Surface Science 581 (2005) 169177

www.elsevier.com/locate/susc

Surface studies of low molecular weight photolysis

products from UV-ozone oxidised polystyrene
M.R. Davidson, S.A. Mitchell, R.H. Bradley

Advanced Materials and Biomaterials Research Centre, School of Engineering, The Robert Gordon University,
Aberdeen AB25 1HG, United Kingdom
Received 13 October 2004; accepted for publication 19 February 2005
Available online 17 March 2005

Abstract
The production of low molecular weight oxidised material during UV-ozone treatment of polystyrene has been studied by XPS, GCMS, FTIR and UV/visible spectroscopy. XPS analysis of the oxidised polystyrene surfaces before and
after washing with water or methanol indicates that the removal of oxidation products and the surface that remains
after washing is strongly dependent on the choice of solvent. Methanol washing removes a greater proportion of the
more highly oxidised carbonyl and carboxyl groups resulting in a surface with a lower oxygen content than that remaining after water washing. Extended exposure to UV-ozone treatment reveals a two-stage oxidation process with monosubstituted benzene rings such as benzaldehyde, acetophenone and benzoic acid being produced at exposure times less
than 15 min. Compounds, more typical of those formed via dehydration reactions of existing oxidised species, are produced at longer exposure times. UVvisible spectroscopy and Fourier transform infrared spectroscopy also conrm the
presence of carboxylic acid, aromatic ketones and esters. Measurements of water contact angle on a 10 min treated surface reveals that methanol washing produces a more hydrophilic surface than water washing, the resulting water contact
angles being 47
and 62
respectively. Ageing of methanol washed surfaces for 24 h leads to a recovery of the water
contact angle back to 62
which suggests some form of post-washing surface relaxation process. Since XPS analyses
show no increase in the oxygen concentration of the methanol washed surfaces after a 24 h ageing period, the increase
in contact angle found with ageing is attributed to the reorientation of very near-surface functional groups i.e. within
the XPS sampling depth.
 2005 Elsevier B.V. All rights reserved.
Keywords: Surface modication; Oxidation; Polystyrene; Surface reorientation; GCMS; XPS

Corresponding author. Tel./fax: +44 1224 262837.

E-mail address: r.bradley@rgu.ac.uk (R.H. Bradley).

0039-6028/$ - see front matter  2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.susc.2005.02.049

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M.R. Davidson et al. / Surface Science 581 (2005) 169177

1. Introduction
The bulk properties of many polymers make
them ideal for a wide range of structural and functional applications. However, their low surface
energy in the natural state limits their use and
pre-treatments are frequently applied which improve polymer characteristics such as adhesion
and printability. Most are essentially oxidative in
nature and spark [1], corona [1], UV-ozone [15],
plasma [6,7] and wet chemical methods [8] have
all been used successfully in the past to modify
polymer surfaces. All of these treatments essentially increase the surface energy and wettability
of the polymer by introducing polar heteroatoms
such as oxygen, nitrogen or a combination of oxygen and nitrogen to the upper few molecular layers
of the surface. This requires some scission of the
polymer backbone and one problem which has
been identied by a number of researchers is that
extended treatment may result in the formation
of a loosely bound surface layer of low molecular
weight scission products [35,9]. This problem is
particularly relevant for treatments which take
place in the gas or vapour phase where the scission
products are left on the polymer surface. When
present, this surface layer has been shown to have
a detrimental eect on adhesion and has been well
studied in terms of mechanical strength for a number of polymer-adhesive systems [8,9].
The hydrophobic nature of polystyrene surfaces, which inhibits the attachment of a wide
range of cell types due to the preferential formation of a surface layer of the non-cell attachment
protein albumin [5]. Recently, this has been overcome by the application of surface oxidation techniques which appear to promote interactions with
adhesion proteins such as bronectin. In this context, the presence of loosely bound polymer scission products, which might signicantly inuence
biological systems, is not well studied. For example, it is likely that water-soluble scission products
may aect the biocompatibility of oxidised polymer materials by causing changes to ionic constitution of cell culture media, or other physiological
uids, contacting the surface [10]. It is also highly
likely that certain possible scission products, such
as aldehydes and ketones, will be cytotoxic.

