solvents such as isopropyl al-
cohol (IPA), acetone, methanol, hexane, ethyl
acetate, toluene and other organic solvents.
During solvent etching some surface
change also takes place along with removal
of contaminants. Solvent swells the amor-
phous and low molecular weight impurities
and portions of polyolefin surfaces, making
it susceptible to the penetration of ink or
coating. LDPE, HDPE and PP surfaces can be
etched by immersing it in hot solvent at 80°C.
Limitations of Solvent Cleaning Method
• Many organic solvents are toxic
• Most of the solvents are flammable
• Some organic solvents can dissolve the
plastic
Surface Treatment by Corona Discharge
Corona discharge treatment is the most
widely used method for improving the ad-
hesion properties of the plastic films such as
polyolefin films prior to lamination. This treat-
ment is used for various polymers such as
polyolefins, polyfluorocarbons, polyesters,
polyvinylchloride, silicone, nylon and others.
Corona discharge treatment incorporates
various functional groups such as carbonyl
• FEBRUAR Y - MARCH, 2008
groups at the polymer surface.
A corona discharge system consists of a
generator, transformer and treater.
The generator takes in low voltage at
lower frequency of 50 Hz and amplifies the
frequency to higher value of 25-30 kHz. Trans-
former increases the voltage to the required
voltage in the range of 15000-30000V. The
treater consists of electrode, dielectric cover
and grounded metal body. The electrode in
the form of a solid bar or segmented elec-
trode is used. Segmented electrode minimises
the sparking. A schematic diagram of a seg-
mented ceramic electrode corona treater is
shown in Fig.1.
Mechanism
Since the voltage used is A.C., the electrodes
become alternatively positive and negative
with respect to each other. The electrons and
protons start moving and changing direc-
tions. Electrons, protons, excited atoms and
ions in the form of corona discharge break
C-C and C-H bonds on the plastic surface
forming radicals. These radicals react with
oxygen and nitrogen in air and forms polar
groups on the plastic surface.
Many factors play an important role in
effective corona discharge treatment such as
power supply, frequency, air gap, dielectric
material & discharge electrode configuration.
Corona discharge treatment lowers the
heat sealing temperature of many polymers.
Polyethylene treated by corona discharge
method can be heat-sealed at temperatures
as low as 75°C; while treated polyethylene
terphthalate film can be heat sealed at 140°C.
Problems Encountered with Corona Dis-
charge Treatment
• Greater level of treatment increases the
blocking tendency of the film.
• Contact of Corona discharge treated film
and metal should be avoided as it erases
the treatment on the surface.
• Additives such as slip additives and other
processing aids reduces the treatment
over time as these additives migrate to
Fig. 1: A schematic diagram of a segmented
ceramic electrode corona discharge treater
CMYK
Fig. 2: Corona treatment system for film blowing
plant
the surface and partially mask the polar
groups formed during the treatment.
Hence the corona discharge treatment
should be carried out just before the print-
ing operations.
The corona treatment system is intro-
duced into the film blowing equipment usu-
ally at the top of the tower as shown in the
Fig.2. Some systems incorporate the treat-
ment midway up the tower or at the base.
Flame Treatment
Flame treatment is widely used for surface
modification of polyolefin surfaces mainly
to improve printability or paintability. Basi-
cally, the process consists of applying heat to
the outer surface of polyolefin’s. The surface
should be hot enough to suffer modifica-
tion while the body remains at much lower
temperature. Sheeting’s below a thickness of
0.6 mm is usually treated by corona discharge
while flame treatment is used for heavier
sheets.
Heat can be applied by means of:
• Hot air
• Infra red radiation
• Flaming
The flaming techniques are very popular
and used extensively for treating blow mold-
ings prior to printing, labeling, or the appli-
cation of other decorative matter.
Mechanism
Flame contains excited species of O, NO, OH,
and NH, which can remove hydrogen from
the surface. The oxidation that follows is
propagated by a free radical mechanism.
