Applied Surface Science 252 (2006) 5076–5082

www.elsevier.com/locate/apsusc

Studies on wettability of medical poly(vinyl chloride)

‘by remote argon plasma
L. Ru a,b, C. Jie-rong a,*
a
College of environmental and chemical engineering, Xi’an Jiaotong University, 710049, China
b
College of environmental and chemical engineering, Xi’an University of Engineering Science &Technology, 710048, China

Received 21 May 2005; received in revised form 24 July 2005; accepted 24 July 2005
Available online 26 September 2005

Abstract

The paper studies surface modification of medical poly(vinyl chloride) (PVC) by remote argon plasma and characterized
surface structure, performance of treated PVC by the water contact angle measurement, X-ray photoelectron spectroscopy
(XPS) and scanning electron microscopy (SEM). Results show that the remote argon plasma makes the surface of the PVC film
higher hydrophilic than the direct argon plasma and does not give remarkable degradation on the PVC film surface. The
hydrophilicity depends on sample position as well as the RF power and the plasma exposure time. The remote argon plasma
contributes more effectively to the dechlorination (Cl/C = 0.01) from the PVC film than the direct argon plasmas (Cl/C = 0.03)
and more effectively to the formation oxygen functionalities on the PVC film surface. These experimental results show the
possibility that remote argon plasma treatment can enhance interaction reactions with argon radicals relative to those with
electron and argon ions.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Remote argon plasma; PVC; Surface modification; XPS; SEM

1. Introduction useful in preparing medical devices or prostheses,

The modification of surface properties of com-
mercial polymers is very important from practical
point of view. Treatment of polymers by plasma of
various gases or direct exposition to electromagnetic
radiation can change their wettability, adhesion,
adsorption, printability, chemical reactivity and
sensitivity to light [1]. Plasma immobilization is
* Corresponding author.
where the good biocompatibility with living tissues is
required [2]. The characteristic feature of plasma is
their action only on thin surface layer, whereas the
bulk of substance remains unchanged and modified
material keeps the mechanical properties.
The main reactions occurring on polymer surface in
plasma are etching, cleaning, crosslinking, grafting
and other chemical reactions (addition, substitution,
formation of functional groups) dependent on the
presence of active species in plasma [3]. However, so

0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.07.045
 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082
far, researches about plasma surface modification have
merely been limited to a mixed atmosphere con-
stituted by all active species [4]. How much do the
different active species contribute to surface mod-
ification?
Supported by National Natural and Science
Foundation Council of China, we put forward an
innovative idea—remote plasma, that is, taking
advantage of the different life-spans of various active
particles such as electrons, ions and free radicals (the
rate constants of electrons-positive ion recombination
and radicals and recombination are 10
7 and
10
33 cm6/s, respectively) to make them separated
at a special plasma field and attain super pure and high
free radicals concentration at a distance from the
plasma discharge region. The paper studies surface
modification of medical poly(vinyl chloride) (PVC)
by remote argon plasma to obtain favorable surface
performance.
2. Experimental part
2.1. Materials
Medical PVC film(20 mm thickness, made by
Blood Center of Shanghai) was cut into pieces of
dimensions 10 mm  7 mm. Prior to the experiment,
the film was washed with distilled water and dried
naturally at room temperature.
2.2. Remote plasma treatment
A self-designed reactor was used. In Fig. 1, we
show the ‘‘Remote plasma’’ reactive system. The
Fig. 1. Schematic structure of remote plasma reactor: (1) RF
generator; (2) matching system; (3) gas bottle; (4) valve; (5) mass
flow meter; (6) inductance coil; (7) reaction chamber; (8) sample;
(9) vacuum gauge; (10) electromagnetic valve; (11) vacuum pump.
5077
reactor includes four parts-gas inlet, reaction chamber,
gas exhaust, power supply and matching network (SY-
500 W power supply and SP-II matcher which are
made in Chinese Academy of Science Micro-
electronics Center). The reaction chamber is Pyrex
glass tube (length 1000 mm, diameter 45 mm), where
inductance-coupling discharge is applied.
The PVC films were positioned on the carrier to be
treated by remote argon plasma. The purity of argon
was more than 99.99%. The conditions of the
treatment were at an RF (Radio Frequency) power
of 30–180 W, plasma treatment time of 0.5–3.5 min,
and argon flux of 20 cm3/min.
2.3. Contact angle measurement
The measurements were carried out immediately
after plasma treatment. The contact angle was
measured by a contact angle meter (JY-82) made in
Chengde, China. To lessen the effect of gravity, the
volume of each drop was regulated to about 0.2 mL by
a micro syringe. The measurement was carried out at a
20 8C and humidity of 45% RH. The averaged value of
the angles of the both sides of each drop was counted
as one measurement. Each contact angle was
determined from an average of 10 measurements
with a standard deviation of 18.
2.4. X-ray photoelectron spectroscopy
The X-ray photoelectron spectroscopy (XPS) of
the surface of the PVC films treated with the remote
argon plasma were obtained on a ESCALAB MK II
using a nonmonochromatic Mg Ka photon source.
The anode voltage was 10 kV, the anode current
30 mA, and the background pressure in the analy-
tical chamber 5  10
8 Pa. The size of the X ray spot
was 2 mm diameters and the take-off angle of
photoelectrons was 15 8C with respect to the sam-
ple surface. O/C and N/C atomic ratios at the PVC
film surface were estimated from the relative inten-
sity of the O1s core level against the C1s core within
an experimental error of 0.01.
2.5. Scanning electron microscopy
The surface morphology of the PVC film was
examined using scanning electron microscopy (SEM)
5078 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082