A number of studies have discussed and identied some of the possible chemical constituents of
the low-molecular weight oxidised layer produced
when polymer surfaces are exposed to an oxidising
environment [1121]. In the case of polystyrene it
has been shown that oxidation occurs by Norrish
type I and II mechanisms yielding a number of
photo-oxidation products including acetophenone
and benzaldehyde [1114]. However, these earlier
studies take no account of the reactions between
low molecular weight photo-oxidation products.
These processes clearly have the potential to result
in a far wider range of products than those predicted by the reactions between the UV-ozone
and polymer chain alone. The present study attempts to investigate reactions occurring between
components of the low molecular weight layer by
exposing polystyrene surfaces to extended UVozone treatment times.
It is clear that the removal of low molecular
weight oxidised material (LMWOM) is potentially
one of the most important stages in the pretreatment of polymers for biomedical applications.
Inecient washing procedures could be the cause
of a number of problems in medical implants [22]
and debris that remains on the surface of a biomedical implant or a tissue culture surface that is
not covalently bonded to the surface will inevitably interfere with the biological environment surrounding that surface. Denitive identication of
the debris and development of adequate washing
procedures are thus critical.
This paper considers important aspects UVozone oxidation, a process which has signicant
potential for controlling the biocompatibility of
polymer surfaces for use in tissue culture and
implant development. Using polystyrene as a
substrate we consider rstly the inuence of UVozone treatment on PS surface properties and the
nature of LMWOM formed. We then investigate
the chemical nature of the surfaces after LMWOM
removal by methanol and water washing.

2. Experimental
Untreated polystyrene cell culture dishes were
used as-received in this study. The polystyrene

M.R. Davidson et al. / Surface Science 581 (2005) 169177

dishes were treated in a commercial UV-ozone unit

(Jelight Company Inc., USA) which has been described in detail previously [23]. The low molecular
weight material was removed from the dishes by
washing with approximately 2 ml of either HPLC
grade methanol or doubly distilled water with gentle agitation on a rocking platform for 60 min.
Contact angles were measured using 20 ll drops
of doubly distilled water placed on UV-ozone treated polystyrene dishes after drying in ambient laboratory conditions for 1 h. No measurements were
taken from unwashed surfaces due to dissolution
of low molecular weight oxidised material inuencing the measured wettability. All contact angle
measurements were made on initial contact between water and surface to avoid absorption and
consequent swelling of the oxidised polystyrene.
Equilibrium contact angles of a 20 ll air bubble
were measured using a sessile bubble technique
[24]. Here the substrate is inverted and immersed
under the uid of interest which in this work was
either water or phosphate buered saline.
The surface chemistry of the polystyrene dishes
was studied before and after washing by highresolution X-ray photoelectron spectroscopy. The
experimental parameters used in this study are described in detail elsewhere [25]. Elemental compositions were calculated from peak areas obtained
from the narrow spectra, after subtraction of a
linear background, using the sensitivity factors
provided by the instrument manufacturer (Vision
Library sensitivity factors, Kratos Analytical)
which correct for the photoionisation cross-section,
transmission of the energy analyser and the inelastic mean free path of the photoelectrons. Analysis
of standard materials with known chemical stoichiometry indicate that the error in the calculation of
the chemical composition is approximately 5%.
The XPS quantication results presented in this
paper are mean values of at least three repeat measurements and are given with the standard deviation of those measurements allowing accurate
intercomparison of sample surfaces.
GCMS experiments were performed on a Hewlett Packard 5890 Series II gas chromatograph
equipped with a 30 m 0.2 mm ID ZB5 column
with 0.25 lm lm thickness and a HP 5971A quadrupole mass selective detector. Helium was used as

