Research note: the effects of plasma treatment and conditioning of the wetting behavior of

polypropylene

György Bánhegyi

Medicontur Medical Engineering Ltd., Herceghalmi út 1, 2072, HUNGARY

Abstract

Gas plasma treatment of non-polar polymers to increase wettability and adhesion is a well-established
technology. The decrease of the contact angle and partial recovery after room temperature and high-
temperature annealing is also well known. In this study, we have tried to compare the effects of various
dry and wet annealing schedules on the advancing and receding angles of as received and oxygen
plasma-treated samples. The observed changes proved to be more complex than anticipated,
especially those of the non-plasma-treated samples. One of the unexpected findings is that however
small is the water absorption by non-treated polypropylene, it significantly influences the wetting
properties. Dry annealing at room temperature and at 50 °C decreases the absorption energy in both
non-treated and plasma-treated samples, while wet annealing increases it, again in both cases. Drying
of the wet annealed samples result in a new “equilibrium” not completely identical with the original
state. There is a complex interplay between swelling, structural reorganization and molecular
orientation worth further studying.

Keywords: Adhesion, wetting, polypropylene, thermal conditioning, wet conditioning

1. Introduction

It is a well-known fact that non-polar polymers, as polyolefins (polyethylene, polypropylene, and their
copolymers), cannot be wetted well by high-energy fluids, like water, due to their low surface energy.
Therefore, before printing, painting, adhesive bonding, or grafting reactions, it is advisable to increase
the surface energy by AC plasma treatment [1] (low pressure [2] or ambient pressure [3] plasma),
corona treatment [4], flame treatment [5], UV treatment [6], acid etching [7], or other techniques. A
common consequence of these treatments is the formation of polar groups (hydroxy, keto- or carboxyl
groups) on the surface that interact with the polar media and improve wettability. Besides surface
analytical techniques such as ATR-FTIR (attenuated total reflection infrared spectroscopy [1]) or XPS
(X-ray photoelectron spectroscopy [1]), the best-known technique to detect and monitor changes in
surface energy is the measurement of water contact angles [8]. The ATR-FTIR technique probes a
surface layer in the order of micrometers, XPS in the order of nanometers, while contact angle
measurements are the most surface-specific: even a monomolecular layer can substantially alter the
wetting properties.

The most frequently used techniques of water contact angle measurements include sessile drop and
captive bubble techniques [9]. Using the static contact angle measured by the sessile drop technique
(Young angle, θY), it is possible to calculate the adhesion energy of the liquid (Wadh) to the surface using
directly measurable quantities (see Equation (1)):

𝑊𝑎𝑑ℎ = 𝛾𝐿𝑉 (1 + 𝑐𝑜𝑠θ𝑌 ) (1)

where ϒLV is the specific surface energy of the liquid in air, that can be measured independently. The
experimentally determined Young angle may exhibit some droplet-size dependence, but droplets in
the order of 10-20 μl on cleaned and reasonably smooth surfaces provide reproducible average values
with a standard deviation of a few degrees, which is usually enough for practical studies. It should be
noted that the so-called apparent (global) contact angle (for a consistent nomenclature, see [10]) –

1
measured within a relatively short time after placing the droplet onto the previously cleaned and dried
surface – are prone to various, not-too-well defined influencing factors, such as the evaporation of the
droplet itself (that can be eliminated by using a closed test environment with the saturated vapor of
the wetting liquid), metastable states, random effects of the actual landing conditions of the droplet,
etc. Nevertheless, this is the only direct and relatively easily available datum. If we want to measure
values relevant for surface physics, we have to make the surface molecularly smooth, use saturated
vapor atmosphere, apply minuscule vibrations to remove metastable states and run the contact angle
test for hours (although even this may not be long enough if, e.g., surfactants are also present in the
wetting liquid [11]).

The specific surface energy of the solid itself can be determined only by measuring the contact angles
with various liquids, using approximations for the polar and non-polar components of the specific
surface energy of the wetting liquids (see, e.g., [12] and [13]). We do not go into details as we did not
apply this approach.

