Contrib. Plasma Phys.

41 (2001) 6, 562−572

Plasma-Induced Surface Functionalization of Poly-

meric Biomaterials in Ammonia Plasma
K. Schröder, A. Meyer-Plath, D. Keller, W. Besch,
G. Babucke, A. Ohl
Institut für Niedertemperatur-Plasmaphysik, 17489 Greifswald, Germany
e-mail: schroeder@inp-greifswald.de

30 April 2001, in final form 3 October 2001

Abstract

Plasma-chemical modification is frequently used to improve the adaption of polymer sur-

faces to biological environments. In this regard amino functional groups play a key role.
They provide an excellent basis for subsequent modifications with specific biomolecules. It
would be of great value to get an amino functionalization independent of the specific ma-
terial in use. The paper reports on an investigation concerning the feasibility of such an
universal plasma functionalization procedure. Two different downstream microwave plasma
sources were taken to apply a procedure, which was developed for high-grade modifica-
tion of polystyrene (PS), to a number of other polymers including polyetheretherketone
(PEEK), polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polycarbonate
(PC), polyethylene (PE), polymethylmethacrylate (PMMA) and fluorinated polymers. In
many cases, very similar results were obtained. At maximum 5% of the surface were covered
by nitrogen functional groups. In some cases, about 50% of total nitrogen functional groups
were amino groups. The results suggest that a downstream ammonia plasma treatment in-
deed is a fairly universal method for high performance amino functionalization of polymeric
biomaterials.

1 Introduction

One of today’s most challenging tasks of surface processing technology is the modifica-
tion of polymers for biomaterial applications. In this field, unique requirements have
to be met by the materials and, especially, their surfaces. Implants, for instance, have
to preserve their mechanical properties in the corrosive biological environment over
time spans covering ten years and longer. At the same time, bio compatibility has to
be guaranteed. Therefore a reliable suppression of negative feedback of the artificial
material to the surrounding living tissue is mandatory.
Additionally, often a tight, specific microscopic interconnection of artificial and
natural matter is necessary. This is of special importance for adherence dependent
cells. Most animal cells are adherence dependent. An answer to these requirements is
to favor surface modification techniques which allow to covalently bond biomolecules.
The initial step of such a modification technique is to equip the surface with functional
groups available for subsequent (bio) chemical reactions. Plasma processes exhibit sev-
eral benefits for this purpose. The manifold of plasma species capable of producing
surface functional groups allows a high flexibility in the chemical sense. The preser-
vation of the bulk material’s chemical and mechanical properties during the process
is a major concern since many artificial implant and cell culture materials are heat-
sensitive polymers. If they are processed in the afterglow regime, thermal load on the

c WILEY-VCH Verlag Berlin GmbH, 13086 Berlin, 2001 0863-1042/01/06/11-0562 $ 17.50+.50/0

ÿ
K. Schröder et al., Functionalization of Polymeric Biomaterials 563

substrate can be held at a negligible level and bulk material changes can be avoided.
Further, plasma activation, as being a gas phase process, reduces the risk of leaving
leachable substances on the surfaces.
The present paper contributes to the discussion of other possible advantages of
plasma treatment. The specific properties of cell-to-biomaterial interface are dom-
inated by the respective biomolecule coating of the biomaterial. This implies that
a successful biomolecule coating could be achieved on different substrate materials
if it were possible to furnish these materials with the same initial functionalization.
The advantages of such an universal functionalization process are evident. It could
widen the availability of materials for specific biomaterial applications and facilitate
the establishment of standard coatings.
Here, we present results of an investigation on the feasibility of an universal func-
tionalization using ammonia plasmas. Such a processing is a method to create amino
functional groups on polymer surfaces. Amino groups provide an excellent basis for
subsequent surface modification techniques since they allow to bond biomolecules with
high selectivity. Usually, ammonia plasma treatment creates a number of different
nitrogen-containing functionalities. Typically, the ratio of nitrogen to carbon at the
surface is below 10% and the -NH2/N-ratio is in the order of 10−20% [1]. This ratio
leaves room for improvements. In an afterglow treatment a -NH2/N-ratio of 50% at
the surfaces was reported for PE treatment using radio frequency discharges [2].
For the present investigation microwave plasma processing was employed. It was
developed for the purpose of chemical micropatterning of polystyrene surfaces for
local control of cell attachment [3, 4]. This required high-grade surface modifications.
Typically, for ammonia plasma treatment a N/C-ratio of about 4% with a -NH2/N-
ratio of 50% were obtained [5].
In this paper, this modification procedure was applied to a number of
hydrocarbon-based polymers including polyethylene (PE) and polystyrene (PS), and
oxygen-containing polymers like polyetheretherketone (PEEK), polyethylenetereph-
thalate (PET), polyethylenenaphthalate (PEN), polycarbonate (PC), and polymethyl-
methacrylate (PMMA). Additionally, the fluorinated polymers (fluorcarbons) fluori-
nated ethylene propylene copolymer (FEP) and polytetrafluoroethylene (PTFE) were
included in the investigation.
All of these materials are in use as biomaterials. PS and PC are used for cell
culturing equipment and a number of containers for different purposes. PEEK and
PE are used for bone implants and prostheses. PET and PTFE are in widespread use
for vascular graft. PEN is still under investigation for vascular graft.