171

a carrier gas at a ow rate of 1 ml min 1. The washings from six dishes were combined in a glass vial
and the solution was concentrated by allowing
the solvent to evaporate overnight at ambient conditions. Approximately 1 ll of the concentrated
washings was used for each GCMS analysis. A
solvent delay of 4 min was used to ensure the complete removal of the methanol and prevent damage
to the detector. A consequence of the solvent delay
was that it was not possible to identify the more
volatile oxidation products removed from the polystyrene surface. The mass spectrometer was limited
to the detection of ions with mass-to-charge (m/z)
ratios <250. Identication of the chemical species
present was achieved using the NIST/EPA/NIH
mass spectral library. To conrm the identity the
mass spectrum produced from the unknown compound was manually compared with those proposed by the software. Further conrmation of
identication was achieved by comparing the retention times and mass spectra of the unknown compounds with reference compounds if available.
UVvisible analysis was performed on the
methanol washings of UV-ozone treated PS dishes
using a Perkin Elmer Lambda 2 spectrophotometer between 400 and 210 nm.
FTIR spectroscopy was used to study the chemical changes in free-standing polystyrene lms
before and after UV-ozone treatment. The lms
were produced by spin coating a clean silicon
wafer with a solution of polystyrene in chloroform. The polymer lms were then detached from
the wafer by soaking in water and axed to a supporting frame and dried in ambient conditions for
approximately 1 h prior to FTIR analysis. Transmission FTIR measurements were performed on
a Perkin Elmer Spectrum GX FTIR system with
a resolution of 8 cm 1, averaging over 25 scans.
All FTIR measurements on oxidised surfaces were
performed within 1 h of UV-ozone treatment.

3. Results and discussion

3.1. Analysis of UV/ozone treated PS surfaces
Fig. 1 shows the surface oxygen concentration
of the UV-ozone treated polystyrene as a function

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M.R. Davidson et al. / Surface Science 581 (2005) 169177

Fig. 1. Oxygen concentration of the washed and unwashed

UV-ozone treated PS surfaces. The lines shown are guides to
the eye.

of exposure time and the eects of water or methanol washing on residual oxygen levels. For the
unwashed surfaces, saturation of the oxygen concentration occurs after approximately 180 s suggesting that from that time onward the rate of
evolution of volatile gaseous products equals the
rate of oxidation of unreacted polymer. UV-ozone
treatment for periods >900 s give no further increase in surface oxygen concentration.
Comparing the behaviour for the two washed
surfaces, it is of note that methanol washing removes a greater proportion of the surface oxygen-containing material than water washing.
Presumably, this is due to the greater solubility
of the low-molecular weight oxidised material in
methanol compared to water. XPS analysis of
the methanol and water washed surfaces after ageing for 24 h under ambient laboratory conditions
(21
C, 40% RH) indicates no signicant dierences from the freshly prepared surfaces.
The change in surface chemistry resulting from
the oxidation process has been studied by analysis
of the carbon 1s peak. A typical example of the
functional group distribution obtained from polystyrene surfaces UV ozone treated for 900 s is
shown in Fig. 2(a) unwashed, (b) water washed
and (c) methanol washed. For each spectrum the
C 1s envelope can be resolved into ve chemically
shifted components: CC/CH at 285.0 eV; alcohol/ether at 286.5 eV, carbonyl at 288.0 eV;
carboxyl/ester groups at 289.0 eV and a peak

Fig. 2. Peak tted Carbon 1s XP spectrum for 900 s exposed

UV-ozonePS (a) unwashed, (b) water washed and (c) methanol washed. Showing a typical functional group distribution.

due to pp* shake-up satellites at a shift of

291.4 eV as previously reported [23]. The relative
intensities of the peaks gives further chemical
information about the eects of washing which is
summarized in Table 1.
The measured surface oxygen concentration decreases from 38 at.% for an unwashed surface to
values of 30 at.% and 22 at.% for surfaces washed
respectively with water or methanol. Washing with

M.R. Davidson et al. / Surface Science 581 (2005) 169177

173

Table 1
Summary of the peak t results for a 900 s exposed polystyrene surface before and after water and methanol washing
Sample

[O] (at.%a)

CC/CH (%)

COR (%)

C@O (%)

OC@O (%)

pp* (%)

Unwashed
Water washed
Methanol washed

37.7 (0.3)
29.5 (0.9)
21.8 (1.1)

