Journal of Materials Processing Technology 121 (2002) 373–382

Cold plasma treatment of polypropylene surface:

a study on wettability and adhesion
Luigi Carrinoa, Giovanni Moronib, Wilma Polinia,*
a
Dipartimento di Ingegneria Industriale, Università degli Studi di Cassino, via G. di Biasio 43, 03043 Cassino, Italy
b
Dipartimento di Meccanica, Politecnico di Milano, P. za Leonardo da Vinci 32, 20133 Milano, Italy
Received 29 February 2000; accepted 15 November 2001

Abstract

The increasing use of polymeric materials in high technological fields, such as automotive, has forced the need to overcome some of their
limitations by means of innovative processing. In the automobile industry a complex and critical process is used in order to enhance both
wettability and adhesive properties of polypropylene bumper surfaces. Cold plasma treatment represents an efficient, clean and economic
alternative to activate polymeric surfaces.
The present work deals with air cold plasma treatment of polypropylene surfaces. Particularly, the influence of AC electrical discharge cold
plasma parameters on wettability and adhesion of polymeric surfaces was studied. Also, the nature of the relationship between wettability and
adhesion was investigated. Owing to the complexity of plasma–workpiece interaction, an experimental approach was followed. A set of
process variables (voltage, time and air flow rate) was identified and used to conduct some experimental tests on the basis of design of
experiment techniques. The experimental results show that the proposed plasma process may considerably increase polypropylene wettability
and adhesion properties. These outcomes represent the first step in trying to optimise the polymeric adhesion by means of this non-
conventional manufacturing process. # 2002 Elsevier Science B.V. All rights reserved.

Keywords: Cold plasma; Polypropylene; Wettability; Adhesion; Car bumpers

1. Introduction surfaces. A plasma is an ionised gas containing both charged

Polypropylene is heavily used to manufacture bumpers in
the automotive industry because of its lightness, its resis-
tance to both air agents and impact. It is formed by long
saturated hydrocarbon chains that contribute to its chemical
inactivity and prevent anchoring of paints. This is the cause
of bumper black colour. However, to meet aesthetic require-
ments of the automotive market, polypropylene has to
become more suitable for painting. In the automobile indus-
try a complex and critical process is used in order to enhance
both wettability and adhesive properties of polypropylene
bumper surfaces. It consists of three steps: (1) acid solvent
cleaning to remove grease and dust from surfaces; (2)
flaming to increase surface energy; (3) primer application
to reinforce adhesion of the coat on the bumper surfaces.
Cold plasma surface treatment is known as a powerful
process used to modify surface characteristics of both metal-
lic and polymeric materials. Therefore, it represents an effi-
cient, clean and economic alternative to activate polymeric
*
Corresponding author.
E-mail address: polini@unicas.it (W. Polini).
and neutral particles, such as electrons, ions, atoms, mole-
cules and radicals. There are two kinds of plasma: cold and
hot. The difference is the temperature of the heavy species: it
is similar to the electrons (104–105 K) in a hot plasma, while
it is lower than 773 K in a cold plasma (or non-equilibrium
plasma). Moreover, the working pressure of a cold plasma is
generally lower than the one of a hot plasma or atmospheric
pressure: this allows the production of chemical reactive
species at low temperatures.
Many applications of cold plasma exist nowadays: hard-
ening of tools, dies or metals, manufacturing of semicon-
ductor integrated circuits, coating (anti-corrosion, thermal or
electrical). The treatment of composite materials by means
of a cold plasma allows both the increase of their surface
wetting properties and the improvement of their mechanical
strength in terms of adhesion between fibres and matrix, as
shown in [1,2]. An important characteristic of cold plasma
deposition is the possibility of obtaining coatings with
different compositions along the thickness by changing
the process conditions to minimise the interface between
metal and coating, as reported in [3,4]. The use of cold
plasmas for surface activation of polymers allows the