Table 1 RF power, and the sample position. The contact angle

Dispersion, polar and hydrogen bond components of surface free
measurements were carried out immediately after
energy of reference liquids at 20 8C (10
5 N cm
1)
finishing the plasma treatment experiments to mini-
No. Liquids g dL g pL g hL gL
mize changes in the surface properties. Regardless of
1 Water 29.1 1.3 42.4 72.8 the treatment conditions (the plasma treatment time,
2 Methylene iodide 46.8 4.0 0.0 50.8 the RF power, and the sample position), the PVC films
3 Ethyleneglycol 30.1 0.0 17.6 47.7
treated with the argon plasma showed smaller contact
angles than the original PVC film, and their surfaces
in a JEOL instrument (Model JSM–5800, Japan) after became hydrophilic. The hydrophilicity showed a
vacuum coating the specimens with gold. strong dependence on the plasma treatment time, the
RF power, and the Sample position. Figs. 2–4 show
2.6. Surface free energy measurement typical effects of the plasma treatment time, the RF
power, and the sample position on the hydrophilicity.
The liquids used in measuring the contact angle of In these figures, the hydrophilicity is evaluated by the
the film are shown in Table 1. According to Yamaishi contact angle of water (u).
[5], The surface free energy gL of the liquid can be A short time treatment of 1 min, as shown in Fig. 2,
divided into three components: dispersion component shows a large decrease in contact angle from 107 to
g dL , polar component g pL , and hydrogen bonding 30 8C. After this initial large decrease, the contact
component g hL . angle continues to decrease but the decrease is small: u
The surface free energy of PVC can be evaluated by at a plasma treatment time of 3 min is 22 8C, and that
the extended Fowkes equation as follows: at 8 min is 21 8C. The effects of the RF power were
qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi also observed: For example, u for the PVC films
g L j ð1 þ cos u j Þ ¼ 2 g dS g dL j þ 2 g pS g pL j þ 2 g hS g hL j modified at RF powers of 30, 60, and 90 W are 29, 22,
and 22 8C. The sample position effect is distinguished
where subscript Lj represents standard liquids used, S from the plasma treatment time and RF power effects.
represents solid to be measured, superscripts d, p, and Fig. 4 shows u for the PVC film modified with the
h represents dispersion, polar and hydrogen bond argon plasma for 3 min as a function of the sample
components of surface free energy, respectively. position, u at sample positions of 0–40 cm decreases.
The above equation can be solved by using a three- On the other hand, u at sample positions of more than
dimensional determinant, and the surface free energy 40 cm rises up by increasing the sample position.
can be obtained by the following equation:
g S ¼ g dS þ g pS þ g hS