2 Experimental

2.1 Plasma processing

Extending the applicability of an established plasma process to new materials or alter-
native plasma reactors is a critical step in plasma science and technology. Very often,
a set of process parameters will fail to give comparable results in different experimen-
tal setups. The reasons for this are parameters which are not easily controllable, like
reactor wall conditioning, reaction gas impurities and substrate contamination. Ni-
trogen plasma treatment of polymer surfaces is known to be sensitive against oxygen
contamination of the processing environment [6]. Special measures must be taken to
avoid these complications or to diminish their influence. For this reason, the present
564 Contrib. Plasma Phys. 41 (2001) 6

coaxial line
tuning plunger

rectangular
waveguide

microwave

rectangular waveguide
conical line microwave tuning plunger
field applicator

microwave window
parabolic reflector
field applicator microwave antenna
microwave window

magnetron
active
plasma zone
optical window

substrate table
active
plasma zone

conncetion
to load-lock
substrate table vacuum vessel

stainless steel
UHV-vessel front door

Fig. 1: UHV plasma reactor system. Fig. 2: Low-vacuum plasma processor.

investigation employed two different plasma reactors. The first reactor, see fig. 1, in
UHV technique, allows excellent control of physical boundary conditions. It was used
for the evaluation of optimal process parameters for amino functionalization. The sec-
ond one was used to test these parameters under mass-production-like conditions with
a higher degree of impurities in the reaction environment. In both reactors surface-
wave-sustained microwave plasmas and a downstream position of the substrate were
used. The UHV plasma reactor is part of a multi step plasma reactor system. It con-
sists of a load lock chamber, a specimen storage magazine, a surface analytical system
and three plasma reactor chambers which are connected by a vacuum transfer tunnel.
The system was designed and built to allow detailed investigations of various aspects
of plasma-assisted surface modification of polymers. A description of this system is
given in [7]. The UHV reactor consists of a cylindric stainless steel reactor vessel with
60 ` volume with four large-diameter quartz observation windows on the cylinder walls.
A microwave plasma source is coupled to the reactor via a quartz microwave window
on top of the cylinder. All vacuum sealings are either metal UHV-sealings or differ-
entially pumped o-ring pairs. The base pressure of the reactor is below 5×10−7 mbar.
Substrates are always introduced via the load lock. In conjunction with a clean-gas
supply system and oil-free turbomolecular vacuum pumps a low contamination of the
processing environment and reaction gas is ensured. Figure 1 shows a schematic cross
section of this reactor.
The microwave plasma source of this reactor is a newly-designed, home-made one
[8]. It uses a conical-line microwave field applicator to generate a toroidal plasma just
below the microwave coupling window. In connection with an adjustable substrate
table position the toroidal plasma structure can be used to counteract the effects of
diffusional transport and wall recombination. This way, radial species distributions
with improved homogeneity can be obtained in downstream position for samples with
K. Schröder et al., Functionalization of Polymeric Biomaterials 565

up to 20 cm diameter. For the ammonia plasma treatment investigated here, a down-

