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CMYK

C TECHNOLOGY
OVER STORY

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

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

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CMYK

• Ultra violet resistance of the plastics can groups at the polymer surface.
be improved for exterior applications. A corona discharge system consists of a
generator, transformer and treater.
Methods for Surface Modifications The generator takes in low voltage at
Various methods are used for the surface lower frequency of 50 Hz and amplifies the
modification such as frequency to higher value of 25-30 kHz. Trans-
• Solvent cleaning and etching former increases the voltage to the required
• Mechanical abrasion voltage in the range of 15000-30000V. The
• Chemical etching treater consists of electrode, dielectric cover
• Additives and grounded metal body. The electrode in
• Flame treatment the form of a solid bar or segmented elec-
• Corona discharge trode is used. Segmented electrode minimises
• Plasma treatment the sparking. A schematic diagram of a seg-
• Ultra violet irradiation mented ceramic electrode corona treater is
The most often used methods are sol- shown in Fig.1.
vent cleaning and etching, corona discharge Mechanism
for films, flame treatments for moulded ar- Since the voltage used is A.C., the electrodes
ticles, plasma treatment and UV treatment become alternatively positive and negative
method. with respect to each other. The electrons and
protons start moving and changing direc-
Solvent Cleaning and Etching tions. Electrons, protons, excited atoms and
Polyolefin's constitute Solvent cleaning and etching is one of the ions in the form of corona discharge break
the most often surface most common techniques of surface treat- C-C and C-H bonds on the plastic surface
ment. The surface of plastic is normally con- forming radicals. These radicals react with
treated materials. The
taminated with grease and dust which comes oxygen and nitrogen in air and forms polar
good chemical from various sources such as mold release groups on the plastic surface.
resistance and the agent, rust preventives, lubricants, dust etc. It Many factors play an important role in
is because of these foreign matters, adhe- effective corona discharge treatment such as
non-polar nature of the sion of paint, ink or adhesive to the plastic power supply, frequency, air gap, dielectric
polyolefin's surface surface becomes very difficult. material & discharge electrode configuration.
prevent a good To improve the adhesion of the paint, ink Corona discharge treatment lowers the
or adhesive, the surface of the substrate is heat sealing temperature of many polymers.
adhesion of the cleaned using solvents such as isopropyl al- Polyethylene treated by corona discharge
printing ink as well as cohol (IPA), acetone, methanol, hexane, ethyl method can be heat-sealed at temperatures
acetate, toluene and other organic solvents. as low as 75°C; while treated polyethylene
labels.
During solvent etching some surface terphthalate film can be heat sealed at 140°C.
change also takes place along with removal
Problems Encountered with Corona Dis-
of contaminants. Solvent swells the amor-
charge Treatment
phous and low molecular weight impurities
and portions of polyolefin surfaces, making • Greater level of treatment increases the
blocking tendency of the film.
it susceptible to the penetration of ink or
coating. LDPE, HDPE and PP surfaces can be • Contact of Corona discharge treated film
and metal should be avoided as it erases
etched by immersing it in hot solvent at 80°C.
the treatment on the surface.
Limitations of Solvent Cleaning Method • Additives such as slip additives and other
• Many organic solvents are toxic processing aids reduces the treatment
• Most of the solvents are flammable over time as these additives migrate to
• 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
Fig. 1: A schematic diagram of a segmented
various functional groups such as carbonyl ceramic electrode corona discharge treater

38 THE ECONOMIC TIMES POLYMERS • FEBRUAR Y - MARCH, 2008


CMYK

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
Fig. 2: Corona treatment system for film blowing scanned over it at controlled speed.
plant To treat the large areas or complicated
the surface and partially mask the polar shapes special multiple or robotized systems
groups formed during the treatment. have been in use.
Hence the corona discharge treatment Flame Treatment Apparatus for Polymer Films
should be carried out just before the print- A schematic representation for the flame
ing operations. treatment of polymer film is as shown in the
The corona treatment system is intro- Fig.3
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 Fig.3: Diagram of a flame treater for the polymer films
while flame treatment is used for heavier
sheets. This equipment resembles the corona
Heat can be applied by means of: treatment apparatus in that the central drum
• Hot air is used as the base for the plastic sheeting.
• Infra red radiation The plastic goes over the drum and under a
• Flaming series of burners similar to those found in a
The flaming techniques are very popular gas furnace. Plasma treatment is a
and used extensively for treating blow mold-
Factors Affecting the Correct Flaming Treat- very efficient method
ings prior to printing, labeling, or the appli-
ment
cation of other decorative matter. for modifying plastic
• A good non-luminous fishtail flame surfaces. Polyethylene
Mechanism should be used. The use of oxygen in-
Flame contains excited species of O, NO, OH, stead of air tends to make the treatment surfaces can be
and NH, which can remove hydrogen from more effective.
effectively treated by
the surface. The oxidation that follows is • The surface to be treated should be lo-
propagated by a free radical mechanism. cated on the side of the blue part of the inert gas plasma
Equations for the reactions, which can occur flame so that the flame impinges on the generated by a radio
during simple thermal oxidation of hydro- surface well above the blue portion. In-
ner core length should be around 0.25” frequency field.
carbon takes, place in three steps: Initiation,
Propagation and Termination. to 0.75” while the distance from inner core
Surface of the polymer exposed to simple tip to the surface about 0.25”.
thermal oxidation greatly affects ease of oxi- • Flame contact time: Flame contact time is
dation. Highly branched polymers oxidise at generally a fraction of second but de-
a much more rapid rate than a linear poly- pends on:
• Flame intensity