Besides “static” contact angles, it is usual to determine the advancing (θA) and receding (θR) contact
angles [9,14], which are supposed to be identical on ideally smooth and homogeneous surfaces, but
differ on non-ideal surfaces due to surface roughness (physical heterogeneity) and to the uneven
distribution of polar groups (chemical heterogeneity). It should be noted that according to the
consistent nomenclature [10], the use of “static angle” should be avoided, and advancing and receding
angles should be considered as members of the family “apparent (global) contact angles,” representing
the two (thermodynamic) limits of the apparent contact angles under equilibrium conditions. The
situation is complicated further by the fact that the experimentally determined advancing and receding
angles also exhibit relaxation (i.e., long-term change on the order of hours, sometimes even days [15]).
The advancing and receding angles tend to converge on stable surfaces even if they are not
homogeneous. What is especially intriguing is the fact that the time dependence of the advancing and
receding angles is not even necessarily monotonic. The possible reasons for this unexpected behavior
are discussed in [15]. A theory proposed to explain the contact angle relaxation phenomenon [16]
points out that the same model applies to the time-dependent spreading and forced wetting (which is
truly dynamic in the sense that the angles are measured on surfaces in movement relative to the
wetting liquid). It should be noted, however, that the timescale of the relaxation phenomena treated
by the molecular model described in [16] is in the order of seconds. At the same time, those of the
instabilities presented in [15] is in the order of hours, so they are probably caused by different
mechanisms.

The degree of surface heterogeneity can be conveniently characterized by the hysteresis energy (Whyst)
defined by Equation (2):

𝑊ℎ𝑦𝑠𝑡 = 𝛾𝐿𝑉 (𝑐𝑜𝑠𝜃𝑅 − 𝑐𝑜𝑠𝜃𝐴 ) (2)

where ϒLV has the same meaning as in Equation 1.

The two effects (i.e., geometrical and chemical heterogeneities) cannot always be easily distinguished
from each other. In terms of chemical heterogeneity, the advancing contact angle is determined by
the least polar, the receding angle by the most polar domains of the surface. There are various ways
of determining θA and θR, as, e.g., by gradually increasing and decreasing the volume of the droplet on
the surface, or measuring the contact angles on a sheet sample moved upwards or downwards in a
liquid, or pumping up and down a liquid column in a capillary. Knowing θA and θR, in principle, it is
possible to calculate a “theoretical” Young angle (θYtheor) for the surface using Equation (3) [17]. It is
assumed that the heterogeneity is caused by chemical heterogeneity alone, there are two kinds of sub-

2
surfaces: a less polar one characterized by Young angle of θA having a surface-portion of f1 and a more
polar one characterized by Young angle of θR having a surface-portion of f2 (where f1+f2=1):

𝑐𝑜𝑠𝜃𝑌𝑡ℎ𝑒𝑜𝑟 = 𝑓1 𝑐𝑜𝑠𝜃𝐴 + 𝑓2 𝑐𝑜𝑠𝜃𝑅 (3)

If the relation θA> θYtheor> θR holds (as it theoretically should), Equation (3) can be used to estimate the
relative importance of the most and least polar surface fractions. The experimentally observed values
do not always obey theory, which can be attributed to various factors: differences in the measurement
methods, the “non-binary” nature of the surface (i.e., there is a whole distribution of polarities, not
only two discrete values), and surface roughness. If the contact angle hysteresis is caused only by
surface roughness on low-energy surfaces, it is assumed that with diminishing surface roughness θA
and θR converge, the hysteresis diminishes too, and the convergence value is equal to the equilibrium
θY value. The validity of this concept was proven experimentally on PP surfaces using ethylene glycol
as a wetting liquid [18]. Moreover, the surface area ratios between the ideal and real (rough) surface
areas estimated from the diminishing θA and θR values were compared with experimental values
measured by AFM (atomic force microscopy), and reasonable agreement was found.

The assessment of surface energetics on polymer surfaces is complicated by further factors: the non-
rigid nature of polymers (mobility, recrystallization, and the like) and by the possibility of swelling by
the wetting liquid (however small the latter may be). The phenomenon of contact angle recovery is
well known on plasma-treated non-polar polymer surfaces [8,19]: the initially reduced contact angle
gradually changes back to a higher value if the sample is left to stay in air, or another low-energy
medium, while the lower contact angle values can be “developed” again in contact with water or other
higher energy medium. These effects can be explained by the reorientation mobility of the surface
groups, although occasionally other factors, such as the diffusion of low molecular additives, must be
invoked.

In this note, we present the results of a background study raised by practical needs, which may have
implications also for theoretically oriented scientists. Not being an academic institution and due to
confidentiality, we concentrate on the wetting angle results and only mention further test results
related to the surface composition and surface roughness without detailed analysis and discuss briefly
possible additional extensions of our findings. In this study, we compared the wetting characteristics
of polypropylene (PP) samples with and without plasma treatment, exposed to dry annealing, ambient,
and elevated temperature liquid water exposure. The effects of repeated drying and wet exposure
were also studied to see the reversibility of these effects.