stream substrate location 10 cm below the microwave window was found to be suited
for various heat-sensitive polymers. The absorbed (i.e. forward) microwave power was
700 W for a treatment duration of 77 s. The ammonia gas flow was 15 sccm at 0.1 mbar
total pressure. The second plasma reactor which was used to test the amino functional-
ization process under conditions comparable to mass-production is a customer-specific
version of the V55G low-pressure plasma processor by PLASMA-finish Corp., Ger-
many. A schematic cross section of this reactor is given in fig. 2. The reaction vessel
is an aluminium cube with a volume comparable to that of the UHV vessel, i.e. in-
ner dimensions of 40×45×34 cm3 (width×depth×height). As before, the microwave
plasma source is located on top of the chamber. It uses a parabolic microwave field
reflector to generate a large-area planar microwave plasma below the coupling window.
The location of the substrate table can be varied. The main difference between the
two plasma systems consists in the different contamination levels. The low-pressure
plasma processor is equipped with a clean-gas supply and an oil-free vacuum pump,
likewise. But this pump is a mechanical roots type multistage dry pump and all seal-
ings are o-ring sealings. Therefore the base pressure of the vessel is only 10−1 mbar,
i.e. 5 orders in magnitude higher than that of the UHV system. Moreover, substrates
are introduced to the reaction chamber using a large front door. This means that the
discharge chamber is exposed to air during every substrate transfer.
Also for the process parameters a slight modification had to be accepted, i.e. these
parameters were comparable but not equal to the UHV system. The optimum position
for polymer substrates was found to be 20 cm below the coupling window. The pressure
was maintained at 0.2 mbar. The applied microwave power was 500 W. The treatment
duration was 160 s.

2.2 Substrate materials

Various polymer materials were used as substrates for plasma-chemical modification.
Polystyrene (PS) wafer with a diameter of 47 mm were prepared by punching out the
bottom of a commercially available cell culture dish (FalconTM , Product No. 1016). For
all other polymers, quadratic pieces of 2 cm width were cut from untouched sheet ma-
terial. Poly(ether ether ketone) (PEEK) and bioFOLIETM (FEP) were purchased from
Reichelt Chemietechnik (Heidelberg, Germany) and Satorius (Göttingen, Germany),
respectively. In the case of bioFOLIE, the untreated backside was plasma treated. All
other polymers were supplied by Goodfellow (Bad Nauheim, Germany). Table 1 gives
a summary of the used polymers, the chemical structure of their repetition units and
product numbers of the suppliers.
The polymer materials can be divided into three categories. PS and PE in the first
category are pure hydrocarbons, while the polymers of the second category (PEEK,
PET, PEN, PC, and PMMA) additionally contain oxygen. Of course, oxygen is bound
in different states in the backbone and in side groups. PTFE and FEP com under the
third category. These are perfluorinated polymers.

2.3 Physico-chemical surface analysis

Water contact angle measurements To qualify the wettability of the
surfaces the contact angles were determined by the static sessile drop method (Digidrop
contact angle meter, GBX Instrumentation Scientifique, Romans, France) using ultra
566 Contrib. Plasma Phys. 41 (2001) 6

Name Abbreviation Supplier Chemical structure of repetition unit

Product No.
CH CH2

Polystyrene PS FalconTM, 1016

n

Polyethylene PE Goodfellow, CH2 CH2

ET 303 050 n

O
Polyetherether- PEEK Reichelt 48921 O O C
ketone n

O O
Polyethylene- PET Goodfellow, O CH2 CH2 O C C
terephthalate ES 301 445 n

O O
Polyethylene- PEN Goodfellow, O CH2 CH2 O C C

naphthalate ES 301 445 n

CH3 O
Polycarbonate PC Goodfellow, O C O C

CT 301 260 CH3

n

CH3
Polymethyl- PMMA Goodfellow, CH2 C

methacrylate ME 303 050 COOCH3

n

Polytetrafluoro- PTFE Goodfellow, CF2 CF2

ethylene FP 301 350 n

Fluorinated FEP Satorius, CF2 CF

ethylene bioFOLIE, CF3
CF2 CF2
propylene IV-76 077 316 m n

copolymer

Tab. 1: Polymers used in plasma treatment.

pure water (Milli-QPF Plus ultra pure water system, Millipore GmbH, Germany) as
test fluid. In any case, the resulting contact angle was taken as the mean square value
of at least 5 individual measurements. These measurements were performed within 60
min after removing from the vacuum system.