0924-0136/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 0 1 3 6 ( 0 1 ) 0 1 2 2 1 - 3
374 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382
modification of surface characteristics to obtain improved
bonding without affecting bulk properties [5–9]. The inter-
action between a polymeric surface and a cold plasma flow
can be an ablation, a cross-linking or a surface activation,
depending on the gas and material tested [10].
Ablation consists of the removal from a surface of both
molecular layers and organic residues. This effect is due to
the continuous bombardment of a surface by plasma parti-
cles and by electromagnetic radiation, as well as by fluid
dynamic interactions between the gas flow and the surface. It
also produces an increase in surface’s roughness [11]. This is
a very important phenomenon that can be exploited for
adhesive purposes: roughness increases the number of che-
mical links between coating and substrate.
Cross-linking is due to the interaction between two or
more radicals to establish covalent links. The bombardment
and the radiation given out by plasma particles causes the
breakage of polymer macro-molecules and the concurrent
creation of free radicals. In this way a cross-linked poly-
meric layer is rapidly formed, which is characterised by a
molecular weight and by a melting temperature higher than
the one of a non-treated polymer.
Activating a surface by means of a cold plasma flow
means to increase the layer energy and this is determined by
the capture of polar groups by the surface. The polymer
superficial critical tension can be increased 4–5 times,
corresponding to a strongly increase in wettability.
Fig. 1. Cold plasma equipment.
Some examples of the described phenomenon can be
observed with oxidising plasma, which uses oxygen, air or
nitrogen oxides. As a matter of fact, polymers such as poly-
ethylene and polypropylene, are constituted by long hydro-
carbon chains with high chemical inertness. In these cases,
cold plasma represents an alternative to warm mixture of nitric
and chromic acid, which are prohibited by legislation.
The present work aims to study the relationship between
the cold plasma variables and polypropylene wettability and
adhesion. The nature of the relationship between wettability
and adhesion was investigated too. Owing to the complexity
of plasma–workpiece interaction, no validated theory cur-
rently exists to predict the changes in these properties with
process variables. Therefore, the hereinafter experimental
approach was followed. A set of process variables was
identified and used to conduct some experimental tests on
the basis of design of experiment (DOE) techniques. In
Sections 2 and 3, plasma equipment and an experimental
plan are presented. In Sections 4 and 5 the methodologies,
instruments and results related to wettability and adhesion,
respectively are reported.
2. Experimental apparatus
A plasma is generally obtained by an electrical discharge
passing through a gas. It is generated by either direct current
 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382
(DC with 50–60 Hz), or radio frequency (RF with 1.5–
50 MHz), or microwave (MW with 150–104 MHz) power
applied to a gas.
In our case, the plasma is produced using an AC electrical
discharge with a 50 Hz frequency. The transformer clamps
are connected with two electrodes, which are inside a
reactor. The gas is confined in it and is submitted to pressures
around 1000 Pa. The electric field generated is able to
accelerate the particles and to transfer kinetic energy to
them. Their consequent motion causes a chain reaction,
which increases the concentration of charged particles
(ionisation of neutral species). In this way a cold plasma
is generated. The electric apparatus supplies a voltage at the
electrodes, varying from 0 to 30 kV, with 30 mA as current
maximum. The gas distributor operates in the pressure range
of 300–9000 Pa and the flow rate interval is 10–500 dm3/h.
The details of this equipment are reported in [12] and are
shown in Fig. 1.
3. Experimental plan
A large number of process variables affects the cold
plasma results: flow rates of the different gases, total pres-
sure in the reactor chamber, substrate temperature and bias,
reactor geometry and material, electrode material and dis-
tance between electrodes, tensioned electric power applied
to the plasma [10]. Because of the complexity of the surface
treatment and of the fairly recent development of cold
plasma technology, the selection of process variables is still
largely empirical.
A set of experimental tests was designed by means of a
factorial experimental plan. The designed plan is given in
Table 1. The available reactor imposed some process vari-
ables: reactor geometry and material, electrode material and
distance between electrodes. Among the many other vari-
ables that influenced the treatment outcomes, only three
were selected and considered as factors in the experimental
phase. The selection was made considering the influence on
the surface treatment as seen in preliminary tests. The levels
of the single process variables were chosen in order to
adequately cover all the possible experimental conditions,
which are consistent with polypropylene thermal stability.
The tension levels were uniformly spread along the reactor
capability range, its maximum value is related to the highest
plasma gas temperature. The flow rate was chosen as 20, 40
Table 1
Experimental plan
Process variables Number of levels Values
Tension (kV) 3 10, 20, 30
Air flow rate (dm3/h) 3 20, 40, 60
Treatment time (s) 3 30, 75, 120
Replications 5
Measured surfaces 135
375
and 60 dm3/h, and the corresponding pressure inside the
reactor was 1300, 1600 and 2000 Pa. The use of a flow rate
over 60 dm3/h would involve a very high pressure and
temperature inside the reactor which would be not consistent
with polypropylene thermal stability. The time levels were
selected in order to study polypropylene reactivity to quite
long treatments. The gas used in the experiment was air,
which is the cheapest used in cold plasma treatment. The
small dimensions of our reactor prototype imposed the
dimensions of our rectangular test piece (60
20 mm2
area). The surfaces to be treated were placed at a distance
of 40 mm from the glow discharge to avoid possible surface
overheating. A steel support was used for the test piece
positioning. As shown in Table 1, each test was replicated
five times, yielding a total of 135 measured surfaces. The
experiments were performed in a random sequence, to
reduce the effect of any possible systematic error [13].
4. Wettability
As often happens when the same topic is shared by many
fields, every field has developed its own terminology, so that
different definitions of what is meant by ‘wetting’ exist [14].
In general, it is connected with the area covered by a liquid
drop put on a solid surface. It varies on the basis of the liquid
and surface and it is measured by the contact angle, defined as
the angle between the drop and the surface, as shown in Fig. 2.
When the contact angle has a value near zero, it is said that the
liquid is wetting the surface perfectly, otherwise it is said that
it is not wetting the surface [14]. In ASTM D724 standard the
procedure to measure the contact angle is described.
Under an energetic point of view, surface wettability
follows Young’s equation concerning the equilibrium
between the three interface surface energies solid–liquid
(gsl), liquid–gas (glg), and solid–gas (gsg):
glg cos y ¼ gsg  gsl (1)
In ASTM D2578 standard the procedure to measure the
surface energy is described. Both the ASTM D724 and
ASTM D2578-99a standards were applied in our experiment.
4.1. Contact angle measurement
The procedure used to measure the contact angle is based
on the ASTM D724 standard. Five distilled water drops
Fig. 2. Contact angle and gas–liquid–solid related tensions.
376 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382
Fig. 3. Drop positions.
(10 ml volume) were uniformly dispersed on each surface by
a micrometer pipette, as shown in Fig. 3. The image of each
single drop was acquired by a video-camera connected to a
computer. The contact angle’s (y) value was calculated by
measuring the base (b) and height (h) of the drop profile and
using the relationship:
 
