SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 2003; 35: 301–309

Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/sia.1533

Surface modification of PVC endotracheal tubes by

oxygen glow discharge to reduce bacterial adhesion
D. J. Balazs,1∗ K. Triandafillu,2 Y. Chevolot,1† B.-O. Aronsson,3 H. Harms,2 P. Descouts3
and H. J. Mathieu1
1
Materials Science Department, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne, Switzerland
2
Department of Environmental Science and Technology, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne, Switzerland
3
Group of Applied Physics—Biomédical, University of Geneva, 1211 Geneva, Switzerland

Received 5 July 2002; Revised 2 December 2002; Accepted 2 December 2002

A d.c. oxygen glow discharge was used to modify medical-grade poly(vinyl chloride) (PVC) to study how
surface chemistry and hydrophilicity influence Pseudomonas aeruginosa adhesion. The effects of plasma
exposure time on the resulting surface, including chemical composition, wettability and roughness, were
assessed using x-ray photoelectron spectroscopy, contact angle measurements and atomic force microscopy
analysis. A significant alteration in the hydrophilicity of the native PVC surface was observed after oxygen
glow discharge treatment. The water contact angle decreased from ∼80◦ to 8–20◦ , with a weak dependence
of the exposure time used. The change in surface wettability resulted from the incorporation of oxygenated
functional groups, including esters, ketones and acids, as indicated by XPS analysis. The amount of oxygen
incorporation was shown to be essentially independent of plasma exposure time. However, prolonged
plasma exposure resulted in increased surface roughness. Bacterial adhesion efficiency was evaluated
for PVC modified by 120 s of plasma exposure, because this exposure time was determined to yield the
maximum decrease in contact angle. Oxygen plasma treatment of native PVC was found to yield a 70%
reduction in bacterial adhesion for the four strains of Pseudomonas aeruginosa tested. Copyright  2003
John Wiley & Sons, Ltd.

KEYWORDS: surface modification; poly(vinyl chloride); bacterial adhesion; oxygen plasma; x-ray photoelectron spectroscopy

INTRODUCTION is desirable. We are developing an approach based on sur-

Biomaterials are defined as materials of either synthetic or
natural origin that are intended to interact or be in con-
tact with biological systems.1 Some biomaterials, such as
endotracheal devices, have become a source of nosocomial
infection. Data from 4500 infected intensive-care patients
across Europe demonstrate that Pseudomonas aeruginosa is
one of the most prevalent bacterial strains found in a clin-
ical environment, being responsible for 30% of nosocomial
infections, 47% of which are pneumonia.2 Extended intuba-
tion with an endotracheal device is one of the greatest risk
factors for ventilator-associated pneumonia (VAP),3 where
colonization of the intubation device and trachea by P. aerug-
inosa occurs in >90% of VAP cases, 40% of which lead to
death despite aggressive antibiotic therapy.2 Therefore, a
strategy to reduce bacterial adhesion to endotracheal devices
Ł Correspondence to: D. J. Balazs, Materials Science Department,
Swiss Federal Institute of Technology (EPFL), 1015 Lausanne,
Switzerland. E-mail: dawn.balazs@epfl.ch
† Present address: Laboratoires Goëmar, UMR 1931
CNRS/Laboratoires Goëmar, F-29660 Roscoff, France.
Contract/grant sponsor: University of Geneva.
Contract/grant sponsor: Common Program on Biomedical
Engineering and Research.
Contract/grant sponsor: EPFL.
face modification of the polymer used for this application:
medical-grade poly(vinyl chloride) (PVC).
Bacterial colonization of a surface is a complex pro-
cess that occurs over several steps, including an initial
adhesion phase, followed by the molecular process of firm
attachment.4 The final step in the sequence includes substra-
tum colonization and biofilm formation.5,6
The initial adhesion phase is largely governed by physic-
ochemical interactions between the bacteria and substrate.5,6
Transport of the bacterial cells to the surface occurs through
long-range interactions, such as diffusive (Brownian motion)
and convective transport, or active movement.7 Once in
close proximity, short-range interactions become significant
to bacterial attachment. As discussed by Van Loosdrecht
et al.,8 the initial adhesion process is commonly explained
by colloid chemical theories like the one of Derjaguin, Lan-
dau, Verwey and Overbeek (the DLVO theory). The DLVO
theory considers that bacterial cells behave as colloidal par-
ticles and thus interprets the total interaction forces, Gibbs
energy
Gtot , between bacteria and the substrate to be the
sum of repulsive electrostatic energy
GE  and the attractive
energy of London–van der Waals forces.7,9 According to
this accepted theory, initial bacterial adhesion can be pre-
vented by altering the physicochemical interactions between
the bacteria and substrate. In the case of P. aeruginosa it

Copyright  2003 John Wiley & Sons, Ltd.