2. Experimental

2.1. Materials

The PP sample studied was Bormed HD850 MO, a multi-purpose injection molding grade of Borealis
AG (Vienna, Austria). 25.4*25.4*1 mm slab samples were injection molded using a multi-cavity mold
(without mold release agents), their surface was cleaned by isopropanol, dried, and kept in a clean
container to avoid particle deposition before use. We did not make special efforts to make the sample
surface extremely smooth beyond that of the typical smoothness of the injection mold insert. The
surface roughness (Ra) of the wetted sample surfaces was on the order of 100-200 nm (0.1-0.2 µm).

2.2. Methods

An Ossila contact angle goniometer (Ossila, Sheffield, UK) was used for the contact angle
measurements. Three samples were tested under each condition, and three sessile drops (distilled

3
water) of 10 μl volume were placed on each plate (both sides of the slab). The sessile drop contact
angles (θY) were evaluated at both sides of the droplet using the software provided by Ossila.

Our goal was to use test methods applicable under industrial conditions; therefore, we did not use a
saturated vapor atmosphere but reduced the test times to about 10-30 seconds after drop placement
to avoid the deformation of the droplet shape by evaporation. We measured more droplets to obtain
reliable averages and standard deviations, which were higher than under ideal conditions.

The advancing and receding angles were evaluated using the videos taken on the slab samples
immersed into (θA) and removed from (θR) water in a beaker. The velocity of the probe (not controlled)
was in the order of 1 mm/sec, and at a certain point, the movement was stopped, and the video frames
were evaluated after a few seconds. Three slides were image-processed during both immersion and
removal. The angles were determined using the angle evaluation plugins of the freely available ImageJ
software (NIH, Maryland, USA). The averages and the standard deviations are given.

The gas plasma treatments (wherever applicable) were done using a Nano plasma chamber (Diener
Electronic GmbH, Ebhausen, Germany). The samples were placed onto a silica tray; the gas was pure
oxygen, the pressure was 0.3 mbar, the frequency used was 13.56 MHz, the power was 180 W, the
standard treatment time was 8 min, although occasionally other treatment times were also tried.

Some XPS measurements were also made at a subcontractor using a PhI5000 VersaProbe spectrometer
(ULVAC PHI, INC., Chigasaki, Japan), but here only some general conclusions will be disclosed.

The surface roughness measurements were made using an Olympus Lext OLS 4000 confocal laser
microscope (Tokyo, Japan). Here we quote the Ra values only.

2.3. Conditioning

The notation of the samples and their conditioning schedules are summarized in Table 1 for the non-
plasma-treated samples, used for comparison, and in Table 2 for the plasma-treated samples.

As shown by the colored stripes, the conditioning schedules denoted by Roman numbers are the sums
of subsequent treatments; new sample sets are used only in stages I and VIII. One can see that first,
we studied the effect of dry annealing at 50 °C (1 day and 1 day + 1 week). Then, the annealed samples
were exposed to ambient temperature and elevated temperature (50 °C) wet treatment (both for 2
days) to see how much the wet environment “develops” the polar groups (additives or oxidized groups)
in the material. The elevated temperature is supposed to accelerate the “development” (reorientation)
of the polar groups. It has to be noted that due to the low density of the PP sample, it had to be fixed
mechanically to stay under water instead of floating on the surface. After the wet treatment, the
surplus water was blown away from the sample surface without drying it, and the contact angle tests
were performed immediately. Then, after the wet treatment, the samples were dried first at room
temperature, followed by a longer, elevated temperature, annealing (50 °C). We wanted to know
whether the original (non-treated) condition returns or we reach another equilibrium state. We also
performed the room temperature and the elevated temperature (50 °C) water soaking experiment on
samples that were not previously annealed in air – to see the differences. (In the last series of
measurements, only the Young-angles were measured, the advancing and receding angles not.) In the
case of the plasma-treated samples, we measured both the surfaces directly exposed to the plasma
and the other side too, which contacted the silica substrate. Interestingly, despite the fact that plasma
exposure indicators do not detect measurable change on the downside of the PP samples, the contact
angle did show changes, as we will see. The wetting energies (Equation (1)) were calculated from the

4
sessile drop Young angles. We also calculated the hysteresis energy (Equation (3)) from the advancing
and receding contact angles. In all these calculations, 71.98 mN/m was used for γLV [20].

3. Results and discussion

The results of the sessile drop analysis are summarized in Table 3, Fig. 1, and Fig. 2.