4bh
y ¼ arcsin (2)
4h2 þ b2
The hypothesis is that the drop falls and sets on the surface
with an exact spherical shape.
The measurement system capability was evaluated as
suggested in [15]. As a matter of fact, in any problem
involving measurements, the observed variability ðs2tot Þ is
due to variability in the product itself ðs2prod Þ, and to mea-
surement uncertainty or gage variability ðs2mis Þ:
s2tot ¼ s2prod þ s2mis
To evaluate the measurement system variability, the drop
contact angle of 20 non-processed polypropylene samples
was measured. Each drop was placed in the centre of each
single sample and it was measured two times. Fig. 4 shows
the X and R charts for these data.
The X chart presents a point outside the control limits, but
the measurement process is under control. In fact in this case
the X chart shows the discriminating power of the equip-
ment, that is its capacity to distinguish among different
products. The R chart allows to estimate the measure-
ment error, because it represents the difference between
Fig. 4. Control charts for equipment capability analysis.
Fig. 5. Surface energy estimate (ASTM D2578).
measurements made on the same sample using the same
equipment. Starting from the estimation of R, s2mis is esti-
mated using the following relation:
R 2:54
^2mis ¼
s ¼ ¼ 2:25 (4)
d2 1:128
where d2 depends on the sample size.
In the hypothesis of a gaussian distribution, 6^ s2mis is a
good estimate of measurement system capability: in our case
it is equal to 13.508. The uncertainty of the drop contact
angle measurement is 2^ s2mis , that is 4.58. As it can be seen in
(3) Fig. 4, the contact angle average is equal to 86.118. This is
the angle of contact of non-treated polypropylene surfaces,
and it was taken as the reference for contact angle analysis.
4.2. Surface energy measurement
Another procedure used to measure surface wettability is
based on the ASTM D2578-99a standard. Wetting solutions
having surface tensions from about 30
103 to
70
103 N/m are used. These solutions are mixtures of
formamyde (HCON2) and ethylene glycol monoethyl ether
(Cellosolve1: CH3CH2OCH2CH2OH). One mix is spread
on a 650 mm2 area of the surface to test. If it appears
uniformly along the surface for more than 2 s, Fig. 5(a),
it is necessary to repeat the test with a higher surface tension
mix. On the contrary, Fig. 5(b), if it breaks into drops in less
than 2 s, it is necessary to use a lower surface tension mix.
The test is stopped when the mixture breaks into drops in
about 2 s. This method estimates the surface energy of the
polypropylene. To proceed with painting, car manufactures
impose 46
103 N/m as the surface energy lower bound.
5. Wettability results
To evaluate the influence of plasma variables on wett-
ability, multifactorial analysis of variance on the contact
angle measurements was used [16]. It was carried out in
three steps. The fundamental hypotheses of the ANOVA
 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382 377