XPS analysis X-ray photoelectron spectra were recorded using a mul-

tichannel electron analyser (EA125 U5, Omicron, Taunusstein, Germany) and the Mg
kα line at 200 W. To minimize sample damage short data acquisition times of around
30 min were used. The samples from the low-vacuum plasma system were transferred
to XPS after about one day storage at air. The XPS measurements were performed
after reaching a basic pressure in the XPS chamber of about 10−9 mbar. All results
reported here were obtained using a 10◦ takeoff angle between the surface normal and
the axis of the analyzer lens. The analytical approach to amino group densities is
rather difficult. The application of IR spectroscopic techniques is limited to specifica-
tion preparation methods (e.g. thin films on reflecting substrates, flexible substrates
K. Schröder et al., Functionalization of Polymeric Biomaterials 567

in fixed positions), because of normal IR sampling depth of at least 1 µm is very large

compared to plasma effects with a modification depth of some nanometres. XPS is a
powerful tool in surface analysis, but amino groups can not be quantitatively distin-
guished from other nitrogen containing groups. Until now, quantification of different
aminated ions by SIMS spectroscopy seems to be impossible. Fluorescence labelling
of amino groups can be easily performed [9], the quantification in terms of densities
in a surface layer is complicated. On the other hand, XPS measurement with chem-
ical derivatization has been developed to enhance the analytical capability of XPS
with respect to chemical specificity, see equation 1. If the requirements of conversion
and side reactions can be controlled [10] this approach can be used for at least semi
quantitative estimations. Gas phase processes are advantageous. In the case of amino
groups, successful derivatization with 4-trifluormethylbenzaldehyde has been shown
[2, 11].

O
NH2 + HC CF3 (g) N CH CF3 + H2O (1)

Following this argumentation, XPS measurement with chemical gas-phase deriva-

tization is a reliable tool for amino group diagnostics introduced by plasma processes.

3 Results and Discussion

As mentioned before, the here-reported process originates from investigations on amino

functionalization of polystyrene. The most important aspect of the investigations on
polystyrene was that there was no strong dependence of surface functionalization from
treatment duration, if a duration of at least 10 s is applied. This is true for both
plasma processing systems. Figure 3 gives an example for the time dependence of the
functionalization effects determined for the low-pressure plasma processing system.
A N/C ratio of 2.5% is introduced while more than 50% of the nitrogen could
be estimated to be amino groups. This gives a −NH2/C ratio of about 1.5%. The
reduction of water contact angles from 78◦ to 50−60◦ shows the increased wettability
which is important for enhanced cell growth. A small minimum at a treatment time
of 40 s is found. This could indicate the existence of impurities of the plasma, which
can be overcome by a prolonged treatment time. For this reason a longer treatment
duration was set as the standard in treatment of different polymers.
Different from the low-pressure plasma processing system the UHV reactor system
gave the chance to investigate the modification in more detail. Especially, quasi in
situ XPS measurements could be performed. This means that plasma treated samples
could be transferred to the XPS-spectrometer under very clean high vacuum conditions
(better than 10−7 mbar, preventing contact to oxygen and water). Note, that in this
case also plasma treatment is performed in a reaction gas phase which is widely free of
oxygen. This means, that plasma surface interactions during treatment and subsequent
surface reactions after contact of plasma treated samples with ambient air can be
distinguished. In figure 4 results of investigations concerning these differences are
given for different oxygen-containing polymers. Comparing the O/C ratios before
NH3 plasma treatment and after air contact all substances except PMMA exhibit only
small differences. Without the knowledge of the in situ values this would support
the thesis that during treatment only minor changes of the polymer surface occur
568 Contrib. Plasma Phys. 41 (2001) 6

Fig. 3: Dependence of water contact angle, N/C and −NH2 /C ratio from treatment duration
in the low pressure plasma reactor.

