INTRODUCTION
Flame treatment is an industrial process used to improve wetting and adhesion
properties of polyolefin films (BOPP Bioriented Polypropylene; OPP - Oriented
Polypropylene; PE, PET, PS, etc.) and 3D components, such as automobile
body parts (bumpers, dashboards, headlights, etc.) and blow-molded bottles.
Polyolefin materials, and in particular PP (polypropylene) have many good
properties as: low cost; can be worked and shaped quite easily; can get good
mechanical properties, if properly worked; are very good electric insulators.
Anyway they are apolar on their surfaces, which are characterized by very poor
energies. This is the reason why they need to be treated, in order to make
possible their coating with inks, paints, adhesives, metal, and other materials
typically coupled with polyolefins, in industrial applications as flexible
packaging or automotive production.
FLAME CHEMISTRY
Activation of polyolefin surfaces by flame is realized by means of two actions:
• breaking of carbon - hydrogen links along the polymer
surface, thanks to flame high temperature, developed
by the combustion process. Theorical temperatures,
reached using C1–C3 hydrocarbon combustibles, are
between 1700 °C and 1900 °C. As first step in the
surface oxidation process, hydrogen abstraction is far
the more likely one, in comparison with breaking of a
C–C link along the macromolecular backbone. Links
C–C type are infact shielded, from radicals external
attacks, by means of hydrogen and metyl groups
surrounding the molecule backbone (cage effect). In
addition, the mobility of radicals –C° type, coming
from an eventual scission of C–C links, is really
reduced (because of radicals –C° dimensions), so high
is the probability of a recombination, after the scission,
between radicals –C° and °C-.
• Insertion of oxygen based groups – contained inside
the flame area - in correspondence of broken links
points, along the macromolecular chains. The oxygen
so transferred to the polymer surface acts as a bridge
between the polymer itself and the second material to
be coupled with it.
Premixed laminar flame - in which the fuel and the oxidizer are thoroughly
mixed prior to combustion - is produced by radical/chain reactions occurring in
a combustion system, formed by an oxidizer (generally air) and a combustible
(in a solid, liquid or gaseous state). Here will be considered just the last case,
being only gaseous combustibles typically hydrocarbons (natural gas,
methane, propane, LPG, etc.) – used for polyolefins surface flame treatment.
Chain branching step produces a radical pool, according to the following
oxyhydrogenation reactions:
(1) H + O2 → O + OH
(2) O + H2 → H + OH
(3) H2 + OH → H2O + H
(4) O + H2O → OH + OH
The sequence [Eqs. (1) - (4)] is of great importance in the oxidation reaction
mechanics of any hydrocarbon, in that it provides the essential chain branching
and propagating steps as well as the radical pool for fast reaction to occur.
It is this radical pool that develops the oxygen based groups inside the flame,
used to activate the polyolefin surface (2nd factor of action of the flame). First
factor being flame temperature.
BOPP SURFACE FLAME OXIDATION MECHANISM
BOPP surface oxidation by flame is in Literature defined as a Free Radical
Degradation, beginning with radicals attack on tertiary carbon of the
macromolecular backbone. The initial step in oxidation of polymers by a flame is
so passing through polymer-radical formation by hydrogen abstraction. H
abstraction along macromolecular chain is far more likely to occur respect to
carbon-carbon link breaking, because of cage effect exerted by methyl and
hydrogen group towards C-C link and because of lack of mobility of the C atoms,
after the link breaking, so they form again the link. Polymer-radical formation
occurs primarily by reaction with the O atoms, H atoms and OH radicals found in
the flame. Thermal energy from the flame could also generate polymer radicals
(alkyl radicals R). Hydroxyl OH radicals are considered from literature the ones
playing most important role in the film surface oxidation, since are the ones
characterized by highest concentration and highest reactivity (reaction rate
constant for OH radical is at least two order of magnitude higher than the ones of
the other radicals present in the flame, as molecular and atomic oxygen radical or
peroxyl radical).
H radicals will tend to compete with the OH and O species terminating the
oxidation step, so, basically H tends to compete to generate less wettable PP
surfaces.