Fig. 6. Main effects plot with regards to voltage supply and drop position.
applicability to the experimental data (residual normality
and homogeneity of residuals variance) were tested for each
step. The main effect plots were used in order to have a
graphical image of the response trend.
First, the influence of plasma variables and drop position
was investigated. The supply voltage and drop position have
shown to be the most significant factors (see Fig. 6). In
Table 2 the analysis output is shown.
An increase of voltage causes a decrease of contact angle
and thus an improvement in wettability. This is probably due
to the increase of plasma ionisation degree that involves an
enhancement of the charged species. The drop position
denotes that plasma process effects are not homogeneously
distributed on the surface. In particular, as shown in Figs. 3
and 6, the wettability improves from the lower part of the test
piece (positions 1 and 2) to the upper and right parts of
the test piece (positions 4 and 5). Moreover, the plasma
interaction with the right and upper parts of the test piece
was more efficient and uniform than with the remaining
zones. This is probably due to the non-uniform plasma
generation in the actual reactor.
To establish the process conditions that lead to improved
wettability and process homogeneity along the sample sur-
face, the ANOVA was carried out for each of the five drop
positions. In this case, the supply voltage is shown to be
significant in every position. Furthermore, there are some
significant interactions: voltage–flow rate for positions 1 and
4, time–flow rate for positions 2 and 5, voltage–time–flow
rate for positions 1 and 3 (Figs. 7 and 8). The pattern of the
contact angle, on the basis of the voltage supply, is in
accordance with that shown in Fig. 6.
When the voltage is at the minimum level (10 kV), an
increase of the flow rate causes an increase of the contact
angle, i.e. a worse wettability. This effect is less evident
when the voltage is 20 kV, while at 30 kV there is an
opposite behaviour. This is probably due to the increase
of pressure inside the discharge tube, connected with the
increase of the flow rate. At a low voltage it produces an
increase in gas impedance and, therefore, a decrease in
ionisation degree. On the other hand, a voltage 30 kV is
so high that gas concentration and ionisable species increase
with flow rate.
With respect to the flow rate–time interaction, it seems
that this pattern changes with measurement position. This is
probably due to a non-uniform gas flow in the reactor.
Finally, all the data were consolidated in order to evaluate
the maximum value of wettability for the whole surface. The
ANOVA results are reported in Table 3.