302 D. J. Balazs et al.
was shown that the surface of various P. aeruginosa strains
(including clinical isolates) was hydrophobic and negatively
charged.10 Incidentally, by modifying the polymer surface
to incorporate hydrophilic functional groups and hence to
increase surface wettability, bacterial adhesion should be
reduced.11,12
One common approach to increasing substrate hydrophi-
licity of polymeric biomaterial surfaces is through the incor-
poration of oxygenated functional groups.11 – 13 This chemical
structural modification is commonly achieved using an oxy-
gen glow discharge.14,15 An interesting feature of plasma
modification is that the surface structure of the polymer can
be modified selectively to improve biocompatibility while
the bulk properties remain largely unaffected.16 – 18
Surfaces in contact with oxygen plasmas are bombarded
by a relatively large concentration of electrons, photons, free
radicals and ions, by which energy is transferred from the
plasma to the substrate.16,18 Each of the different components
of the plasma has a specific role in the surface treatment of
polymers, yielding various effects including surface clean-
ing, ablation, cross-linking and chemical modification.19,20
Liston19 states that each of the four effects are present to
some degree but that one may be favoured over the others,
depending on the substrate, gas chemistry, the reactor design
and the operating parameters. Therefore, an understanding
of the various roles of each of the plasma components and
their subsequent effects is essential to the correct interpreta-
tion of the various changes that oxygen plasma modification
has on the PVC surface. For a detailed description of the
roles of the various plasma species in the glow discharge
treatment of polymers, the reader is invited to consult the
reviews of Hudis21 and Sheu.22
This paper investigates the effects that oxygen plasma
exposure time has on the native MallinckrodtTM PVC sub-
strate, including evaluation of changes in surface wetta-
bility, roughness and oxygen content, using surface char-
acterization techniques such as x-ray photoelectron spec-
troscopy (XPS), contact angle measurements and atomic force
microscopy (AFM). This paper then describes the effects that
the changes produced by oxygen plasma treatment have on
Pseudomonas aeruginosa adhesion to PVC substrates.
MATERIALS AND METHODS
Substrate preparation
The substrate used for plasma modification and bacterial
adhesion assays was PVC issued from Mallinckrodt Hi-
LoTM endotracheal tubes, which was flattened to allow
microscopic counting of bacteria. The flattening procedure
was as follows: the PVC tube was split and cut into pieces
of 2 ð 1 cm2 ; the pieces were then heated below the melting
point of PVC between two clean, glass microscope slides
for 90 s at 180 ° C. In order to validate the method, XPS
and contact angle measurements were performed before
and after the flattening procedure. The flattening procedure
did not alter significantly the chemical nature of the PVC
substrate, because the atomic concentration and assigned
components to high-resolution spectra did not differ within
experimental error. In addition, contact angle measurements
Copyright  2003 John Wiley & Sons, Ltd.
did not show significant variation within experimental error,
and values prior to and after flattening were 78 š 3° and
82 š 3° , respectively. Therefore, all further experiments were
performed on flattened MallinckrodtTM PVC substrates,
referred to hereafter as native PVC.
Plasma treatment
A custom-made plasma system, described elsewhere,23 was
used for the oxygen plasma surface modification. Briefly,
an electrical discharge was obtained by applying a 1.5 kV
d.c. voltage over 10–30 Pa pure (99.995%) oxygen. In this
apparatus, the cathode was centred at one end of a cylindrical
anode. The flat PVC sample was mounted on an electrically
isolated sample holder and introduced into the anode
(¾10 mm from the cathode) within the positive column of
the plasma. The treatment times evaluated in this study were
varied: 30, 60, 120 and 240 s.
After plasma modification the samples were stored in
ultrapure (18 MÐcm) deionized water before any further
use or analysis, to prevent ageing affects. Immediately before
analysis the samples were dried with pure nitrogen flow.
Samples used in bacterial tests were taken directly from the
water to the adhesion media, without letting the surface
water film dry.
Analysis by XPS
The XPS analysis was performed using an imaging Kratos
Axis Ultra (UK) x-ray photoelectron spectrometer equipped
with a conventional hemispherical analyser. The x-ray source
employed was monochromatized Al K˛ (1486.6 eV) operated
at 150 W. Spectrum acquisition is performed under ultra-
high vacuum (UHV, 10
9 Torr) conditions. Analysis was
performed on a 0.21 mm2 (300 µm ð 700 µm) sample area
using a take-off angle of 90° relative to the substrate sur-
face. The pass energies were 80 and 20 eV for wide-scan and
high-resolution elemental scans, respectively. Charge com-
pensation was performed with a self-compensating device
(Kratos patent) using field-emitted low-energy electrons
(0.1 eV) to adjust the main C–C component to 285 eV. The
data reduction (atomic concentration, shift, curve fitting,
etc.) was performed with CasaXPS Version 2.0.69 software.
The operating software, Vision2, corrects for the transmission
function. The sensitivity factors were 0.278, 0.891, 0.780, 0.328
and 2.957 for C 1s, Cl 2p, O 1s, Si 2p and Fe 2p, respectively.
Prior to XPS analysis, all samples were outgassed overnight
under UHV conditions, due to water uptake during storage.
Contact angle measurements
Surface wettability was determined using digitized images
of 3 µl sessile water drops. The apparatus used was a
horizontally mounted microscope equipped with a CCD
camera. The contact angle was measured directly from
the computer-generated image of the ultrapure deionized
water droplet. All cited values are the average of three
measurements per sample, taken on both the left and right
sides of the water droplet. The precision of the obtained
angles was š3° .
Surf. Interface Anal. 2003; 35: 301–309
 Oxygen plasma treatment of PVC endotracheal tubes 303