A COMPARISON WITH CORONA TREATMENT
When using flame, the depth of Oxygen incorporation in the treated PP is
between 5 and 10 nanometers versus a depth of about 50 nanometers in case of
corona treatment. So with flame there is a more extensive oxidation
concentrated in a shallower surface region, that results in an higher wettability.
Corona treated PP (and in general polymers as PET, PE, and others) are
characterized by the presence, on their surface, of LMWOM. This presence is
much higher when increasing corona watt density applied to the material
(literature refers this as overtreatment). LMWOM stands for Low Molecular
Weight Oxidized Materials. These oxidized materials are produced on corona
treated PP surface because of C-C links breaking (this reaction is known in
literature as -scission reaction) and consequent weight lowering.
CHEMICAL COMPOSITION OF A CORONA TREATED SURFACE
CH3 CH3 PP SURFACE
CH2-CH-CH2-CH-CH2
CORONA TREATMENT
CH3 CH3
CH2-C-CH2-CH-CH2
OXYGEN
CH3 CH3
CH2-C-CH2-C-CH2
OOH
CHEMICAL COMPOSITION OF CORONA TREATED SURFACES
CH3 CH3
CH2-C-CH2-C-CH2
OOH
b-scission reaction C=O
O
CH3
C-OH
CH2-C Low molecular
weight
OOH C=O
O Þ alkoxy radicals RO° Þ LMWOM
LMWOM are oxidized materials water soluble or other solvent (as acetone or
methanol) soluble and generally more weakly anchored to the PP surface. Atomic
oxygen radical is the precursor of LMWOM formation, passing through alcoxy
radicals (RO) formation. Literature states that when an hot flame impinges the
cold (at about 400 K) PP surface, many radicals present in the flame (that is
produced by a radical reaction) are destroyed. This destruction doesn’t affect OH
radicals concentration – since they are far the more present radicals in the flame,
but there is a big impact on atomic oxygen radicals, that strongly diminish their
concentration. The following formation of alcoxy radicals – from which
LMWOM develop – is so negligible in case of flame; with flame LMWOM could
eventually form (as an alternative way respect to the one represented by RO
radicals) starting from carboxilate/peroxy groups (COO), but these groups
scission to form alkoxy groups is too slow to account for a significant formation
amount of LMWOM. Moreover formation of COO groups can be kept under
control with flame, working with an air/gas ratio not too gas lean (so not too
oxygen rich). The same phenomenon doesn’t occur with corona treatment, where
alcoxy radicals, that are present in a large extent, are involved up to 50% in the
eta-scission reaction types, so forming LMWOM. In a PP flame treated surface,
instead IMWOM (Intermediate Molecular Weight Oxidized Material) are present,
that are bigger than LMWOM, with higher weight, not soluble to water and other
polar solvents and so more strongly anchored to the PP surface. This fundamental
difference between corona and flame treatments, along with the fact that corona
produces a deeper treatment than on a web treated by flame, is the cause for an
higher surface energy of a flame treated film than a corona treated one. Among
web producers there is the folk to measure the wettability after treatment on the
web, through the specification ASTM D2578. This test is very simple to perform,
very fast also and can give to the operator immediately the idea if his machine is
correctly working. By the way ASTM D 2578 doesn’t tell everything about the
web surface after treatment.
Two films having same ASTM D2578 dyne level can have a huge difference in
terms of surface energy. And what really cares in terms of processability of the
web after the treatment is the surface energy it has, not the wettability.
A corona treated web can show a good wettability, thanks to the presence of
oxidized material on its surface (LMWOM), but these materials are weakly tied to
the film surface, so they are easily taken away from the surface itself, according to
typical delamination phenomenon.
This means that using corona you get a good fresh (on line) treatment, but then
you get a poor treatment for applications as printing, laminating and metallising
and you get a strong decay of treatment (aging phenomenon) few weeks after the
treatment. Flame treatment is characterized by an higher anchored oxidation type
of the polymer surface, than the one possible treating the web by corona, as
measured by ESCA (XPS–X ray photoelectron spectroscopy) technique.