Table 2
ANOVA output (symbol  stands for significant variable)

Factor Levels Values

Voltage (kV) 3 10, 20, 30

Time (s) 3 30, 75, 120
Air flow rate (dm3/h) 3 20, 40, 60
Drop position 5 1, 2, 3, 4, 5
Source DF Seq SS Adj SS Adj MS F P
Voltage 2 1898.46 1898.46 949.23 40.62 0.000
Time 2 232.40 232.40 116.20 4.97 0.007
Flow rate 2 249.84 249.84 124.92 5.35 0.005
Position 4 801.83 801.83 200.46 8.58 0.000
Voltage  time 4 617.47 617.47 154.37 6.61 0.000
Voltage  flow rate 4 733.81 733.81 183.45 7.85 0.000
Voltage  position 8 78.78 78.78 9.85 0.42 0.908
Time  flow rate 4 61.68 61.68 15.42 0.66 0.620
Time  position 8 171.95 171.95 21.49 0.92 0.499
Flow rate  position 8 96.11 96.11 12.01 0.51 0.846
Voltage  time  flow rate 8 579.54 579.54 72.44 3.10 0.002
Voltage  time  position 16 265.11 265.11 16.57 0.71 0.786
Voltage  flow rate  position 16 392.08 392.08 24.50 1.05 0.403
Time  flow rate  position 16 646.56 646.56 40.41 1.73 0.038
Voltage  time  flow rate  position 32 906.44 906.44 28.33 1.21 0.199
Error 54 12618.14 12618.14 23.37
Total 674 20350.21
378 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382

Fig. 7. Contact angle pattern as a function of voltage–flow rate.

Table 3
ANOVA for aggregated data

Factor Levels Values

Voltage (kV) 3 10, 20, 30

Time (s) 3 30, 75, 120
Air flow rate (dm3/h) 3 20, 40, 60
Source DF Seq SS Adj SS Adj MS F P
Voltage 2 1887.36 1887.36 943.68 38.46 0.000
Time 2 226.88 226.88 113.44 4.62 0.010
Flow rate 2 245.28 245.28 122.64 5.00 0.007
Voltage  time 4 609.46 609.46 152.36 6.21 0.000
Voltage  flow rate 4 726.23 726.23 181.56 7.40 0.000
Time  flow rate 4 63.29 63.29 15.82 0.64 0.631
Tension  flow rate  time 8 589.40 589.40 73.68 3.00 0.003
Error 648 15898.92 15898.92 24.54
Total 674 20246.81
 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382 379

Fig. 8. Contact angle as a function of time–flow rate.

To identify the plasma variables that provide the best

wettability, it was determined which condition, among the
27 possibilities, has a distribution of the contact angle
characterised by minimum values of both mean and standard
deviation. The data follow a Gaussian distribution, as pre-
viously verified during the validation of ANOVA approach.
The contact angle average values and the boxplot of the best
experimental conditions are shown in Table 4 and Fig. 9 [12].
Among the conditions which minimise the angle of
contact and, therefore maximise the surface wettability,
the treatment condition 10 kV, 30 s, 20 dm3/h is the most
economic one. Comparing all the results only on the basis of
the voltage supply, the 30 kV condition gives the better
average increase of the surface wettability (y10 kV ¼ 66:49 ;
y20 kV ¼ 65:77 ; y30 kV ¼ 62:63 ). Fig. 9. Boxplot of the best conditions in terms of wettability.
380 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382