Atomic force microscopy

Atomic force microscopy was used in contact mode and
lateral force mode to characterize the surface topography
and friction of oxygen-modified and native PVC samples.
Measurements were done with an Auto Probe CP system
(Park Scientific Instruments, Sunnyvale, CA, USA). The
system used is equipped with a piezoelectric scanner to allow
a maximum scan size of 100 µm. A MicroleverTM cantilever
of silicon nitride with a force constant of 0.50 N m
1 was
used. The roughness, Rrms , was calculated after a first-order
line-by-line flattening procedure of the topographical data
from the 10 ð 10 µm2 images.

Bacterial adhesion
The PVC exposed to oxygen plasma treatment for 120 s was
evaluated for bacterial adhesion efficiency by using native
PVC patches as controls according to the following methods. Figure 1. Wide-scan spectra of native and 120 s oxygen-
Batch adhesion experiments were carried out in glass plasma-modified PVC.
vials containing either native or oxygen-modified PVC
patches and filled to the top with degassed phosphate- Table 1. Atomic percentages and elemental ratios for the
buffered saline (PBS). After the bacterial suspension was native and oxygen-plasma-modified PVC (average over four
added, the vials were placed on a slantwise rotating wheel, samples)
to avoid sedimentation of bacteria, and incubated at room
temperature. After 2 h of incubation, the vials were opened C 1s O 1s Cl 2p Si 2p Fe 2p
and rinsed with cell-free PBS. The patches were removed (%) (%) (%) (%) (%) Cl/C O/C
carefully from the vials to prevent dewetting as much
Native 73.6 9.8 14.6 2.0 — 0.200 0.13
as possible, placed on a microscope slide and covered
30 s 71.1 24.9 0.4 3.6 — 0.006 0.35
immediately with a coverslip. The slides were observed
60 s 74.6 23.0 0.4 2.0 — 0.005 0.31
under a light microscope (magnification ð 1250; BX-60,
120 s 67.4 26.1 0.3 3.5 2.7 0.005 0.39
Olympus Optical Co. Ltd, Tokyo, Japan) equipped with
240 s 71.9 24.3 0.5 2.0 1.3 0.007 0.34
a digital camera (SenSys, Photometrics Ltd, Tucson, USA).
The number of adhered cells was counted for six randomly
chosen locations per coupon. Each experiment was done in (typically used as a heat stabilizer in the form of a carboxylate
triplicate. Levels of adhesion were given as numbers of cells salt in the fabrication of PVC).25 Another polymer additive
per square centimetre and calculated by averaging the values detected was a phthalic acid ester (di-isooctyl-phthalate),
of the 18 adhesion locations obtained for the three patches. which is commonly used as a PVC plasticizer.25,26 Moreover,
it should be noted that there is a significant amount of oxygen
RESULTS AND DISCUSSION present on the native PVC surface (9.8 š 0.6%), which is not
a typical element found in standard PVC. Because both
Analysis by XPS carboxylate salts and phthalic acid esters contain oxygen,
this is one explanation for the presence of oxygen. Moreover,
Determination of the elemental chemical composition because the PVC is intended for medical application, the
Analysis of the native PVC by XPS detected silicon, chlorine, tube is sterilized with ethylene oxide following production,
carbon and oxygen, as illustrated by the wide-scan spectra which may also explain the presence of oxygen on the
(Fig. 1). The surface composition and elemental ratios of native PVC surface. Finally, XPS also detects the presence of
these elements for both native and oxygen-plasma-treated organic silicon on the native PVC surface, which most likely
PVC are represented in Table 1. Elemental composition data appears as a result of the production process, because surface
from XPS wide-scans of the native MallinckrodtTM PVC show contamination to the level detected (>2.0%) has not been
that the chlorine content is significantly lower (14.6 š 0.6%) observed in our laboratory. It should be noted also that XPS
than that expected for standard PVC samples (33%), which do also detects organic silicon prior to the flattening procedure,
not contain additives or plasticizers. The difference observed indicating that it is not a result of the flattening procedure.
compared to standard PVC does indeed result from the Generally, wide-scan spectra of the oxygen-treated PVC