3. Results and discussion

3.1. Contact angle of water on the argon plasma-

treated PVC film

The PVC films were positioned at a constant

distance of 0, 20, 40, 60, and 80 cm from the center of
the RF coil in the Pyrex glass tube of the reactor and
were exposed to the argon plasma at RF power levels
of 30, 60, 90, and 120 W. The modification of the PVC
film by the argon plasma was investigated from the
water contact angle on the surface of the treated PVC Fig. 2. Effect of plasma treatment time on the contact angles to
films as a function of the plasma treatment time, the water of PVC (RF power: 60 W; sample position: 40 cm).
 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082
Fig. 3. Effect of RF power on the contact angles to water of PVC
(treatment time: 3 min; sample position: 40 cm).
These values indicate that the argon plasma exposure
at a sample position of 40 cm is a better way for
hydrophilic modification than that at a sample position
of 0 cm. Here we call the argon plasma treatment at a
sample position of 40 cm the remote argon plasma
treatment to distinguish it from conventional argon
plasma treatment, which is done at a sample position
of 0 cm. We also call conventional argon plasma
treatment direct argon plasma treatment. From these
results, we conclude the following: (1) The argon
plasma makes the surface of the PVC film hydrophilic;
Fig. 4. Effect of sample position on the contact angles to water of
PVC (power: 60 W; treatment time: 3 min).
5079
(2) the hydrophiIicity depends on the sample position
as well as the RF power and the plasma treatment time
and (3) remote argon plasma treatment (at a sample
position of 60 cm) leads to higher hydrophilic than
direct argon plasma treatment (at a sample position of
0 cm).
3.2. Surface morphology of remote plasma-
treated PVC film surface
The contact angle measurement shows that the
remote argon plasma treatment leads to higher
hydrophilic than direct argon plasma treatment. A
main difference between the remote and direct argon
plasmas is a relative concentration between argon
radicals and charged species such as argon ions and
electrons. The argon radicals in the remote argon
plasma zone are in higher concentration than the
charged species. On the other hand, both charged
species and argon radicals in the direct argon plasma
zone are in high concentration. Therefore, we expect
that the surface modification with the remote argon
plasma will escape from degradation of the PVC film
surface initiated by heavy collision of the charged
species. Surface morphology of the PVC film treated
with the remote argon plasma was examined with
scanning electron microscopy (SEM) in order to
investigate how the PVC film surface was damaged
by the plasma treatment. The PVC films, which were
treated with the remote and direct argon plasmas at
60 W for 3 min were used as specimens for SEM
measurements. Fig. 5 shows SEM pictures of the
PVC film surfaces treated with the remote and direct
argon plasmas. The remote argon plasma-treated
PVC film surface is as smooth as the original PVC
film, but the direct argon plasma-treated PVC film
shows a rougher surface. There are numerous lumps
all over the surface of the direct argon plasma-treated
PVC film. This comparison shows that the remote
argon plasma treatment caused no change in surface
morphology, but the direct argon plasma treatment
led to a large change in surface morphology.
Therefore, we conclude that the remote argon
plasma does not initiate remarkable degradation on
the PVC film surface with hydrophilic modification.
On the other hand, the direct argon plasma initiates
heavy degradation on the PVC film surface with
hydrophilic modification.
5080 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082
Fig. 5. Scanning electron micrograph of plasma-treated PVC film (power: 60 W; treatment time: 3 min).
3.3. Effect of plasma surface modification on
surface free energy of PVC
Table 2 shows the surface free energy and its
components of the PVC. It shows that surface free
energy of the medical PVC film is increased after
modification by remote plasma. Compared with
untreated sample, its surface free energy (gS)
increased more than two-fold. The surface free
energy’s polar (g pS ) and hydrogen(g hS ) components
increase from 0.8%, and 0% to about 52.1%, and
15.3%, respectively. Dispersion (g dS ) decreases from
99.2% to about 32.5%. Accordingly, it can be
concluded that the improvement of surface wettability
largely lies in the increase of the g pS and g hS .
3.4. Chemical composition of remote argon
plasma-treated PVC film surface
Atomic composition of the PVC films treated with
the remote argon plasma was determined by XPS. The
specimens for the analysis were the PVC films, which
were set-up at sample positions of 0 and 60 cm from
the center of the inductance coil and treated with the
argon plasma at 60 W for 3 min. Table 3 shows the
Table 2
Dispersion, polar and hydrogen bond components of surface free
energy of the PVC( 10
5 N cm
1)
Sample g dS g pS g hS gS
Original PVC 48.3 0.4 0 48.7
Remote argon 28.2 45.2 13.3 86.7
plasma-treated PVC
Power: 60 W; treatment time: 3 min; Ar flow: 20 cm3/min
atomic composition (O/C and Cl/C atom ratio) for the
PVC films treated with the remote and direct argon
plasmas. The atomic composition was determined
from XPS analysis. The PVC films treated with the
remote and direct argon plasmas, as shown in Table 1,
show some decreases in the Cl/C atom ratio (the Cl/C
atom ratio is 0.01 and 0.03, respectively.) compared
with the original PVC film (the Cl/C atom ratio is
0.14). It is obvious that the remote and direct argon
plasma treatments initiated the dechlorination of the
PVC film. The remote argon plasma treatment gives a
lower Cl/C atom ratio (Cl/C = 0.01) than the direct
argon plasma treatments (Cl/C = 0.03). This indicates
that the remote argon plasma contributes more
effectively to the dechlorination from the PVC film
than the direct argon plasmas.
The PVC films treated with the remote and direct
argon plasmas also contain small amounts of oxygen
moieties. Although the original PVC film already
contains oxygen moieties (the O/C atom ratio is 0.06)
before the plasma treatments, the argon plasma-
treated PVC films contain a larger amount of oxygen
moieties: the O/C atom ratio for the remote and direct
argon plasma-treated PVC films is 0.18 and 0.15,
respectively. The generation of the oxygen moieties
Table 3
Chemical composition of the remote and direct argon plasma-treated
PVC film
Kind of Surface treatment conditions Atom composition
plasma
RF power Treatment O/C Cl/C
(W) time (min)
No 0.06 0.14
Remote 60 3 0.18 0.01
Direct 60 3 0.15 0.03
 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082 5081