41.9
55.8
66.4

20.1
17.8
17.4

13.8
9.5
7.0

19.7
12.3
4.0

4.5
4.6
5.2

Oxygen concentration given as mean standard deviation.

either solvent results in a small reduction in COR

but removes a greater proportion of C@O and
OC@O functionalities. Indeed, methanol removes
50% of the C@O and 80% of the OC@O groups.
The pp* signal is not signicantly aected by
water washing but there is an increase in its intensity after methanol washing to that recorded for
untreated polystyrene which indicates a more eective dissolution of low molecular weight material
and subsequent exposure of un-modied polystyrene within the sampling depth of XPS (5
10 nm).
The FTIR spectrum (not shown) from the spincoated polystyrene lm compares well with reference spectra for PS [26]. Bands found at 700 and
755 cm 1 can be attributed to c-vibrations of the
monosubstituted benzene ring; absorbances between 3125 and 2800 cm 1 result from CH
stretching vibrations of the monosubstituted benzene ring and polymer backbone; and stretching
vibrations of the substituted benzene rings at
1450 cm 1.
The bands resulting from UV-ozone treatment
are typical for carbonyl stretching in aromatic
ketones of the acetophenone type at 1690 cm 1
and 1720 cm 1 for aliphatic ketones [11,27].
Other carbonyl-containing groups such as carboxylic acids and aliphatic esters account for the
band at 1740 cm 1. At higher wavenumbers, i.e.
1770 cm 1, peroxyacids and anhydride compounds typically absorb. Further evidence for the
formation of acetophenone and carboxylic acids
groups from GCMS and UVvisible spectroscopy is presented later.
For all surfaces, UV-ozone treatment results in
a reduction in water contact angle for exposure
times up to approximately 180 s with little change
thereafter.
The sessile contact angles for the methanol
washed surfaces are 1015
lower than those from

the water washed, at corresponding UV exposure

times, even though the oxygen concentration of
the methanol washed surfaces is approximately
10 at.% lower than the corresponding water
washed surfaces. This is surprising since it is generally accepted that the water wettability of most
polymers is inversely related to surface oxygen
concentration. However, methanol is a hydrophilic
solvent that has been shown to remove water of
hydration from polymer surfaces [28] which might
explain the reduction in measured surface oxygen
level. It is also known that surface functional
groups can undergo reorientation to minimise free
energy in a given interfacial environment, this is
also likely to aect contact angle [29]. For example, during water contact angle measurements,
contact with the droplet may cause the polar
groups in the upper surface to orientate outward
to present a more hydrophilic surface. Applying
these arguments to the present study, the water
washed surface will be more hydrated and hence
have a more random orientation of surface functional groups. In contrast, the functional groups
at the methanol washed surface, which has been
dehydrated, will experience a more abrupt surface
environment change when they contact the water
droplet and the driving force for the outward orientation of the functional groups will be greater.
The resulting surface will be more hydrophilic
and a lower water contact angle will result. This
approach has previously been used to explain the
behaviour of hydrogel surfaces where a highly hydrated, hydrophilic, polymeric network which
would be expected to have a very low water contact angle, is found to be hydrophobic due to the
inward orientation of hydroxyl groups [30].
When the methanol washed surfaces are stored
in air at 20
C, subsequently measured water
contact angles correspond to the values for
water washed surfaces as shown in Table 2. This

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M.R. Davidson et al. / Surface Science 581 (2005) 169177

Table 2
Summary of the contact angle and sessile bubble measurements from water and methanol washed UV/ozone treated PS
UVO treatment
time (s)

0
30
60
120
180
300
600
900
a
b

Water contact angle (
)

Sessile bubble angle (
)

Water
washed

Methanol
washed

Methanol washed
(aged 24 h)a

Deionised H2O

PBSb

Water
washed

Methanol
washed

Water
washed

Methanol
washed

90.5
77.8
68.0
64.3
63.8
61.5
59.5
59.8

90.5
60.0
54.6
49.9
51.2
48.4
49.2
47.2

90.5
74.6
62.3
60.9
57.2
59.9
58.4
58.6

87.3
57.0
47.1
50.9
52.5
49.7
52.2
53.4

90.4
64.7
63.1
57.1

59.8
56.8
57.8

82.3
41.0
41.8
41.7
42.6
41.5
40.7
41.9

82.2
40.4
40.6
42.9

39.9
41.6
40.1

(0.7)
(1.7)
(1.5)
(0.5)
(1.1)
(0.7)
(0.7)
(1.3)