presence of polymer additives, such as plasticizers and heat substrates detect similar elements to the native PVC samples.
stabilizers, and eventually also from x-ray degradation,24 In addition, iron is observed for the samples treated for 120 s
although care was taken to minimize this affect by applying and 240 s. Table 1 illustrates the net decrease in chlorine
a power of only 150 W from the monochromatized x-ray content (dechlorination) following oxygen plasma treatment,
source. One polymer additive was identified using XPS and because the chlorine atomic percentage drops from the native
time-of-flight (ToF) SIMS analysis (data not shown) of the value of 14.6 š 0.6% to an average of 0.38 š 0.05% for the
native PVC samples, which illustrated the presence of zinc oxygen-plasma-treated samples. The Cl/C ratio illustrated

Copyright  2003 John Wiley & Sons, Ltd. Surf. Interface Anal. 2003; 35: 301–309
304 D. J. Balazs et al.

in Table 1 shows a trend that confirms dechlorination of the
PVC following oxygen plasma modification. Therefore, it
can be concluded that the 30 s oxygen plasma exposure time
is sufficient to yield dechlorination.
In addition, the oxygen atomic percentage values for
all of the exposure times investigated illustrate a signif-
icant increase following exposure of the native PVC to
oxygen plasma. Table 1 and Fig. 2 illustrate the >2.5-fold
increase of the oxygen atomic percentage following oxygen
plasma treatment. The XPS wide-scan data show that 30 s of
plasma exposure is sufficient to produce oxygen incorpora-
tion (Fig. 2) for native PVC substrates. Moreover, the oxygen
atomic percentages and O/C elemental ratios do not vary sig-
nificantly, within experimental error, for the range of plasma
exposure times investigated. However, to understand the
effects that varying the plasma exposure time has on the
native PVC substrates, the C 1s and O 1s high-resolution
scans were examined in detail.
Figure 2. Oxygen 1s atomic concentration as a function of
oxygen plasma exposure time.
Finally, it should be noted that for the longer plasma
exposure times of 120 s and 240 s there is evidence of a
slight incorporation of iron: 1.3% and 0.6%, respectively.
The presence of iron is explained as ablation of the
stainless-steel plasma electrode from where the iron ions
are deposited on the PVC sample. The presence of iron on
the oxygen-modified PVC surface does not significantly alter
bacterial adhesion, within experimental error, as compared
to oxygen-modified samples that do not contain iron (this is
discussed below).
Determination of the binding states of the elements
The C 1s and O 1s high-resolution spectra were studied
in detail to identify the chemical binding states for our
native and oxygen-plasma-modified materials. The peak
fitting parameters are summarized in Table 2.
Figure 3 shows the high-resolution C 1s and O 1s of a
native and 120 s plasma-modified PVC, clearly showing the
modification in surface chemistry obtained following oxygen
plasma treatment. Qualitative analysis of the high-resolution
C 1s confirms the dechlorination following plasma treatment,
where evidence includes the complete disappearance of the
C2 –C–Cl and net decrease of the C5 –Cl contribution.
Figure 3 also illustrates the apparition of oxygenated
functional groups, such as esters like the C4 –O–C O
(286.9 eV) and C6 O (288.0 eV) contributions. The ether/
alcohol groups (C3 –O) already present in native PVC
substrates do not vary, within experimental error, following
plasma modification for any of the exposure times evaluated.
However, the O–C7 O contributions do show an increasing
trend following oxygen plasma modification, where the
highest percentage is achieved for the samples modified for
240 s. There are two possible explanations for this increase.
First, because the O–C7 O contribution is in fact a
component of carboxylate salts and phthalic acid ester
plasticizers,25,26 one might consider that with increasing
exposure time there is surface degradation that results in
an increased amount of plasticizer on the surface. Ions
that bombard a polymer surface dissipate their energy