Equations for the reactions, which can occur
during simple thermal oxidation of hydro-
carbon takes, place in three steps: Initiation,
Propagation and Termination.
Surface of the polymer exposed to simple
thermal oxidation greatly affects ease of oxi-
dation. Highly branched polymers oxidise at
a much more rapid rate than a linear poly-
mer such as polyethylene, unless the
branches are sufficiently bulky to sterically
hinder oxidation. If the polymer contains both
aliphatic and aromatic moieties; only the ali-
phatic portion is oxidised.
Flame Treatment of Moulded Article
Light surface oxidation by flame treatment
of moulded article with a non-luminous
flame. The surface is first thoroughly cleaned
to remove dirt and grease. The apparatus
consists of the one or more flames, which are
held at a fixed distance from the sample and
scanned over it at controlled speed.
To treat the large areas or complicated
shapes special multiple or robotized systems
have been in use.
Flame Treatment Apparatus for Polymer Films
A schematic representation for the flame
treatment of polymer film is as shown in the
Fig.3
Fig.3: Diagram of a flame treater for the polymer films
This equipment resembles the corona
treatment apparatus in that the central drum
is used as the base for the plastic sheeting.
The plastic goes over the drum and under a
series of burners similar to those found in a
gas furnace. Plasma treatment is a
Factors Affecting the Correct Flaming Treat- very efficient method
ment
for modifying plastic
• A good non-luminous fishtail flame surfaces. Polyethylene
should be used. The use of oxygen in-
stead of air tends to make the treatment surfaces can be
more effective.
effectively treated by
• The surface to be treated should be lo-
cated on the side of the blue part of the inert gas plasma
flame so that the flame impinges on the generated by a radio
surface well above the blue portion. In-
ner core length should be around 0.25” frequency field.
to 0.75” while the distance from inner core
tip to the surface about 0.25”.
• Flame contact time: Flame contact time is
generally a fraction of second but de-
pends on:
• Flame intensity
THE ECONOMIC TIMES POLYMERS • FEBRUARY - MARCH, 2008 39
CMYK
Corona discharge
treatment is the most
widely used method for
improving the
adhesion properties of
the plastic films such
as polyolefin films
prior to lamination.
This treatment is used
for various polymers
such as polyolefins,
polyfluorocarbons,
polyesters,
polyvinylchloride,
silicone, nylon and
others.
40 THE ECONOMIC TIMES POLYMERS
• Air to gas ratio
• Wall thickness
• The design of the part
• The type of flame used and
• The distance of the burner from the
article for flame treatment
The gas is burned using 10-15% excess
air over the stoichiometric ratio, in order to
obtain an oxidizing flame with a tempera-
ture of 1090-2760ºC.
Benefits of the Flame Treatment
• Higher treatment levels
• Low treatment decay rates
• Suitable for various product shapes and
sizes
Limitations of the Flame Treatment
• Flame treatment is not suitable for moul-
ded three dimensional objects where the
distance between the flame and the sub-
strate can vary.
• Sheets having thickness less than 0.6mm
are not suitable for flame treatment. Also
treatment cannot be used for films due
to high shrinkage in films.
• Melting occurs if the flame is too close.
• Open flame, particularly in or near a paint-
ing operation is usually forbidden for
safety reasons.
Applications
• Flame treatment is most often used to
improve ink adhesion to molded PE and
PP surfaces.
• Flame treatment is also used for acetal,
acetal copolymers and for polyethylene
terephthalate.
• Round containers can be treated on all
sides by rotating the container by drop-
ping it through a ring burner.
Modification by Ultraviolet Irradiation (UV)
UV irradiation produces surface modification,
which improves the wettability and
bondability of the plastics. Photons, usually
those with low wavelength, are energetic
• FEBRUAR Y - MARCH, 2008
species which are used to activate many
chemical reactions. A typical example of UV
action on polymer surfaces is their degrada-
tion by the sun exposure.
In most cases, modification is carried out by
• Introducing functional groups to the
material surface by
• Applying UV light to oxidize the material
surface or
• By allowing the material to contact a gas
or sensitizer to cause a photochemical
reaction.