Table 4
Contact angle averages ðyÞ for the 27 experimental conditions

Experiment ID Parameter values y sW

3
1 10 kV, 30 s, 20 dm /h 60.268 4.558
2 10 kV, 30 s, 40 dm3/h 68.238 5.268
3 10 kV, 30 s, 60 dm3/h 66.218 4.648
4 10 kV, 75 s, 20 dm3/h 63.718 4.688
5 10 kV, 75 s, 40 dm3/h 67.788 5.748
6 10 kV, 75 s, 60 dm3/h 67.158 5.128
7 10 kV, 120 s, 20 dm3/h 67.698 5.008
8 10 kV, 120 s, 40 dm3/h 68.508 5.768
9 10 kV, 120 s, 60 dm3/h 68.898 3.188
10 20 kV, 30 s, 20 dm3/h 65.338 3.508
11 20 kV, 30 s, 40 dm3/h 65.188 4.248
12 20 kV, 30 s, 60 dm3/h 65.348 4.098
13 20 kV, 75 s, 20 dm3/h 64.038 4.888
14 20 kV, 75 s, 40 dm3/h 65.068 5.458
15 20 kV, 75 s, 60 dm3/h 65.368 6.358
16 20 kV, 120 s, 20 dm3/h 66.828 3.358 Fig. 10. Adhesive test: (a) passed test; (b) failed test.
17 20 kV, 120 s, 40 dm3/h 65.978 4.708
18 20 kV, 120 s, 60 dm3/h 68.878 5.368
19 30 kV, 30 s, 20 dm3/h 63.488 5.208
20 30 kV, 30 s, 40 dm3/h 63.068 4.958 substrate. In Fig. 10 the two possible situation of samples
21 30 kV, 30 s, 60 dm3/h 61.598 4.658 which pass or fail the adhesive test are shown. The second
22 30 kV, 75 s, 20 dm3/h 65.258 4.708 standard measures the resistance of paint film to water. The
23 30 kV, 75 s, 40 dm3/h 62.598 5.458 painted samples are dipped in distilled water at a tempera-
24 30 kV, 75 s, 60 dm3/h 62.908 6.498
ture of 60 3 8C for 24 h inside a thermostatic cell. Then
25 30 kV, 120 s, 20 dm3/h 60.718 5.138
26 30 kV, 120 s, 40 dm3/h 63.978 5.028 the samples are stabilised in air at room temperature and the
27 30 kV, 120 s, 60 dm3/h 60.118 5.008 squaring test is carried out after 2, 4, 6, or 24 h, after removal
from the thermostatic cell. The sample will pass the wet test
if the paint film on all the small squares in the squaring area
resist to the pull at least in one of the four attempts.
Finally, in order to evaluate whether our plasma process is In our experiment we measure adhesion in three possible
adequate for car manufacturers, we estimated the surface situation: dry tests with and without primer, and a wet
energy with the ASTM D2578-99a standard, as described in test with primer. Twenty seven samples of 60
80 mm2
Section 4.2. For all the experimental conditions the results dimensions were processed by cold plasma according to
were acceptable, i.e. greater than 46
103 N/m the surface different experimental conditions, as reported in Table 1. A
energy lower bound. replication was used for each experimental condition. The
samples were painted, according to Fiat procedure, and were
subjected to the squaring test (dry test). At first a PPG primer
6. Adhesion 2K1 was used to increase compatibility between paint and
substrate. Then a paint layer of PPG paint VR 8231 was
Adhesion is the joining of two different materials,
whereas cohesion is the joining of different parts made
by the same materials [14]. A good adhesion can be guar-
anteed if the adhesive adequately wets the substrate of the
two materials. Therefore, adhesion and wettability are two
related properties.
The adhesive tests were performed at the Polymeric
Material Laboratory of Fiat Auto Firm in Cassino. They
have followed both the Fiat standard 50461 (dry test) and the
Fiat standard 50180 (wet test). The first one corresponds to
ISO 2409 and gives a qualitative evaluation related to the
adhesion of inorganic and organic coating by a squaring test.
The squaring test consists in cutting the paint film in small
squares, covering the area with an adhesive tape, and pulling
it strongly. The sample will pass the test if the paint film
on all the small squares in the squaring area resist to the
pull, which means that the paint remains anchored to the Fig. 11. Samples from the dry adhesive test without using primer.
 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382
Fig. 12. Results of water resistance test after 2, 4, 6, and 24 h: (a) 10 kV, 30 s, 20 dm3/h condition; (b) 30 kV, 120 s, 20 dm3/h condition.
applied because it represents one of the most critical colour
in term of adhesion for bumpers. Finally a catalysed resin
was used to give brightness to paint.
In the second case the samples were painted without using
the primer and the squaring test were performed on them.
Finally a wet test was carried out on a reduced number of
samples: the plasma conditions, which have given the better