Fig. 6. C1s spectra for the remote and direct argon plasma-treated PVC films at an RF power of 60 W for 3 min.

Fig. 7. O1s spectra for the remote and direct argon plasma-treated PVC films at an RF power of 60 W for 3 min.

may be due to postreactions of carbon radicals with
oxygen in air after the plasma treatment. Carbon
radicals are formed by means of abstraction reactions
of chlorine atoms from the PVC surface by argon
radicals and by means of the bond scission of the C–Cl
and C–C bonds by electron and ion bombardment.
Conclusively, the main reaction initiated by the remote
and direct argon plasmas is the dechlorination reaction
of the PVC film surface. The remote argon plasma has
a higher capability for dechlorination than the direct
argon plasma.
The PVC films treated with the remote and direct
argon plasmas at 60 W for 3 min were used as
specimens for the XPS measurement. The two films
have high hydrophilic surfaces: u is 20 8C for the
remote argon plasma-treated PVC film and 27 8C for
the direct argon plasma-treated PVC film. C1s, and O1s
spectra for the specimens are shown in Figs. 6 and 7.
The C1s spectra for the remote and direct argon
plasma-treated PVC films, as shown in Fig. 6, are
decomposed into three components: CH groups at
284.6 eV; C–Cl and C–O groups at 286.1 eV; C O
and C(O)O groups at 288.0–289.0 eV. The relative
concentrations of the three components are summar-
ized in Table 4. The remote and direct argon plasma-
treated PVC films, as shown in Table 4, show a large
decrease in the CH groups and increases in the C–O,
and C O groups compared with the original PVC
film.
The remote and direct argon plasma-treated PVC
films showed good O1s spectra for the decomposi-
tion. The spectra, as illustrated by dotted lines in
Fig. 7, are decomposed into two components, which
appear at 531.8–531.9 and 533.6–533.7 eV. The first