Using corona treatment is possible to get, as shown on the above slide an oxygen
level % measured by ESCA in the order of 14 and higher (see below image),
increasing the treater watt density; but just a minor amount - about 5% is the
anchored one; the rest is given by LMWOM. In the case of flame treatment all the
oxidized material is well anchored on the film surface.
This difference is well underlined by a simple test: water washing of corona and
flame treated samples. Surface chemistry of corona treated film is strongly
affected by water washing, with a significant loss of surface oxidation and a
noticeable increase in the advancing contact angle of water.
Corona treated surfaces have an O/C ratio, at ESCA, up to 0,23, becoming, after
water washing, 0,08. In the case of flame O/C ratio is 0,18 before washing and
still 0,18 after washing. This is a clear evidence of the presence of water soluble
LMWOM on the corona treated PP, while flame treated PP has no detectable
LMWOM, since the O/C ratio does not vary with the water washing.
oxygen level vs Power
14
Threshold for formation of LMWOM in litterature = 8,3 Wmin/m²
12
10
Oxygen level %
8
Anchored oxygen level = 4,8%
6
Threshold for formation of LMWOM= 9,8 Wmin/m²
0
0 5 10 15 20 25 30 35 40
Power density (Wmin/m²)
Basing on this difference in surface chemistry and in surface energy, after flame
treatment and after corona treatment, much different is also film behaviour in its
performances. Presence of LMWOM first of all can explain higher treatment
decay observed in corona treated surfaces, respect to flame treated ones.
Treatment decay or aging depends much also on film composition and additives
presence inside it, but, considering same type of film, corona treated will always
decay faster than flame treated, because of the presence of the above reported
LMWOM.
FLAME TREATMENT APPLICATIONS ON MET AND PRINT BOPP
Metallised film after corona will present poor performances both in terms of
barrier to water vapour and to oxygen if compared to the ones of flame treatment.
Also metal adhesion after flame will be at least 30% higher after flame than after
corona and also much more lasting with the time. This last difference is well
underlined by REXAM tests, from which it is possible to see that starting metal
adhesion to substrate is much lower and also much faster dropping when film is
corona treated than one it is flame treated. This is confirmed by the fact that if
flame treated film is then corona treated (for example for refreshing treatment, as
in use in many converters facilities) REXAM test will give poor adhesion of the
metal if compared to the adhesion coming from just flame treated film. This
because corona is introducing LMWOM materials on the flame treated surface,
modifying its chemistry.
For printing applications particularly significant to explain the difference in
surface adhesion between corona and flame treatments is the results of an
experimentation run in esseCI lab. Different samples of the same film, both
corona and flame treated were analysed. The corona and flame treated samples
presented same treatment level, according to ASTM D2578 specification.
On the two samples series (flame and corona treated) were then spread different
types of Sun Chemical inks (Demachem, Multilam), nitrocellulose based inks,
modified using polyurethanes resins, by means of a metering rod (wire size 06),
according to TAPPI T552pm-92 specification. The samples were then dried, cured
in an oven equipped with a forced air circulating system, at 70°C for 10 seconds,
as per the ink producer recommendations. After the samples preparation, these
were used in two kinds of tests:
1. manual peeling test: according to the inks producer
specifications was performed both slow and fast peeling,
using an ASTM tape, 45° inclined respect to the sample
surface;
2. automatic peeling test: using a tensile strength testing
machine (dynamometer) – Zwick Roell type – in order to
measure the adhesion strength of the samples. The ASTM
tape has been fixed at one clamp of the dynamometer, and
the sample on the other clamp.
The inks used in the tests are generally used with a diluent (ethil acetate) and an
adhesion promoter. In the case of the test here reported no adhesion promoter has
been used, to underline the film treated surface strength and energy, coming just
from the surface treatment (corona or flame), so to check just the treatment
contribute to adhesion. Absolutely macroscopic is the difference in behaviour
between corona treated and flame treated surfaces, both in the manual and in the
automatic peeling test, in terms of ink surface removed by the tape, and in terms
of bond strength (in case of flame treated ink/film bond strength keeps around
400g; with corona treated samples well lower than 200g).