results in terms of wettability (10 kV, 30 s, 20 dm3/h and
30 kV, 120 s, 60 dm3/h), were chosen. Four samples were
tested for each process condition.
7. Adhesion results
The 27 samples passed the dry adhesive test when using
the primer. The dry adhesive test carried out without using
primer was passed by all the samples, even if a separation
between paint and substrate was observed in some areas of
the sample (Fig. 11). As a matter of fact, the standard
prescribes not to consider what occur outside the squared
area. However, an explanation to this phenomenon may
come from the dimensions of the used test pieces: we
consider a bigger test piece with respect to the one used
to evaluate the contact angle to conduct two tests on the same
sample. The dimensions of the two squaring areas approxi-
mately corresponds to the contact angle test piece dimen-
sions: the reactor chamber was designed to treat this smaller
test piece. Therefore, these tests show that cold plasma
activation enables the elimination of the primer.
The water resistance test (standard Fiat 50180) has pro-
vided the results shown in Fig. 12. For the process condition
10 kV, 30 s, 20 dm3/h the paint layer is separated from the
substrate on almost the whole the squared area, when the
squaring test is performed after 2, 4 or 6 h after water
immersion. However, the squaring test was passed after
24 h from water immersion. Therefore, the process condi-
tion 10 kV, 30 s, 20 dm3/h results acceptable. The samples
obtained with the 30 kV, 120 s, 20 dm3/h condition pass the
381
test in all the four cases. Therefore, under this condition, the
plasma process brings to the greater increase of the poly-
propylene adhesion property.
8. Conclusions
ANOVA analyses have demonstrated that voltage, vol-
tage–time and the voltage–flow rate interactions signifi-
cantly influence wettability. In particular, an increasing
voltage improves wettability. This is probably due to an
increase in ionisation degree. In this case, a stronger activa-
tion process is generated by the growth of number of charged
particles in the plasma. In relation to the interaction between
voltage and air flow rate, an increase in air rate at voltage
levels 10 and 20 kV worsens wettability. This probably
occurs because an air rate increase produces a decrease in
the number of charged particles, as a consequence of the
major air impedance. It is possible to observe the opposite
behaviour (increasing the flow rate, improves the wettabil-
ity) at high voltage (30 kV). In this case, the voltage is so
high that it is not influenced by impedance and increase in air
rate. As a matter of fact an increasing air rate raises the
number of ionisable species.
The best results in terms of wettability are obtained for
condition 10 kV, 30 s, 20 dm3/h and the corresponding
contact angle is equal to about 608. The contact angle of
non-treated polypropylene material is about 868. Therefore,
the contact angle reduction connected with plasma surface
treatment is equal to about 30%.
The dry and wet adhesion tests on samples painted using a
primer have shown a good adhesion of the paint film, ind-
ependently of the process conditions. Also the dry adhesion
tests on samples painted without using a primer have shown a
good adhesion of the paint film. Consequently, by using a
plasma process, it is possible to avoid the use of a primer.
However, the water resistance of samples painted without
using a primer has still to be investigated more in depth.
382 L. Carrino et al. / Journal of Materials Processing Technology 121 (2002) 373–382
Finally, we may say that adhesion and wettability are
two related properties. However, in order to quantitatively
correlate these properties, a better characterisation of poly-
propylene adhesion property, based on ISO 4624, is cur-
rently matter of further study.
Acknowledgements
This work was carried out with the funding of the Italian
MURST (Ministry of University and Scientific and Tech-
nological Research) and CNR (National Research Council
of Italy). The authors are grateful to Fiat Auto Cassino and
especially to Mr. Riefoli and Mr. Vecchio for their support in
the experimental work. A special thanks to engineer Raffaele
Frattaioli for participating in the experimental work.
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