Table 4
Atom composition of PVC film surface treated with the remote and direct argon plasma
Kind of Surface treatment conditions C1s components (%) O1s components (%)
plasma RF power (W) treatment time(min) C–H O–C C–Cl C O O–C O O C O–C
Nonr 83 15 2 100
Direct 60 3 67 19.0 14 40 60
Remote 60 3 73 18 9 53 47
5082 L. Ru, C. Jie-rong / Applied Surface Science 252 (2006) 5076–5082
component at 531.8–531.9 eV is assigned the O C
groups, and the other is assigned to the O–C groups.
The relative concentrations of components are
summarized in Table 4. The remote and direct argon
plasma treatments lead to distribution of oxygen
functionalities, decreases in O C groups, and increase
in O–C groups. This indicates that predominant
oxygen functionality formed by the remote and direct
plasma treatments may be O–C groups.
4. Conclusion
Surface modification of the PVC film by the remote
argon plasma treatment has been investigated from a
viewpoint of comparison with the direct argon plasma
treatment. Results are summarized as follows:
1 Both remote and direct argon plasmas make the
surface of the PVC film hydrephilic. The hydro-
philicity depends on the sample position as well as
the RF power and the plasma exposure time. The
remote argon plasma leads to higher hydrophilic
than the direct argon plasma.
2 The remote argon plasma does not give remarkable
degradation on the PVC film surface with hydro-
philic modification. On the other hand, the direct
argon plasma gives heavy degradation on the PVC
film surface with hydrophilic modification.
3 The remote and direct argon plasma treatments
initiate the dechlorination of the PVC film. The
remote argon plasma treatment gives a lower Cl/C
atom ratio (Cl/C = 0.01) than the direct argon
plasma treatments (Cl/C = 0.03). This indicates that
the remote argon plasma contributes more effec-
tively to the dechlorination from the PVC film than
the direct argon plasmas.
4 The remote argon plasma treatment as well as the
direct argon plasma treatment form oxygen
functionalities on the PVC film surface. Main
oxygen functionalities formed by the remote argon
plasma treatment are C–O groups.
Acknowledgements
The authors thank the financial support of the
National Natural and Science Foundation Council of
China 20174030, the specialized research Fund for the
Doctoral Program of Higher Education 20010698007,
the Scientific Research Star Fund for the Study Abroad
Returnee and the key Scientific Technique item of
Shaanxi province (2001[345]).
References
[1] R. Zeng, Z. Pang, H. Zhu, et al. Surface modification of ion
exchange membrane (nafiontm) the enhancement of cation
selectivity by plasma polymerization process, Chem. J. Chin.
Univ. 22 (4) (2001) 687–690.
[2] T.M. Ko, S.L. Cooper, Surface properties and platelet adhesion
characteristics of acrylic acid and allylam ine plasm a treated
polyethylene, J. Appl. Polym. Sci. 47 (1993) 1601–1619.
[3] H. Kaczmarek, J. Kowalonek, A. Szalla, A. Sionkowska, Sur-
face modification of thin polymeric films by air-plasma or UV-
irradiation, Surf. Sci. 507–510 (2002) 883–888.
[4] J. Chen, J. Yan, Y. Zhang, Surface modification of medical PVC by
remote oxygen plasma, Compos. Interface. 11 (2) (2004) 123–130.
[5] J. Chen, Studies on the surface wettability and surface structure
of polyester treated with low temperature plasma, Chem. J.
Chin. Univ. 18 (3) (1997) 466–471.