(0.7)
(1.0)
(1.2)
(1.5)
(1.5)
(1.3)
(1.3)
(1.2)

(0.7)
(0.3)
(1.5)
(1.4)
(1.7)
(0.6)
(1.1)
(2.1)

(1.1)
(0.8)
(2.0)
(1.3)
(0.8)
(1.5)
(1.2)
(0.8)

(0.9)
(1.7)
(0.7)
(0.8)
(2.1)
(1.1)
(1.6)

(1.2)
(1.1)
(0.6)
(1.4)
(1.4)
(0.7)
(0.5)
(0.9)

(0.6)
(1.9)
(1.1)
(1.2)
(0.9)
(1.1)
(0.7)

Aged for 24 h under water.

Phosphate buered saline.

hydrophobic recovery is most likely due to the

reorientation or diusion of polar functional
groups into the bulk polystyrene to create a more
thermodynamically favourable interface [6].
Equilibrium contact angles were also measured
using the sessile bubble method [24] in water and
phosphate buered saline (PBS) [31] these results
are also given in Table 2. The aim of the PBS
experiments was to gain some insight into the
liquidsolid interface behaviour during interactions with cells and proteins at pH 7.2. It can be
seen that the angles have a strong dependence on
the immersion liquid. For each treatment time
the PBS wets the surface better than water, giving
contact angles that are 10
lower. The angle measured for PBS on both water washed and methanol
washed surfaces is approximately constant at 41

(1
) for all oxygen concentrations. The sessile
bubble measurement in PBS is unquestionably
inuenced by the adsorption of anions onto the
polymer surface and although, in this respect,
not a true contact angle, does give useful information regarding the nature of the oxidised polystyrene surface when exposed to an aqueous
biological environment.

Daw et al. [32]. Dishes were UV-ozone treated

for up to 1 h and washed with 1 ml of doubly distilled water. The washing water was then removed
from the surface and used to measure the contact
angle on a clean (untreated) polystyrene dish.
The resultant contact angle data is shown in Fig.
3. A reduction in contact angle is observed as a
function of UV-ozone treatment time i.e. as the
amount of water-soluble low molecular weight
fragments dissolved in the water increases. A similar technique has been used in a number of previous studies [19,32] to show that low molecular

3.2. Analysis of LMWOM

The removal of low molecular weight oxidised
material was demonstrated using a contact angle
measurement adapted from the method used by

Fig. 3. Contact angles measured on reference surfaces

untreated polystyrene dishes using the water containing
LMWOM removed from UV-ozone treated dishes. Also shown,
the interfacial tension of the water after being used to wash UVozone treated polystyrene dishes.

M.R. Davidson et al. / Surface Science 581 (2005) 169177

weight fragments were present on polymer surfaces. In these studies the observed decrease in
contact angle was given as evidence of a reduction of the surface tension of the water by the dissolution of material from the polymer surface.
However, the liquidvapour tension was not measured in either study [19,32].
In the present study, measurements of the
liquidvapour interfacial tension by the pendant
drop method [33] show minimal decrease over
the 60 min treatment time as seen in Fig. 3. Using
Youngs equation [34] it can be shown that the decreases in the liquidvapour interfacial tension
would not account for the observed decrease in
contact angle. We believe the observed reduction
in contact angle is a result of a lowering of the solidliquid interfacial free energy due to hydrophobic interactions i.e. the displacement of water
molecules from the polystyrenewater interface
by the adsorption of low molecular weight oxidised material from the washing solutions.
The UVvisible spectra obtained (not shown)
from the methanol washings from the UV-ozone
treated polystyrene dishes show a broad absorbance below 300 nm typical of substituted benzene rings [35]. An absorbance at 238 nm, typical
of acetophenone [36], is present in all UVvis spectra with an intensity increasing with UV-ozone
treatment time. Other absorbances at 250 nm
and 230 nm can be tentatively attributed to benzaldehyde and benzoic acid respectively [36].
GCMS results obtained from the methanol
used to wash polystyrene dishes UV-ozone treated
for 5, 15 and 30 min are shown in Fig. 4.
It can be seen that the total ion ux increases,
corresponding to an increased concentration of
low molecular weight material in the methanol
washings, with UV-ozone treatment time. For
many of the photolysis products the mass spectra
were of sucient quality to give some degree of
certainty as to their identication. A number of
the peaks remain unidentied owing to the low
quality of the mass spectrum; absence of the compound from the chemical library; or a mixture of
compounds being present at that retention time.
The GCMS results show that UV-ozone treatment of polystyrene results in the production
of a variety of substituted benzene compounds

