Macromol. Mater. Eng.

2002, 287, 871–880 871

Full Paper: Standard dry surface modification reactions resulting surfaces can also serve as a potential way to induce
have been applied to partially deacetylated chitosan without silica-like domains that can function as diffusion barriers.
affecting its bulk properties. Chitin, extracted from shells Irradiation of chitosan solutions shows that UV/ozone indu-
of Penaeus vannamei, yielded chitosan with a degree of ces depolymerization. In both cases, i.e., plasma and UV/
acetylation of 70% and molecular weight of 250 000 D. The ozone reactions, the main active component to surface
copolymer consists of (b-(1-4)-2-2-acetamido-D-glucose) modification appears to be UV irradiation with a wavelength
units linked to (b-(1-4)-2-amino-D-glucose) units. Since the below 360 nm.
main interest of this work was to study the surface properties
of films on substrates, a method to cast this material onto Al-
coated silicon wafers had to be developed. X ray photoelec-
tron spectroscopy (XPS) has been used to determine the
surface composition of the unmodified films and to follow
modification changes. The films were treated in either an
oxygen plasma environment or under UV/ozone irradiation.
Water advancing contact angle measurements and infrared
spectroscopy (FTIR) were used to complement XPS mea-
surements. The films appeared to orient on the silicon wafer
surface in the type II chitin structure. The rates of oxidation
are faster for the plasma process but they result in similar
changes to those induced by UV/ozone treatment. Atomic
force microscopy (AFM) clearly shows the advantage of the
milder modification reaction without much change in surface
morphology. The oxidation processes, as detected by XPS,
proceed without much alteration of the amine nitrogen atoms
but carbonyl containing moieties are formed as a function of
treatment time. Specific reactions with a fluorosilane to
measure the activity of hydroxyl groups indicate that at short AFM surface profile for oxygen plasma treated film in barrel
treatment times, these groups are essentially inactive. The etcher for 1 min.

Dry Processes for Surface Modification of a

Biopolymer: Chitosan
Luis J. Matienzo,* Sarah K. Winnacker
IBM Corporation, Microelectronics Division, Endicott NY 13760, USA
E-mail: lmatienzo@stny.rr.com

Keywords: biomaterials; coatings; ESCA/XPS; FT-IR; functionalization of polymers; modification

Introduction industry, there are efforts to produce environmentally safer

With the current expansion of polymers and their com-
posites in industrial applications, the synthetic sources of
raw materials appear to be limited. These polymers are
mainly non-biodegradable materials. However, the use of
biopolymers and their mixtures with synthetic polymers
can yield enhanced biodegradation rates.[1] Natural poly-
mers are abundant and also biodegradable.[2–4] For this
reason, a new generation of environmentally friendly ma-
terials has emerged and may replace current sources in
industrial applications. Even within the microelectronics
products which include polymer coatings and compo-
sites that are halogen-free,[5] flexible polymeric packages
without chromium layers for copper metallization[6] and
solder-based formulations that contain reduced lead or are
lead-free.[7,8] Industrially, synthetic polymers are modified
to provide specific compatibility, durability or properties
dictated by their expected use. These modifications are
applied by heterogeneous or homogeneous phase reactions
and in many cases, only dry processes are economically
feasible. Although chemical modification of biopolymers is
usually performed by reactions in solutions, dry processes