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CMYK

• Air to gas ratio species which are used to activate many


• Wall thickness chemical reactions. A typical example of UV
• The design of the part action on polymer surfaces is their degrada-
• The type of flame used and tion by the sun exposure.
• The distance of the burner from the
In most cases, modification is carried out by
article for flame treatment
The gas is burned using 10-15% excess • Introducing functional groups to the
material surface by
air over the stoichiometric ratio, in order to
obtain an oxidizing flame with a tempera- • Applying UV light to oxidize the material
surface or
ture of 1090-2760ºC.
• By allowing the material to contact a gas
Benefits of the Flame Treatment or sensitizer to cause a photochemical
Corona discharge • Higher treatment levels reaction.
treatment is the most • Low treatment decay rates • Allowing UV irradiation graft poly-
widely used method for
• Suitable for various product shapes and merization to occur at the material sur-
sizes face.
improving the UV lamps are widely used for the treat-
Limitations of the Flame Treatment
ment of polymer surfaces and the apparatus
adhesion properties of • Flame treatment is not suitable for moul-
involves essentially a lamp and sample illu-
the plastic films such ded three dimensional objects where the
mination device, which makes selective irra-
distance between the flame and the sub-
as polyolefin films diation of substrate possible.
strate can vary.
UV irradiation system consists of a UV
prior to lamination. • Sheets having thickness less than 0.6mm source, the Coating and the Substrate as
are not suitable for flame treatment. Also
This treatment is used shown in Fig.4.
treatment cannot be used for films due
for various polymers to high shrinkage in films.
such as polyolefins, • Melting occurs if the flame is too close.
polyfluorocarbons, • Open flame, particularly in or near a paint-
ing operation is usually forbidden for
polyesters, safety reasons.
polyvinylchloride, Applications
silicone, nylon and • Flame treatment is most often used to
improve ink adhesion to molded PE and
others.
PP surfaces.
• Flame treatment is also used for acetal,
acetal copolymers and for polyethylene
terephthalate. Fig.4: Schematic of UV treatment
• Round containers can be treated on all
sides by rotating the container by drop- Lamps are operated between 250-370 nm
ping it through a ring burner. 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.
Modification by Ultraviolet Irradiation (UV) • Light energy can be focused on the sur-
face of the material.
UV irradiation produces surface modification, UV treatment shows improvement in ad-
which improves the wettability and hesion but the time taken for the treatment
bondability of the plastics. Photons, usually is high hence for commercial purpose this
those with low wavelength, are energetic treatment is not feasible.

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CMYK

Plasma Treatment tion. Only a small number of electrons present


Plasma treatment is a very efficient method for in the gas have high energies.
modifying plastic surfaces. Polyethylene sur- The energy of electrons present in low
faces can be effectively treated by inert gas temperature plasma is in the range of 1 to 10
plasma generated by a radio frequency field. eV which causes the ionization and excita-
The utilization of plasma is a typical dry method. tion in the molecule of gas.
The activated particles react with the
Application of Plasma Treatment polymeric material so that polymeric radicals
Plasma treatment has developed into a com- are produced on the surface layer of the
mercial important method for difficult to treat material. The polymeric radicals eventually
surfaces. It is used in the industry to improve cause the surface layer to be oxidised, cross-
the painting performance of plastic motor linked or decomposed. It should be noted
vehicle bumpers and the printability of films. that the effects of the plasma reactor depends
Difference between Plasma Treatment,Corona to a great extent on the type of plasma reac-
Discharge Treatment and Flame Treatment tor, the oscillation frequency, the high fre-
Plasma differs from corona and flame treat- quency output, the gas type the flow rate
ment in that plasma treaters are operated at and pressure of the gases, the treatment time,
less than atmospheric pressure. This differ- the position of the sample and so on.
ence is the primary reason for it’s seldom use • Crosslinking: It has been reported that
in industry for adhesion promotions. In ad- when a polymeric material is plasma
dition a system under a partial vacuum in- treated in an inert gas such as helium or
herently requires a batch process which also argon; cross linkage are introduced into
lowers cost effectiveness. the surface layer of the material.
• Oxidation and Decomposition of Polymer
Instrumentation Surfaces: When polymers are plasma treated
A simplified diagram of a plasma treater is as under relatively mild conditions, oxidation
shown in Fig.5. reactions generally occur. As a result oxy-
The material to be treated is placed in a gen atoms can be introduced into poly-
vessel that is evacuated. The pressure in the meric surfaces. Studies indicate that enhanc-
ing wettability by plasma treatment results
in high bonding strengths.

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Nov-Dec (1998)
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THE ECONOMIC TIMES POLYMERS • FEBRUARY - MARCH, 2008 41