• Allowing UV irradiation graft poly-
merization to occur at the material sur-
face.
UV lamps are widely used for the treat-
ment of polymer surfaces and the apparatus
involves essentially a lamp and sample illu-
mination device, which makes selective irra-
diation of substrate possible.
UV irradiation system consists of a UV
source, the Coating and the Substrate as
shown in Fig.4.
Fig.4: Schematic of UV treatment
Lamps are operated between 250-370 nm
wavelengths.
Effectiveness of UV treatment
The effectiveness of UV treatment depends
on:
• The intensity of UV source
• The distance between the UV source and
sample
• The coating of benzophenone
• The time of exposure
Advantages
UV irradiation treatment has various advan-
tages
• Reaction occurs at ordinary temperature
and pressure.
• Selective reaction is possible.
• Light energy can be focused on the sur-
face of the material.
UV treatment shows improvement in ad-
hesion but the time taken for the treatment
is high hence for commercial purpose this
treatment is not feasible.
CMYK
Plasma Treatment
Plasma treatment is a very efficient method for
modifying plastic surfaces. Polyethylene sur-
faces can be effectively treated by inert gas
plasma generated by a radio frequency field.
The utilization of plasma is a typical dry method.
Application of Plasma Treatment
Plasma treatment has developed into a com-
mercial important method for difficult to treat
surfaces. It is used in the industry to improve
the painting performance of plastic motor
vehicle bumpers and the printability of films.
Difference between Plasma Treatment,Corona
Discharge Treatment and Flame Treatment
Plasma differs from corona and flame treat-
ment in that plasma treaters are operated at
less than atmospheric pressure. This differ-
ence is the primary reason for it’s seldom use
in industry for adhesion promotions. In ad-
dition a system under a partial vacuum in-
herently requires a batch process which also
lowers cost effectiveness.
Instrumentation
A simplified diagram of a plasma treater is as
shown in Fig.5.
The material to be treated is placed in a
vessel that is evacuated. The pressure in the
Fig.5: Plasma reactor
vessel is increased by the addition of a gas in
which the plasma is to be struck. The most
commonly used gases in plasma treatment
for adhesion promotion is noble gases such
as argon and xenon. Alternately nitrogen,
oxygen and fluorinated gases can also be
used. After the addition of active gas, a radio
or microwave frequency signal is placed on
the coil surrounding the vessel. The coil in-
duces plasma inside the vessel.
Plasma Reaction of Polymers
In low temperature plasma for polymer treat-
ment, relatively few electrons and ions are
present in the gas. This is different from the
high temperature plasma of the sun and in
nuclear fusion. Hence the temperature of the
whole low temperature plasma gas is so low
that the degree of heat resistance of the
material being treated requires little atten-
tion. Only a small number of electrons present
in the gas have high energies.
The energy of electrons present in low
temperature plasma is in the range of 1 to 10
eV which causes the ionization and excita-
tion in the molecule of gas.
The activated particles react with the
polymeric material so that polymeric radicals
are produced on the surface layer of the
material. The polymeric radicals eventually
cause the surface layer to be oxidised, cross-
linked or decomposed. It should be noted
that the effects of the plasma reactor depends
to a great extent on the type of plasma reac-
tor, the oscillation frequency, the high fre-
quency output, the gas type the flow rate
and pressure of the gases, the treatment time,
the position of the sample and so on.
• Crosslinking: It has been reported that
when a polymeric material is plasma
treated in an inert gas such as helium or
argon; cross linkage are introduced into
the surface layer of the material.
• Oxidation and Decomposition of Polymer
Surfaces: When polymers are plasma treated
under relatively mild conditions, oxidation
reactions generally occur. As a result oxy-
gen atoms can be introduced into poly-
meric surfaces. Studies indicate that enhanc-
ing wettability by plasma treatment results
in high bonding strengths.
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THE ECONOMIC TIMES POLYMERS • FEBRUARY - MARCH, 2008 41