Table 2. Peak fitting parameters and area percentages for the native and oxygen-plasma-modified PVC (average over four samples)

Binding
Energy FWHM % Area % Area % Area % Area % Area
Peak (eV) (eV) native 30 s 60 s 120 s 240 s

C 1s
C1 –C/C1 –H 285.0 1.1 30.2 74.1 73.6 79.0 72.5
C2 –C–Cl 285.5
š0.05 34.0 — — — —
C3 –O 286.4 11.5 13.4 12.1 10.5 10.7
C4 –O C O 286.9 — 2.3 3.9 1.7 5.3
C5 –Cl 287.0 20.9 0.4 0.4 0.3 0.4
C6 O 288.0 — 4.5 4.9 3.2 4.8
O–C7 O 289.2 3.3 5.4 5.3 5.7 6.5
O 1s
Fe2 O3 1 530.2 1.35 — — — 18.4 8.1
O2 –Si 531.8
š0.05 19.6 15.0 8.6 13.5 8.3
O3 C 532.0 — 30.2 34.0 24.8 33.4
O4 –C 532.6 55.4 38.9 39.3 28.6 31.1
O5 –C O 533.6 24.9 16.0 18.1 14.8 19.1

Copyright  2003 John Wiley & Sons, Ltd. Surf. Interface Anal. 2003; 35: 301–309

Figure 3. Curve fitting of the high-resolution C 1s and O 1s of native (a) and 120 s oxygen-plasma-modified (b) PVC.
through physical effects such as ablation and electrostatic
charging.22,27 The energy deposited by ion bombardment
can result in surface degradation,21,22 with a subsequent
change in surface topography and morphology due to
removal of a small portion of the freshly functionalized
surface. Therefore, for the longer exposure times eval-
uated one would expect evidence of surface degrada-
tion, seen as changes in surface roughness and contact
angle. Indeed, there is evidence of surface degradation
for the longer exposure times, as discussed in a later
section.
However, there is also evidence of oxygen incorpora-
tion for all exposure times considered, seen as the cre-
ation of C O functional groups in the form of esters
(C4 –O–C O) and ketones (C6 O). Therefore, the sec-
ond reason for the increasing trend of the O–C7 O
contributions is that oxygen plasma modification results
in significant oxygen incorporation, yielding an overall
increase in all oxygenated functional groups. Evidence
of the incorporation of oxygenated functional groups is
seen as an increase in surface wettability,14,15 and is dis-
cussed below.
Copyright  2003 John Wiley & Sons, Ltd.
Oxygen plasma treatment of PVC endotracheal tubes 305
Therefore, as stated by Liston,19 there is indeed evidence
of a mixture of the various plasma effects (surface cleaning,
ablation, cross-linking and chemical modification) in the
current system, according to the XPS data. In the present
situation, the exposure time operating parameter apparently
results in a favouring of the chemical modification and cross-
linking processes for shorter exposure times, whereas for
a longer exposure time the surface degradation process is
slightly favoured.
Contact angle measurements
Improvement of surface wettability is one of the major
interests in biomaterials surface modifications1,13 due to
the fact that most common polymeric biomaterials are
hydrophobic in nature, like PVC. The literature reveals
that oxygen plasma exposure can render most polymer
surfaces hydrophilic.14,15 For this reason, the evolution of
contact angle with increasing plasma exposure time was
evaluated. Contact angle measurements of the various
surfaces indicated that it is possible to modify the surface
of a hydrophobic polymer (hydrophobicity D 82 š 3° ) in
such a way that the surface becomes very hydrophilic.
Surf. Interface Anal. 2003; 35: 301–309
306 D. J. Balazs et al.
Figure 4. Contact angle measurements for the native and
120 s oxygen-plasma-modified (a) PVC. (b) Graph illustrating
the evolution of contact angle for the various exposure
times studied.
Figure 4 illustrates that a sharp decrease in contact angle
to <20° occurred after only 30 s of oxygen plasma exposure,
where the maximal hydrophilicity achieved (7 š 3° ) occurred
following 120 s of plasma exposure. For this reason, the
bacterial adhesion studies were completed with samples
plasma modified for 120 s. In addition, it was observed that
as the plasma exposure time was increased to 240 s the
surface wettability increased slightly as compared to the
minimum achieved after 120 s of exposure.
Wettability changes in polymers following oxygen
plasma treatment are most commonly a result of sur-
face oxidation, unsaturation effects, electrostatic charging
and surface morphology changes.21 Generally speaking, the
active plasma species attack the polymer surface, resulting
in the incorporation of hydrophilic functional groups such
as carbonyl, carboxyl and hydroxyl on the surface of the
polymer.14,15 The increased presence of hydrophilic func-
tional groups following oxygen plasma modification was