The contact angles measured on the non-treated samples (I and VIII) correspond well with each other
and with the values measured on other non-polar polymers as PE (polyethylene) or PP (polypropylene)
[1]-[8]. it is interesting to observe that the standard deviations of the sessile drop angles are higher on
the non-treated samples than on the treated ones, meaning that they are more heterogeneous. There
may be many metastable states where the droplet spreading can be arrested. Dry annealing at 50 °C
increases somewhat the contact angle, and the standard deviation becomes smaller (more
homogeneous surface). The difference between the 1-day and 1-week annealing is negligible. The
effects of high-temperature annealing (above 100 °C) on the surface and bulk properties of PP have
been studied, among others in [21]. Morphological changes are faster near the surface; at this
temperature, the secondary crystallization is negligible, but the relative weight of the mobile and rigid
amorphous fractions may change. Lamellar structures tend to form on the surface, the surface
hardness increases. Apparently, the surface roughness increases with annealing time and temperature
in the order of a few 100 nm, but this should not influence the contact angles considerably. Apparently,
however, not too many efforts were devoted in the literature to studying the wettability changes of
pristine PP under isothermal annealing.

If the previously annealed, non-treated PP is soaked into water at room temperature (IV) the contact
angle decreases significantly and decreases further if the temperature of the water immersion is raised
to 50 °C (V). Room temperature drying brings back the wettability of non-treated PP to condition (IV),
prolonged elevated temperature drying to the original (I) state, but not to the state achieved under
dry annealing conditions (II or III). It seems that although the water uptake of PP specified by
manufacturers is less than 0.01 wt%, it does affect wetting. Most water absorption studies have been
devoted to polypropylene composites with mineral or hygroscopic fillers or to PP-copolymers
containing polar comonomer or graft sidechains. Using the experimental data of water diffusion (D) in
PP (3.1x10-7 cm2/s) [22] and water permeability (P) in polypropylene (density 0.907 g/cm3) of 0.0575
g/mm/m2/d [23] and knowing that P is the product of D and S, the equilibrium solubility, after doing
the math it can be estimated that at room temperature the equilibrium solubility of water in PP is
around 20 ppm, i.e., about 0.002%, two orders of magnitude lower than the typical content of
antioxidants in polyolefins [24]. If this tiny amount of water is equally distributed on the surface of a 1
cm3 PP cube, it would mean about 200 nm thickness, so even a small fraction of the water-uptake
means “thick” phase in terms of molecular dimensions. It is probably distributed in the amorphous
parts of the subsurface layers in interaction with the slightly oxidized main chains and the relatively
polar additives. The presence of water may substantially change the mobility of the molecules in the
subsurface layers. Therefore, it seems reasonable to explain the changes in the wettability of non-
treated PP after soaking by slight water uptake. The elevated temperature soaking may accelerate
both water diffusion into the polymer and increase the mobility of chain rearrangement. If comparing
states (IV) and (V) with (IX) and (X) (in the latter two cases, the wet soaking was applied to non-treated
PP samples, which had not been before annealed under dry conditions), the sessile drop contact angles
are lower in cases (IX) and (X). There is no obvious explanation for this, maybe the previous dry
annealing in cases (II) and (III) somehow stabilized the surface layer and made it more resistant to
water penetration, but it needs further confirmation by closer surface structure studies. It is interesting

5
to note, however, that the adhesion energy of water on the non-treated PP sample soaked in 50 °C
water is close to the value achieved by the plasma treatment itself!

Let us turn our attention to the sessile drop contact angles measured on the plasma-treated samples
(concentrating on the adsorption energy values). XPS investigations have shown that the O/C atom%
ratio changed from 0.0 to about 0.1 after the plasma treatment. The degree of surface oxidation did
not change considerably between the treatment times of 2 and 16 min. The first, somewhat shocking
result of the sessile drop tests was that even on the side which was not directly exposed to the plasma
field (i.e., which were in contact with the silica glass substrate on which the plates were placed)
exhibited a contact angle reduction (and adhesion energy increment) almost comparable with that
observed on the other side, directly exposed to the oxygen plasma. The standard deviations of the
Young angles are much smaller on the plasma-treated samples (both sides!) than on the non-treated
samples, which means that the surface became more homogeneous – at least in the sense that the
disturbing effects arresting the spread of the droplet became more homogeneous. As we will see, the
hysteresis energies exhibit more complicated behavior. The plasma treatment abruptly increases the
water adhesion energy, which gradually decreases if exposed to dry 50 °C annealing (stages II and III),
as expected. In the low-energy air environment, the polar surface groups tend to turn “inside” the
polymer, thus reducing the adhesion energy. However, in stages IV and V, where the samples are
exposed to RT and 50 °C water, the adhesion energy increases again to levels comparable to stage II.
Still, it does not reach the level after fresh oxidation (I). Wet treatment in 50 °C water does not cause
a further increase as compared to the RT water treatment. The adhesion energy achieved in stage V is
nearly the same for the non-treated and the treated samples, suggesting that this effect may be
dominated by water ingress rather than by the reorientation of the polar groups in a high energy
environment (water). The adhesion energy values measured on the non-directly exposed surfaces of
the plasma-treated PP samples follow the same trends. Only the adhesion energy values are somewhat
lower than for the directly exposed surfaces.