Macromol. Mater. Eng. 2002, 287, No. 12 ß WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002 1438-7492/2002/1212–871$17.50þ.50/0
872
for these materials are less commonly used. In fact, a single
reference exists on this type of modification approach for
chitosan. Shin et al. have recently reported improved
chitosan absorption on cotton and poly(ethylene terephtha-
late) using UV irradiation and air plasmas.[9]
Chitosan is the second largest supply of natural biopoly-
mers after cellulose.[10] For this reason, this polymer has
found a tremendous variety of real and potential industrial
applications in the past years.[11–14] Chitin is typically
found in the exoskeleton of marine animals, fungi and some
living plants.[2,15] Cellulose and chitin are polymers that
have similar structures, however, chitin is quite insoluble
for direct applications. Chitin can be made soluble by che-
mical extraction from its source and then through a series of
chemical reactions, chitosan, a soluble material in acetic
acid/water solutions can be produced.[16] Chitosan, as defin-
ed here, is a polymeric material that contains some level of
deacetylated groups when compared to the initial chitin
structure (see Figure 1).
Oxygen plasma and UV/ozone irradiation of polymers
are standard dry processes for the modification of polymeric
materials. The oxidation of polymers in these environments
and their resulting changes have been described else-
where.[17–19] The modified surfaces can contain chemical
groups amenable to reactions as well as different degrees
of surface energies. These changes are necessary to
induce compatibility between dissimilar materials as well
as strong chemical interactions for adhesion purposes. In
other cases, the modification in oxidative environments is
an initial step to create diffusion barriers in organic films
that can compete with more costly standard sputter deposi-
tion methods.[20]
A typical approach to the surface modification of mate-
rials requires the use of complementary techniques such as
X-ray photoelectron spectroscopy (XPS), contact angle
measurements, surface morphology, and the chemical
characteristics of the surface modified layer. Because the
material chosen for this work is a biopolymer, special
care must be made to minimize its decomposition under the
experimental conditions chosen for characterization. The
reported results have been obtained on chitosan films depo-
sited on aluminium-coated silicon wafers.
XPS spectroscopy is a powerful technique for the charac-
terization of insulators and conductors of organic or inor-
Figure 1. Schematic representation of the chemical transformation of chitin
into partially deacetylated chitosan. In the present work, the average x and y
values are 0.7 and 0.3, respectively.
L. J. Matienzo, S. K. Winnacker
ganic origin.[21] XPS analysis of chitosan films has not been
well documented in the literature and in most cases, the
emphasis has been limited to the results of ion complexation
or the reactivity of chitosan in other polymer blends.[22,23]
In addition to this, the XPS spectra of cellulose like ma-
terials has not been well defined and band assignments of
the C1s environments are still in debate.[24–26] The reason
for this is the rather broad nature of the signals and the lack
of adequate reference materials. This study has attempted to
evaluate the high resolution XPS spectra of the C1s, N1s
and O1s regions of chitosan in order to follow spectral
changes with treatment times.
This work describes the effects induced by oxidation of
chitosan films, deposited on aluminium-coated silicon sub-
strates, in both oxygen plasma environments as well as
under UV/ozone irradiation conditions. Additional infor-
mation is presented to propose the degradation mechanism
of the surfaces of these films under the experimental
conditions outlined below.
Experimental Part
Chitosan with a degree of deacetylation of 70% (measured
by infrared spectroscopy) and an average molecular weight of
250 000 D (measured by intrinsic viscosity) was prepared by
standard procedures by the transformation of chitin.[27] The
source of chitosan was shrimp shells of the species Penaeus
vannamei. Self standing films were prepared by dilution of the
deacetylated material in a 2% aqueous acetic acid solution and
by casting onto polystyrene Petri dishes under a nitrogen
atmosphere. Films of chitosan were also deposited onto silicon
wafers (orientation (111)) sputter-coated with 1 000 Å of
Al. Aqueous solutions of chitosan with a concentration of 0.4%
(w/v) in 1% aqueous acetic acid solution were placed in an
ultrasonic bath for about 0.5 h. The Al surfaces were pre-
cleaned in a UV/ozone reactor for 10 min prior to contact with
the chitosan solution. The solution was allowed to evaporate
slowly on the Al surface and when the films appeared to be dry,
they were placed in a vacuum oven at 120 8C for 50 min.
The resulting films had an approximate thickness of 5 000 to
5 500 Å as measured by Nomarski interferometry and also
using a stylus profilometer.
A modified Physical Electronics 5500 Multiprobe spectro-
meter (base pressure of 1
1010 Torr) was used for XPS
measurements. An Al Ka monochromatized source (11 keV
Dry Processes for Surface Modification of a Biopolymer: Chitosan
and 350 W) was used to produce photoelectron emission
from the samples and a flood gun eliminated any charging
of the surfaces under study (sampling spot size of 800 mm).
Most spectra were collected with an angle of 658 to the
analyzer. This condition provides, the deepest sampling (ca.
100 Å) into the films. Variable angle XPS spectroscopy at
angles between 65 and 108 was used to monitor spectral
changes on the C1s region of the spectra as a function of tilting
angle. Survey spectra were taken with a pass energy of 185 eV
over the range of 1 200 and 0 eV. High resolution spectra on the