175

Fig. 4. GCMS total ion chromatograms obtained from

methanol used to wash UV-ozone treated polystyrene dishes.
Treatment times used were 5, 15 and 30 min. The peak labels
represent (a) benzaldehyde, (b) acetophenone, (c) benzoic acid
and (d) isobenzofurandione.

with acetophenone as the major peak in the

total ion chromatogram with a retention time
of 11.53 min. For treatment times longer than
15 min the chromatograph can be divided into
two distinct regions. Below 20 min retention time,
the main peaks originate from direct oxidation
scission products containing a single benzene ring.
Benzaldehyde (peak a) and acetophenone (peak b)
are thought to originate from the loss of acetophenone end groups via Norrish type I and II
reactions respectively [11,12]. Further reactions
involving the acetophenone end-groups yield benzoic acid [27] (peak c). For longer treatment times
benzoic acid makes up an increasing proportion of

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M.R. Davidson et al. / Surface Science 581 (2005) 169177

the chromatogram. The GCMS results are consistent with the XPS analyses given in Fig. 2 and
Table 1, which showed that methanol washing reduced the intensity of peaks attributed to carbonyl
and carboxyl/ester groups. We can now identify
the main photo-oxidation products responsible
for these observations. More complex species such
as 1,3-isobenzofurandione (peak d) are only
present in the chromatogram from the sample
treated for P30 min. Peaks with retention times
greater than 20 min can be attributed to molecules
formed via intermolecular dehydration reactions.
Although the identity of the photo-products
responsible for these peaks cannot be determined
with absolute certainty their mass spectra reveals
a peak at 77 which is characteristic of the presence
of a phenyl group.
A number of previous studies on the oxidation
of polystyrene have suggested that water, carbon
monoxide, carbon dioxide, acetophenone and
benzaldehyde are the main volatile scission products e.g. [11]. However, HPLC and FTIR studies
performed by Mailhot et al. identied acetophenone, benzoic acid, benzaldehyde, methyl benzoate and styrene monomer as being among the
low molecular weight oxidation products removed
by methanol washing [12].

4. Conclusion
UV-ozone treatment of polystyrene results in an
increase in the surface oxygen concentration,
washing with either water or methanol reduces
that surface oxygen by the removal of low molecular weight photolysis products. A greater reduction in surface oxygen is observed when methanol
is used as the solvent which can be attributed to
the greater solubility of the photolysis products
in addition to the removal of water of hydration
from the surface. Analysis of the C1s envelope
shows that the reduction in total surface oxygen
by washing is mainly by the removal of carbonyl
and carboxyl/ether type groups. Paradoxically,
water contact angle measurements show that despite having a lower oxygen content the methanol
washed surfaces are more hydrophilic than those
washed with water. This appears to be a result of

the orientation of surface functional groups when

the methanol washed samples are in contact
with the sessile drop. The absence of this eect
with the water washed surfaces is due to the presence of water of hydration which removes the driving force for the reorientation of the polar
functional groups. GCMS, UVvisible and FTIR
spectroscopy results support this with the identication of the main low molecular weight products
as acetophenone, benzaldehyde and benzoic acid.

Acknowledgments
This work was supported by SHEFC grant
number RDG1008. The authors would like to
thank Mr. John Wood for his assistance with the
GCMS measurements.

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