Hereafter we investigate the advancing (θA) and receding (θR) angles and the hysteresis energy values
(Whyst) measured on the non-treated and treated samples (in the latter case, data for both directly and
indirectly exposed sides will be presented). The numerical values are collected in Table 4, the averages
and standard deviations of the angles are shown in Figure 3, the hysteresis energies in Figure 4.

Let us look first at the advancing and receding angle values. There is a considerable contact angle
hysteresis on the non-treated samples, probably because of the presence of a small degree of
oxidation caused by plastics processing itself and of antioxidants and other polar additives in the
polymer matrix. (It must be remembered, however, that the XPS test performed on the initial samples
could not detect any oxygen on the surface, O/C<0,01%). Surface roughness may also contribute to
the initial hysteresis value. The effect of various treatments on the advancing contact angle for both
treated and non-treated samples are very similar to those observed for the Young angles; compare
Figures 1 and 3. It is not unexpected, as the surface properties are dominated by the least polar
fraction. For the trends, see the discussion related to the sessile drop contact angle data. Another
general observation is that the receding angle of the plasma-treated samples hardly depends on the
treatments at all – be it dry or wet, RT or at 50 °C annealing. It shows that the most polar part generated
by the plasma oxidation is there; only its relative importance in determining the wetting properties
may change. The changes in the hysteresis energy come from the fact that the advancing angle is
changed by the annealing treatments, while the receding angle remains practically constant (at least
for the plasma-treated samples). It can be observed that during annealing the hysteresis energies of
the non-treated and of the plasma-treated samples change in the opposite direction: decrease for the
non-treated and increase for the plasma-treated samples (on both sides directly exposed to the plasma

6
or protected by the supporting silica plate). The trends during wet annealing are more complicated
and cannot be described by simple trends.

4. Conclusion and suggestion for further studies

We hope to have demonstrated that despite the high number of earlier studies still there are not too
well-understood aspects of the wetting properties of non-oxidized and oxidized polyolefin materials
exposed to various dry or wet aging/annealing schedules.

In our opinion, the following aspects are worth studying:

1. Water-uptake of non-treated and plasma-treated polyolefins, distribution of water (surface/bulk,

crystalline/amorphous) in samples annealed ambient air or water, and its effect of the wettability
changes.

2. The effect of the degree of PP oxidation; type, and amount of plastic additives on the water uptake
and wettability.

3. Mobility of the absorbed water (NMR, dielectric spectroscopy, reorientation of absorbed water, and
oxidized side chains).

4. Separating the effects of water content, oxidized group concentration, and surface roughness on
the wettability immediately after oxidation and after various aging/annealing schedules.

5. Structural changes in non-treated and oxidized polyolefin samples (near the surface and deeper)
exposed to dry and wet aging/annealing schedules.

These studies would require specimens made of very well-defined components with precisely
controllable surface roughness values. Much could be learned from such basic studies, both from
theoretical and practical viewpoints.

Acknowledgments
Thanks are due to László Kontur, CEO of Medicontur Ltd. for allowing the publication of these results.
Thanks are due to Norbert Szarka for his meticulous experimental work. Special tanks are due to
Professor Jaroslaw Drelich for the discussions and for providing his reprints and advice.

References

[1] Nihlstrand A., Hjertbeg T., Johannson K.: Plasma treatment of polyolefins: influence of material
composition: 1, bulk and surface characterization. Polymer, 38, 3581-3589 (1997)

https://doi.org/10.1016/S0032-3861(96)00930-5

[2] Mandolfino C., Lertora E., Gambaro C., Pizzorni M.: Functionalization of neutral polypropylene by
using low pressure plasma treatment: effects on surface characteristics and adhesion properties.
Polymers, 11, 202/1-202/13 (2019)

https://doi.org/10.3390/polym11020202

[3] Kehrer M., Rottensteiner A., Hartl W., Duchoslav J., Thomas S., Stifter T.: Cold atmospheric pressure
plasma treatment for adhesion improvement on polypropylene surfaces. Surface and Coatings
Technology, 403, 126389/1-126389/9, (2020)