illustrated above with XPS analysis (Fig. 3 and Table 2).
However, it should be noted that following 240 s of
oxygen plasma exposure the contact angle achieved was
11 š 3° , which is ¾4° higher than the angle achieved for
the samples treated for 120 s. One possible explanation
for this small increase in contact angle is the observed
treatment-induced surface roughening due to increased ion
bombardment,22 which further results in an increased surface
roughness. Surface roughness and topography of the various
samples are discussed in the following section.
Analysis by AFM
Topographical imaging of the native PVC (Fig. 5) sample
showed defects, such as holes and irregular scratches,
of the order of 1–5 µm. The holes are an artifact of the
flattening procedure and appeared due to bubble formation
during flattening.
Oxygen-plasma-treated PVC surfaces (Fig. 5) showed
larger defects of the order of 15–30 µm, and the pits from the
flattening process were observed no longer. Disappearance
of the pits demonstrates the significant effects that the plasma
exposure had on the PVC surface. For longer exposure times
such as 240 s, larger defects were observed that are the
result of other phenomena, such as PVC inhomogeneities,
Copyright  2003 John Wiley & Sons, Ltd.
possible contamination from the UHV chamber and, most
importantly, surface degradation. The evolution of surface
topography as a function of plasma treatment time is
explained below.
The root-mean-square value of the measured roughness,
Rrms , was used to evaluate the time evolution of the
topography (Fig. 6). Oxygen plasma modification did not
significantly alter the surface roughness for treatment times
between 30 s and 120 s, because the Rrms values did not
vary significantly from the 9.3 š 4.7 nm value of the native
sample. However, after 240 s of plasma treatment the Rrms
value increased by sixfold due to the ionic bombardment
discussed previously.22,27
Interpretation of surface analysis results
As mentioned in the introduction, each of the differ-
ent plasma components has a specific role in the plasma
treatment of polymers, yielding various effects includ-
ing surface cleaning, ablation, cross-linking and chemical
modification.19,20,22 In addition, it is known that each of these
processes occurs during plasma treatment, and the result
of the treatment is often a mixture of the aforementioned
phenomena.19 The following interpretation of the various
surface analysis results permits a greater insight into the
processes that might have occurred during oxygen plasma
modification of the MallinckrodtTM PVC.
In the initial stages of plasma treatment, the surface
is activated as a result of bombardment by the electrons,
photons and neutral species of the plasma.19,21,22 The
governing process appears to be a mixture of surface
functionalization and cross-linking nature, which results
in oxygen incorporation and an increase in wettability.
For longer exposure times, the plasma will obtain quasi-
equilibrium and activation and etching processes will start
to compete with each other.22,27 Once the equilibrium within
the plasma leans more towards an etching phenomenon
there is evidence of surface degradation, seen as a change in
surface topography, due to ion bombardment.
For the PVC surfaces studied in this work we found that
activation processes resulted in a constant incorporation
of oxygen over the various exposure times, which was
accompanied by an increase in surface hydrophilicity.
However, etching processes gave an important increase of
the surface roughness after a time delay of ¾240 s.
Bacterial adhesion
Bacterial adhesion efficiency was evaluated for PVC modified
by 120 s of plasma exposure, because it was determined to
yield the maximum decrease in contact angle. Adhesion was
evaluated for four different Pseudomonas aeruginosa strains: a
wild-type PAO1; one mutant (AK44) lacking various surface
structures such as lipopolysaccharides, and two different
clinical isolates (1.1.A1 and 19G12). Figure 710 demonstrates
the 70% reduction in bacterial adhesion achieved following
120 s of exposure to the oxygen glow discharge.
It is believed that the reduction in bacterial adhesion is
achieved following the incorporation of oxygenated func-
tional groups, which in turn render the surface hydrophilic.
With these data, it is not possible to speculate on the effects of
Surf. Interface Anal. 2003; 35: 301–309
 Oxygen plasma treatment of PVC endotracheal tubes 307