which concern only nitrogen functional groups. It would support simple models of
amino functionalization, e.g. that amino radicals produced by gas phase dissociation of
ammonia could react with carbon radicals at the polymer surface which are obtained
by a hydrogen abstraction from methyl (−CH3), methylene (−CH2−) or methine
(methylidine, =CH−) groups, respectively [12].
In contrast to this, the reduction of
the O/C ratio in situ which is visible
in fig. 4 and a reduced amount of aro-
matic rings that was also observed show
that major chemical rearrangements of
the polymer surface occur during plasma
treatment. These reactions are supposed
to be a consequence of etching by atomic
hydrogen. It is known that microwave
plasmas efficiently dissociate NH3 result-
ing in a high density of atomic hydrogen
[13]. Hydration of aromatic ring struc-
Fig. 4: O/C ratios of ammonia plasma treated
tures and of oxygen-containing groups
polymers (UHV plasma reactor system).
like ketones result in reduced stability of
chemical bonds and production of hydroxyl radicals or water (etching). This reduction
of oxygen functionalities is not limited to ketones, i.e. polymers with oxygen in the
side chain. It can also be found in esters (PET, PEN, PMMA) and carbonates (PC).
There is no identifiable correlation of the degree of oxidation after air contact with
structural features of the different polymers. Indeed, it is known that post process
oxydation can generate different functional groups [14]. The structural arrangement
of these groups in the polymer chain can be manifold, comparable to the location of
the carbon-centered radicals produced by hydrogen atom abstraction or photochemi-
cal reactions. It is therefore plausible that no correlation was found. The only detail
which might be assigned to a structural effect is the different behaviour of PMMA. It
is a well known effect that polymers containing longer side chains are more effectively
etched by plasmas than polymers without side chains.
Functionalization of polymer surfaces by an ammonia plasma treatment is not lim-
K. Schröder et al., Functionalization of Polymeric Biomaterials 569

Polymer untreated NH3 plasma treatment

low-vacuum UHV
reactor reactor
O/C O/C
PE 8.8 ± 0.9% 9.2 ± 0.9% 28.7 ± 2.9%
PS 2.8 ± 1.5% 8.9 ± 0.9% 6.0 ± 1.4%
FEP 0% — 1.5 ± 0.2%
PTFE 1.6 ± 0.5% 6.6 ± 0.7% 17.9 ± 1.8%

Tab. 2: Oxygen incorporation by an ammonia plasma

in polyolefines, polystyrene and fluorinated polymers.

Fig. 5: Water contact angles for different polymers after ammonia

plasma treatment in the low-vacuum and the UHV plasma reactor,
respectively.

ited to an introduction of amino groups, other nitrogen-containing groups are produced

simultaneously. Examples for nitrogen functional groups are amines, imines, cyanides
and amides. Using XPS with chemical derivatization after ammonia plasma treatment
an −NH2/N -ratio of 10−40% [2] has been found on PE and of 10−20% [1, 15] on PS.
These selectivity data are lower than the results reported here for different polymers
(fig. 6). An −NH2/N ratio of more than 50% is obtained after treatment of PS, PET
and PEEK in the UHV plasma reactor system, and in the cases of PE, PEN, PC and
PMMA this ratio lies in the region of 30−40%.
Also oxygen containing groups were detected on polyolefines, polystyrene and flu-
orinated polymers (table 2), while only traces of oxygen can be found on untreated
materials.
Changes in oxygen functional groups have already been discussed for PET, PEN,
PEEK and PC. These complex chemical reactions and, possibly, changes in mor-
phology of polymer surfaces, increase the wettability of the hydrophobic polymers
investigated here. A summary of this effect is given in figure 5.
Without any exception, a reduction of contact angle was obtained for all polymers
which have been investigated in both reactors. Typically, the contact angle after am-
570 Contrib. Plasma Phys. 41 (2001) 6

Fig. 6: N/C and −NH2 /C ratios after treatment of different polymers in both plasma reac-
tors.