https://doi.org/10.1016/j.surfcoat.2020.126389

7
[4] Novák I., Pollák V., Chodák I.: Study of surface properties of polyolefins modified by corona
discharge plasma. Plasma Processes and Polymers, 3, 355-364 (2006)

https://doi.org/10.1002/ppap.200500163

[5] Farris S., Pozzoli S., Biagioni P., Duó L., Mancinelli S., Piergiovanni L.: The fundamentals of flame
treatment for the surface activation of polyolefin polymers – a review. Polymer, 51, 3591-3605 (2010)

https://doi.org/10.1016/j.polymer.2010.05.036

[6] Novák I., Chodák I.: Adhesive behavior of UV pre-treated polyolefins. Macromolecular Symposia,
170, 341-348 (2001)

https://doi.org/10.1002/1521-3900(200106)170:1<341::AID-MASY341>3.0.CO;2-6

[7] Wang H., Chen S. J., Zhang J.: Surface treatment of LLDPE and LDPE blends by nitric acid, sulfuric
acid, and chromic acid etching. Colloid and Polymer Science, 287, 541-548 (2009)

https://doi.org/10.1007/s00396-009-2000-9

[8] Morra M., Occhiello E., Gila L., Garbassi F.: Surface dynamics vs. adhesion in oxygen plasma treated
polyolefins. The Journal of Adhesion, 33, 77-88 (1990)

https://doi.org/10.1080/00218469008030418

[9] Drelich J., Miller J. D., Good R. J.: The effect of drop (bubble) size on advancing and receding contact
angles for heterogeneous and rough solid surfaces as observed with sessile-drop and captive-bubble
techniques. Journal of Colloid and Interface Science, 179, 37-50 (1996)

https://doi.org/10.1006/jcis.1996.0186

[10] Marmur A., Della Volpe C., Siboni S., Amirfazli A., Drelich J. W.: Contact angles and wettability:
towards common and accurate terminology. Surface Innovations, 5, 3-8, (2017)

https://doi.org/10.1680/jsuin.17.00002

[11] Drelich J., Zahn R., Miller J. D., Borchardt J. K.: Contact angle relaxation for ethoxylated alcohol
solutions on hydrophobic surfaces. in ‘Contact Angle, Wettability and Adhesion’, (ed.: Mittal K.L.), CRC
Press, Boca Raton, Vol 2, 253-264 (2002).

[12] Zenkiewicz M.: Methods for the calculation of surface free energy of solids. Journal of
Achievements in Materials and Manufacturing Engineering, 24, 137-145 (2007)

No DOI available

[13] Drelich J. W., Boinovich L., Chibowski E., Della Volpe C., Holysz L., Marmur A., Siboni S.: Contact
angles: history of over 200 years of open questions, Surface Innovations, 8, 3–27 (2020)

https://doi.org/10.1680/jsuin.19.00007

[14] Drelich J.: Static contact angles for liquids at heterogeneous rigid solid surfaces. Polish Journal of
Chemistry, 525-549 (1997)

No DOI available

8
[15] Drelich J.: Instability of the three-phase contact region and its effect on contact angle relaxation.
Journal of Adhesion Science and Technology, 13, 1437-1455 (1999)

https://doi.org/10.1163/156856199X00578

[16] De Ruijter M. J., De Coninck J., Blake T. D., Clarke A., Rankin A.: Contact angle relaxation during
the spreading of partially wetting drops., Langmuir, 13, 7293-7298 (1997)

https://doi.org/10.1021/la970825v

[17] Cassie A. B. D.: Contact angles. Discussions of the Faraday Society, 3, 11-16 (1948)

https://doi.org/10.1039/DF9480300011

[18] Kamusewitz H., Possart W.: Wetting and scanning force microscopy on rough polymer surfaces:
Wenzel’s roughness factor and the thermodynamic contact angle, Applied Physics A, 76, 899–902
(2003)

https://doi.org/10.1007/s00339-002-1972-9

[19] Encinas N., Díaz-Benito B., Abenojar J., Martínez M. A.: Extreme durability of wettability changes
on polyolefin surfaces by atmospheric pressure plasma torch. Surface and Coatings Technology, 205,
396-402 (2010)

https://doi.org/10.1016/j.surfcoat.2010.06.069

[20] The International Association for the Properties of Water and Steam Moscow, Russia, June 2014
Revised Release on Surface Tension of Ordinary Water Substance, International Association for the
Properties of Water and Steam, IAPWS R1-76 (2014), available online:
http://www.iapws.org/relguide/Surf-H2O-2014.pdf