Figure 5. Topographical imaging of the native PVC and oxygen-plasma-modified samples, illustrating the time evolution of the
surface with increasing plasma exposure time.

changes in surface roughness on bacterial adhesion. Further
evaluation would necessitate additional experiments.
As mentioned, XPS analysis for the longer plasma
exposure times of 120 s and 240 s shows evidence of a slight
incorporation of iron, which was not found on the surface of
the samples treated for 30 s and 60 s. In order to determine if
the presence of iron alters Pseudomonas aeruginosa adhesion
as compared to 120 s exposure times, bacterial adhesion
assays were repeated for iron-free 60 s samples having a
similar chemical composition and contact angle to samples

Copyright  2003 John Wiley & Sons, Ltd. Surf. Interface Anal. 2003; 35: 301–309
308 D. J. Balazs et al.
Figure 6. Atomic force microscopy measurements for native
and oxygen-plasma-modified PVC, illustrating the evolution of
Rrms for the various exposure times studied.
Figure 7. Evaluation of bacterial adhesion for four different
Pseudomonas aeruginosa strains following oxygen plasma
modification for 120 s of exposure time.
treated for 120 s. The amount of bacterial cells attached to the
60 s oxygen-modified samples was not significantly different
compared to the samples exposed to 120 s of oxygen plasma.
Therefore, it was found that the presence of iron on the
oxygen-modified tube surface does not significantly alter
bacterial adhesion as compared to 60 s oxygen-modified
samples that do not contain iron.
CONCLUSIONS
Surface modification of medical-grade PVC using an oxygen
plasma has been characterized using various techniques
such as XPS, contact angle measurements and AFM. The
effects of plasma exposure time on the resulting surface,
including chemical composition, wettability and roughness,
were assessed. The effects of changes in oxygen content and
hydrophilicity produced by the plasma modifications on
P. aeruginosa adhesion were then examined.
A significant alteration in hydrophilicity of the native
PVC surface was observed after oxygen glow discharge
Copyright  2003 John Wiley & Sons, Ltd.
treatment. The water contact angle decreased from the native
value of ¾80° to 8–20° , with a weak dependence on the
exposure time used.
The change in surface wettability resulted from incor-
poration of oxygenated functional groups, including esters,
ketones and acids, as indicated by XPS analysis. The amount
of oxygen incorporation was shown to be essentially inde-
pendent of plasma exposure time.
Prior to 240 s, plasma exposure time did not significantly
affect the resulting surface morphology. Significant surface
degradation was visible only for the 240 s exposure times,
which yielded the greatest increase in surface roughness.
Results indicated that following 120 s of oxygen plasma
treatment the surface activation processes produced an
increased incorporation of oxygenated functional groups,
which increased surface wettability and resulted in a 70%
reduction in bacterial adhesion.
Acknowledgements
The authors would like to thank C. Granges and D. Favez for their
contributions during their diploma thesis and semester project work,
respectively. We would also like to thank Nicolas Xanthopoulos
for his assistance with XPS analysis. We greatly acknowledge
the financial support of the Common Program on Biomedical
Engineering and Research, the University of Geneva and EPFL
(1999–2002).
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