monia plasma treatment is 20◦ smaller than on the untreated sample. No dependence
on the type of polymer could be found. This is also true for the chemically highly
inert PEEK and PTFE. Typically, water contact angles of less than 70◦ are obtained.
Comparing the nitrogen incorporation and amino functionalization of the differ-
ent materials for the different plasma process systems, the following similarities and
differences can be stated (fig. 6).
The ratio of N/C lies in the range of 2−6%. While it is comparable for both
types of reactors, the amino group density is drastically smaller after a treatment in
the low pressure plasma system. There is an exception from this rule: For PTFE
the N/C ratio is much smaller (only 2.0%, comparable to FEP, 2.1%) in the low
pressure plasma system compared to the UHV reactor system (5.2%). An explanation
of this effect can be attempted considering the main difference between these two
systems. This is the different oxygen content. If the generation of bonding sites
for functional groups on the PTFE surface is assigned to atomic hydrogen only, the
introduction of oxygen to the gas phase could be an additional loss mechanism for
atomic hydrogen. Atomic hydrogen is known to create bonding sites on PTFE, which
are responsible for defluorination, hydrocarbon bond formation and incorporation of
nitrogen containing groups[16]. This also explains the behaviour of PTFE in an oxygen
or nitrogen discharge different from hydrocarbon-based polymers. In the case of PTFE
increased bond strength of the C−F bond (530.5 ± 7.5 kJ/mol in F−C2F5 ) compared
to C−H bond (344.3 ± 11.3 kJ/mol in H−CH2−R) [17] may play an important role.
The downstream ammonia plasma treatment used for amino (−NH2) group func-
tionalization of different polymers yielded −NH2/C-ratios of 1−3% after treatment in
the UHV reactor system (fig. 6). Especially, in the cases of PS, PEEK and PET den-
sities of more than 2% −NH2/C represent high-grade amino functionalizations. These
densities can be further increased by special process conditions [13]. Comparing the
amino functionalization in different plasma reactors (fig 6) reduced densities of amino
groups are observed in the low-vacuum system. This may be explained by a spectrum
of nitrogen containing groups produced in this reactor. Probably, oxygen containing
functional groups (e.g. amides) are introduced or a hydrogen abstraction (formation
of -OH or H2O) occurs during nitrogen entrapment. Thus, the comparison made in
figure 6 suggests, that the process conditions do not influence the functionalization
process itself, but the selectivity concerning the amino group.
K. Schröder et al., Functionalization of Polymeric Biomaterials 571

4 Summary

In the present paper an investigation concerning the feasibility of an universal, stan-

dard plasma surface functionalization procedure is reported. For this purpose down-
stream microwave plasma sources were taken since it is believed that this type of
plasma sources exhibit considerable advantages for polymer surface modification.
First, an ammonia plasma treatment procedure was developed to get optimum amino
functionalization of a selected polymeric biomaterial. Then this treatment procedure
was applied to a number of different materials. In addition, the effect of using different
plasma processing systems was investigated. For this purpose, two different plasma
reactors were used. The first reactor, in UHV technique, allows excellent control of
physical boundary conditions. It was used for the evaluation of optimal process pa-
rameters for amino functionalization. The second one, in low vacuum technique, was
used to test these parameters under mass-production-like conditions with a higher
degree of impurities in the reaction environment. It could be demonstrated that a
set of process parameters which was determined to be useful for the generation of
amino functional groups on polystyrene can be applied to amino functionalization of
aromatic-ring-containing polymers like PEEK, PET, PEN and PC with similar suc-
cess. Also, some more different materials like PE and PMMA could be functionalized
with success. Fluorinated polymers could be functionalized with some limitations. In
general, an introduction of 5% at maximum nitrogen functional groups was observed.
In some cases, amino groups surface densities of more than 2% were obtained. This
means, that about 50% of total nitrogen functional groups were amino groups. These
data hold for the case of the UHV plasma processing system. For the low-vacuum
plasma processing system qualitatively similar results were obtained. Quantitatively,
much lower amino group densities after a treatment in this system are obvious. In
summary, the results suggest that indeed downstream ammonia plasma treatment is
a rather universal method for high performance amino functionalization of polymeric
biomaterials.

Acknowledgements

The authors wish to thank U. Kellner and G. Friedrichs for excellent technical support.
We gratefully acknowledge financial support by the federal ministry for education and
research (Hochschulsonderprogramm III).

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