[21] Wang W., Zhao G., Wu X., Zhai Z.: The effect of high temperature annealing process on
crystallization process of polypropylene, mechanical properties, and surface quality of plastic parts.
Journal of Applied Polymer Science, 132, 42773/1-42773/12 (2015)

https://doi.org/10.1002/app.42773

[22] Kjeldsen P.: Evaluation of gas diffusion through plastic materials used in experimental and
sampling equipment. Water Research, 27, 121-131 (1993)

https://doi.org/10.1016/0043-1354(93)90202-S

[23] Bhadha P.M.: How weld hose materials affect shielding gas quality. Welding Journal 78, 35-40
(1999)

No DOI available

[24] Tolinski M.: Additives for polyolefins. Getting the most out pof polypropylene, polyethylene and
TPO. 2nd Ed. Elsevier, Amsterdam, (2015)

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Figure Captions

Figure 1. Sessile drop contact angles (averages ± standard deviations) measured on non-plasma treated
and plasma-treated samples after various conditioning schedules (for the notation of conditioning, see
Tables 1 and 2).

Figure 2. Adhesion energies calculated from the average sessile drop contact angles measured on non-
plasma treated and plasma-treated samples after various conditioning schedules (for the notation of
conditioning, see Tables 1 and 2).

Figure 3. Advancing (θA) and receding (θR) contact angles (averages ± standard deviations) measured
on non-plasma treated and plasma-treated samples after various conditioning schedules (for the
notation of conditioning, see Tables 1 and 2).

Figure 4. Hysteresis energies calculated from the advancing (θA) and receding (θR) contact angles
measured on non-plasma treated and plasma-treated samples after various conditioning schedules
(for the notation of conditioning, see Tables 1 and 2).

10
Figure 1.

Sessile drop Young angles on non-treated and plasma treated PP samples in

various states of conditioning
120
Dry annealing Wet conditioning followed Wet conditioning without
by drying dry annealing
100

80
Angle (deg)

60

40

20

0
I II III IV V VI VII VIII IX X
Conditioning

theta(Y) non-treated theta(Y) plasma side theta(Y) non-plasma side

11
Figure 2.

Adhesion energy calculated from the sessile drop Young angles on non-treated and
plasma treated PP samples in various states of conditioning
140
Dry annealing Wet conditioning followed Wet conditioning without
by drying dry annealing
120

100
Adhesion energy (mJ/m2)

80

60

40

20

0
I II III IV V VI VII VIII IX X
Conditioning

W(adh) non-treated W(adh) plasma side W(adh) non-plasma side

12
Figure 3.

Advancing and receding angles on non-treated and plasma treated PP samples in

various states of conditioning
120
Dry annealing Wet conditioning followed Wet conditioning without
by drying dry annealing
100

80
Angle (deg)

60

40

20

0
I II III IV V VI VIII IX X
Conditioning

theta(A) non-treated theta( R) non-treated theta(A) plasma side

theta(R) plasma side theta(A) non-plasma side theta(R) non-plasma side

13
Figure 4.

Hysteresis energy calculated from the advancing and receding angles on non-
treated and plasma treated PP samples in various states of conditioning
70

Dry annealing Wet conditioning followed Wet conditioning without

60 by drying dry annealing

50
Hysteresis energy (mJ/m2)

40

30

20

10

0
I II III IV V VI VIII IX X
Conditioning
W(hyst) non-treated W(hyst) plasma side W(hyst) non-plasma side

14
Table Captions

Table 1. Conditioning schedules of the non-plasma-treated samples (RT= room temperature)

Table 2. Conditioning schedules of the plasma-treated samples (RT= room temperature)

Table 3. Sessile drop contact angles (averages and standard deviations), and adhesion energies
measured on non-plasma treated and plasma-treated samples after various conditioning schedules
(for the notation of conditioning, see Tables 1 and 2). n. a. = not applicable.

Table 4. Advancing (θA) and receding (θR) contact angles (averages and standard deviations), and
hysteresis energies measured on non-plasma treated and plasma-treated samples after various
conditioning schedules (for the notation of conditioning, see Tables 1 and 2). n. a. = not applicable.