regions of interest were taken in a 20 eV window with a pass
energy of 5.85 eV. The envelopes from high resolution spectra
were curve-fitted using standard fitting routines with Gaussian-
Lorentzian bands and by selecting a linear background. The
binding energies where initially measured before and after
the addition of a thin layer of C36H74 over a layer of chitosan.
Since no change of band width or position was detected for the
lowest binding energy component in the C1s region, it is
reasonable to assume that this band has a binding energy of
285.0 eV. Further verification of this evaluation was made by
measuring the relative position of the –CF2– group in poly-
tetrafluoroethylene for a film of chitosan and an adjacent film
of the fluoropolymer. This –CF2– group has a binding energy of
292.5 eV versus the binding energy of C37H76 (C1s signal at
285.00 eV).
Advancing contact angles were measured on the organic
films supported by the Al-coated silicon wafer samples using a
Rame-Hart goniometer and a 5 mL drop of water. In all cases,
an average of three measurements was made on each sample.
A Nexus 670 FTIR spectrometer equipped with a Con-
tinuum microscope was used for characterization. Because it
was desirable to compare the degree of deacetylation in the
incoming films as well as those deposited onto the Al-coated
substrates, transmission and reflectance measurements were
made, respectively. Background and sample spectra were taken
with total of 500 scans and a resolution of 4 cm1. The degree
of deacetylation was measured by standard methods using
the absorbance ratios of the amide and hydroxyl bands in the
molecule.[1] The degree of deacetylation was 70% for either
type of sample. FTIR spectra were also used to verify that the
material had the type II chitin structure.
A Nanoscope IIIa instrument (Digital Instruments) was ope-
rated in the atomic force microscopic (AFM) tapping mode.
Samples of silicon coated films were mounted on metallic
studs and images were obtained on a square pattern of
2.2 mm
2.2 mm.
Thermogravimetric analyses of modified and unmodified
films were performed with a Series 7 Perkin-Elmer Thermal
Analysis System. The samples were run as solids in an air
atmosphere between temperatures of 30 to 900 8C at a rate of
40 8C/min. The onset of the decomposition of these films was
estimated to be above 320 8C.
A UVOCS UV/ozone cleaner was used for modifications of
supported chitosan films as well as to clean the metallized
substrates prior to film deposition. The characteristics of this
system have been fully described elsewhere.[17] Surface
modification was induced for various lengths of time. Contact
angle and XPS measurements of equivalent films were taken
after these experiments. In order to determine if molecular
weight changes were induced on the chitosan molecules as a
873
function of irradiation time, solutions of the polymer were
exposed to the effects of UV/ozone treatment. After each
experiment, the viscosity of the solutions was measured using a
calibrated viscosimeter.
A Plasma reactor (Yorktown T Design) was used for pre-
liminary experiments. A full description of this reactor has
been given elsewhere.[28] Since this system contains a higher
dosage of ion bombardment (reactive ion etching mode, RIE),
it produces high etching rates of organic materials. The initial
evaluations indicated that the rate of modification was extre-
mely high in this reactor. A second system with a minimal
contribution from ion bombardment was then selected for
plasma modification. A SPI Plasma PREP II, barrel etcher type
reactor met these specifications. The typical operating pressure
range was maintained at 400 mTorr to obtain an oxygen plasma.
Sample modification was produced on supported films for
specified times. Contact angle measurements and XPS spectra
were collected as described previously.
The density of hydroxyl groups on the initial films and after
treatment was monitored by reaction of the surfaces (30 min at
room temperature) with a 1% (v/v) solution of a 80% meth-
anol-20% water mixture (v/v) of 3,3,3-trifluoropropyltri-
methoxysilane (TFTMSi). The samples were placed in an
oven at 80 8C for 30 min to induce and complete the reaction of
the methoxy groups of the silane with available hydroxyl
groups on a surface.
Results and Discussion
In order to determine the changes introduced on chitosan by
dry surface modification reactions in an oxidizing medium,
it is necessary to understand the XPS signals on the unmo-
dified material, its response to vacuum and stability under
X-ray exposure, and also to deposition onto a substrate.
Figure 1 gives a schematic representation of chitosan co-
polymer with some degree of deacetylation. The values of x
and y are 0.7 and 0.3, respectively. This Figure also includes
the appropriate labeling of carbon environments used in the
interpretation of XPS data. A typical XPS survey spectrum
of the as-received film shows the expected elements, i.e., C,
N, and O but in addition, traces of Ca, Si and Cl can be found
(see Figure 2). These minor components are the result of the
processing of exoskeleton components from the source
material. The theoretical expected atomic composition of
the 70% deacetylated chitosan is 55% C, 36% O and 9% N.
Films produced by the described method give results such
as 61% C, 31% O, 6% N, with the balance being impurities
in the film. These results suggest that the film may contain
some contaminating overlayer or that its surface may not
necessarily be the same as the expected average stoichio-
metry of a bulk film. This latter effect has been reported for
some polymers with some long repeating units and block
copolymers.[29,30] Concerning chitosan, the actual struc-
tural unit arrangement of the material has not been fully
defined and the nature of random vs. block copolymer units
is still under debate.[3]
874 L. J. Matienzo, S. K. Winnacker