Printing
FLAME vs. CORONA SURFACE ADHESION
CORONA TREATED – SLOW PEELING FLAME TREATED – SLOW PEELING
CORONA TREATED – FAST PEELING FLAME TREATED – FAST PEELING
FLAME vs. CORONA SURFACE ADHESION
CORONA TREATED FLAME TREATED
In the below image, the samples (film + tape) on the top were coming after corona
treatment, while the samples on the bottom after flame treatment. It is evidenced
how in corona treated film, ink has moved from the film to the tape, while in
flame treated film, it has been the tape glue to move from the tape to the ink,
thanks to film high adhesion values.
FLAME vs. CORONA SURFACE ADHESION
CORONA TREATED
FLAME TREATED
CONCLUSIONS
Actually flame treatment technology is a mature one, but still characterized by
high improvements margin, as last process developments are demonstrating.
There is no machine able to do everything. Starting from this consideration, it is
anyway out of any question that flame treatment can warrant higher quality on
film treated surfaces, thanks to its higher surface adhesion and surface energy.
This is particularly true in applications as:
• metallisation: where flame treated surfaces,
compared to corona, allow significantly increased
barriers to water vapour (WVTR) and to oxygen
(OTR), as well as improved and longer lasting
adhesion of metal to the film, as widely
demonstrated by REXAM tests;
• printing/lacquering: where flame treated surfaces
allow, compared to corona, to get better printing
quality, improved toner adhesion and improved
visual quality, as well as improved rub-off and
abrasion resistance in flexo, rotogravure and
digital printing applications;
• tapes films.
When treating heat sealable film, flame treater presents a narrower working range
and, depending on process conditions and film type sealability on treated/treated
sides (TR/TR or external/external) can be not as good as when corona is used.
Concerning this point it is important anyway to underline the following: in the
flexible packaging industry treated/treated or Ext/Ext sealability is requested only
in uncommon applications (as overwrapping just for certain kind of biscuits and
tobacco films) or to form bellows. In these cases it is not requested an high
sealing strength, since the resistance of the package is given by the paper pack,
wrapped by the sealing.
So in these cases flame can warrant requested sealing strength also on TR/TR
sides. On all the other flexible packaging applications Fin Seal (sealing is on
untreated/untreated, that is internal/internal side), is always used when Horizontal
Form Fill Seal (HFFS) machines are run (for example with biscuits or long pasta
as spaghetti). In the case of snacks or short pasta used is Lap Seal with Vertical
Form Fill Seal (VFFS) machines, where the seal is on treated/untreated sides, so
external/internal.
In Fin Seal and Lap Seal cases, that are the far majority in flexible packaging
applications, as it is possible to see visiting a food market, flame can warrant
better results than corona, since it doesn’t affect, despite corona, the untreated side
of the film. In the case of chips are used VFFS machines, but with laminates
structures, where printed/treated sides are placed internally, so they do not
interfere with sealability.
In not so common application also a lacquer layer is used on the sides to be
sealed, in this case, again, no issues on sealability coming from flame treatment.
So, flame treatment issues with sealable films is a false problem, in the name of
which makes no sense to renounce to the higher performances of flame treament
over corona treatment as above described.
This is the reason why on an high performances 5-layers BOPP extrusion line
flame treatment has to be present, in bottom position (corona on the top), for
getting best results on all produced type films.
REFERENCES
[1] Lori G. "Aspetti chimico-fisici nell'attivazione di superfici mediante il trattamento
alla fiamma" (1985).
[2] Strobel M., Branch M.C., Ulsh M., Kapaun R.S., Kirk S., Lyons C.S. "Flame
Surface
modification of polypropylene film". J. Adhesion Sci. Technol. Vol.10, No.6 (1996).
[3] Strobel M., Sullivan N., Branch M.C., Jones V., Park J., Ulsh M., Strobel J.M.,
Lyons C.S. "Gas phase modelling of impinging flames used for the flame surface
modification of polypropylene films". J. Adhesion Sci. Technol. Vol.15, No.1
(2001).