15
Tables

Table 1.
receding
advancing (both
plasma temperature Young (both sides sides
Condition sample time treated (degC) water (sessile) average) average)
I 1,2,3 0 no RT no I intital non-treated yes yes yes
II
II 1,2,3 1 day no 50 no III short dry annealing yes yes yes
IV
III 1,2,3 1 week no 50 no V long dry annealing yes yes yes
VI
IV 1,2,3 2 days no RT yes VII ambient wet yes yes yes
V 1,2,3 2 days no 50 yes elevated wet yes yes yes
VI 1,2,3 4 days no RT no ambient dry yes no no
VII 1,2,3 3 weeks no 50 no long elevated dry yes no no
VIII 4,5,6 0 no RT no VIII intital non-treated yes no no
IX
IX 4,5,6 2 days no RT yes X ambient wet yes no no
X 4,5,6 2 days no 50 yes elevated wet yes no no

16
Table 2.

advancing receding
advancing (non- receding (non-
plasma temperature Young (treated treated (treated treated
Condition sample time treated (degC) water (sessile) side) side) side) side)
I 7,8,9 8 min yes RT no I initial treated yes yes yes yes yes
II
II 7,8,9 1 day yes 50 no III short dry annealing yes yes yes yes yes
IV
III 7,8,9 1 week yes 50 no V long dry annealing yes yes yes yes yes
VI
IV 7,8,9 2 days yes RT yes VII ambient wet yes yes yes yes yes
V 7,8,9 2 days yes 50 yes elevated wet yes yes yes yes yes
VI 7,8,9 4 days yes RT no ambient dry yes yes yes yes yes
VII 7,8,9 3 weeks yes 50 no long elevated dry no no no no no
VIII 10,11,12 8 min yes RT no VIII initial treated yes no no no no
IX
IX 10,11,12 2 days yes RT yes X ambient wet yes no no no no
X 10,11,12 2 days yes 50 yes elevated wet yes no no no no

17
Table 3.

treated
treated θY
non- θY Wadh
θY non- standard treated standard Wadh treated standard 2
treated (mJ/m )
condition treated deviation deviation (mJ/m2) non- deviation
Wadh plasma non-
(°) (°) (°) plasma plasma (°)
(mJ/m2) side (°) plasma
side side (°)
side
I 90,2 9,7 71,7 45,0 1,4 122,9 62,2 2,5 105,5
II 100,0 3,5 59,4 70,7 1,9 95,7 79,4 2,1 85,2
III 98,7 2,6 61,1 79,4 3,5 85,2 83,7 2,1 79,9
IV 82,4 4,3 81,4 66,6 1,4 100,6 75,0 4,2 90,5
V 69,8 6,0 96,8 67,2 3,6 99,9 75,3 1,2 90,3
VI 77,2 7,4 87,9 81,5 5,9 82,6 84,1 1,6 79,3
VII 85,2 2,9 78,0 n.a. n.a. n.a. n.a. n.a. n.a.
VIII 89,7 5,4 72,4 45,3 2,3 122,6 63,7 2,8 103,9
IX 76,5 3,2 88,8 64,3 0,1 103,2 75,2 2,5 90,3
X 53,7 4,6 114,5 68,7 5,6 98,1 75,3 3,7 90,2

18
Table 4.

treated
treated θA θR
non- θA θR Whyst
θA non- standard θR non- standard treated standard standard Whyst treated standard treated standard 2
treated treated (mJ/m )
condition treated deviation treated deviation deviation deviation (mJ/m2) (°) non- deviation (°) non- deviation
Whyst plasma plasma non-
(°) (°) (°) (°) (°) (°) plasma plasma (°) plasma (°)
(mJ/m2) side (°) side (°) plasma
side side side
side
I 89,2 2,4 56,0 8,6 32,0 47,6 4,1 27,0 2,2 15,7 69,3 5,4 24,8 2,9 39,9
II 100,2 2,8 67,5 2,6 18,9 71,4 6,3 27,1 2,5 41,1 72,8 2,1 25,9 1,5 43,5
III 102,2 1,9 69,8 0,9 16,5 82,7 2,6 27,7 1,3 54,6 87,7 7,7 26,5 0,8 61,4
IV 91,3 1,8 57,9 6,2 36,4 75,4 5,6 27,7 0,8 45,6 81,6 2,5 29,7 1,7 51,9
V 88,4 2,0 44,5 4,0 46,1 71,5 4,6 28,4 2,6 40,5 77,8 1,5 30,1 3,1 47,0
VI n.a. n.a. n.a. n.a. n.a. 84,9 6,1 26,7 3,3 57,9 83,8 7,1 28,1 4,5 55,7
VII n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a.
VIII 89,9 2,2 59,3 8,6 33,6 51,5 2,1 28,0 0,2 18,7 67,6 0,8 30,0 0,9 34,9
IX 74,8 4,4 48,6 8,8 32,5 74,0 4,0 33,0 6,2 40,5 75,6 3,5 30,2 1,2 44,3
X 55,6 3,3 40,1 1,5 20,1 75,2 3,6 33,1 1,7 41,9 78,1 3,5 32,1 3,8 46,1

19