Figure 2. Survey XPS spectrum of a chitosan film using

monochromatized radiation.

High resolution XPS spectra for the C1s region of

unmodified films as well as those deposited onto aluminium
are similar, thus, showing that the deposition methods do
not alter the initial material. Avacuum dried film at 3
109
Torr gives a truer representation of the XPS spectrum of
chitosan. Indeed, curve fitting of the C1s region of the UHV
dried films yields four different signals whose positions can
be assigned using curve-fitting methods (see Figure 3a).
Since the structure of partially deacetylated chitosan is
quite complex, a first approximation on the expected XPS
spectrum for the C1s region is complicated because gluco-
samine and N-acetylglucosamine segments must be consi-
dered. However, if some solid state NMR data for chitosan
are used, a better interpretation of the overall XPS envelope
can be made. Recently, De Angelis et al have reported the
13
C CP-MAS NMR spectrum of chitosan with a degree of
deacetylation of 9.1%.[31] The NMR data show a total of
eight environments for the carbon atoms of the repeating
unit of the copolymer. Because XPS does not have the level
of resolution provided by NMR, the overall envelope can
only be represented by four different environments in which
the carbon atoms from the glucosamine and N-acetylglu-
cosamine repetitive units are grouped. The various carbon
atoms in the repeating units are labeled in Figure 1. Our
interpretation groups atoms C2 and C6 from the glucosa-
mine units with carbon atoms C2, C6 and C8 from the
N-acetylglucosamine rings into a single environment. A
second carbon environment is produced by C3, C4 and
C5 in the glucosamine segment and C3, C4 and C5 in the
N-acetylglucosamine segment. A third environment is Figure 3. a) High resolution C1s, b) N1s and c) O1s XPS spectra
produced by contributions of C1 atoms in both segments. for chitosan film on Al-coated silicon surface with (111) orientation.
Dry Processes for Surface Modification of a Biopolymer: Chitosan 875

A fourth signal arises from C7 in the acetylglucosamine

unit. The individual bands have positions at 285.1, 286.6,
288.1 and 288.8 eV, respectively. The application of a thin
layer of C36H74 over the chitosan layer only enhanced the
intensity of the lower binding energy component without
any change in band width. This suggested that the band
positions relative to the C1s at 285.0 eV were essentially
correct. An independent experiment using the –CF2– group
in polytetrafluoroethylene as a secondary calibration
standard yielded the expected band positions for hydro-
xylpropyl cellulose when a sample of this material was
analyzed.[32]
For a material with a degree of deacetylation of 70%, the
expected areas should be 36%, 42%, 14% and 8%, respec-
tively. The estimated areas from curve-fitting calculations
are 37%, 43%, 13% and 7%, respectively.
The N1s region of the spectrum contains one dominant
signal at 399.7 eV and one small contribution located at
401.1 eV. These signals correspond to non-protonated
amine groups and those that have been protonated by acid,
respectively. The nitrogen environments on the molecule Figure 4. High resolution C1s XPS spectra of chitosan as a
appear to contain some quaternary nitrogen with an esti- function of tilting angle to the analyzer.
mated concentration of about 7%. The position of the
unprotonated nitrogen signal is in agreement with reported
results for polyacrylamide and polymethacrylamide poly- chitosan and chitin exist in two different crystal structures
mers.[32] Because a single nitrogen environment is expected known as forms I and II. More recently, Okuyama et al.[15]
in the polymer, it appears that the dissolution process in have reported X-ray data with the lattice parameters for
acetic acid is capable of inducing some protonation of the various forms of chitosan. The thickness of a single molec-
amine segments and a few of these groups remain proto- ular layer of the copolymer in the surface plane has been
nated in the dry film. These findings are consistent with reported to be 8.26 Å for anhydrous chitosan, 8.95 Å for
reports by Okuyama et al.[15] on formic acid and acetic acid hydrated chitosan and 10.58 Å for a chitosan/formic acid
reaction products of chitosan. complex. This information is useful in understanding the
The O1s region of the spectrum contains at least three XPS data from the variable angle experiments since at
overlapping signals at positions 531.5 eV (carbonyl groups), shallow angles of 108, more than one molecule in depth is
532.6 eV (–O– groups) and 533.4 eV (–OH groups). sampled and any hydrocarbon overlayer will dominate and
Likewise, the position of the carbonyl groups are similar to
those found in polyacrylamide and the other positions of the
glycosidic and hydroxyl groups are in agreement with
typical ranges for these groups in cellulose.[32] The N1s and
O1s high resolution spectra for chitosan are shown in
Figure 3b and 3c.
Variable angle XPS data for the C1s region are also
informative (see Figure 4 ). For shallower sampling (lower
angles) the intensity of the band assigned mainly to the
second set of atoms decreases drastically and the lowest
binding energy signal predominates and it is rich in hydro-
carbon-like contributions. Variable angle data can provide
an estimate of sampling depth (d) using, to a first approxi-
mation, the equation d ¼ 3l sin y, where, l is the inelastic
mean free path of photoelectrons for carbon in a polymer
and sin y represents the sine of the angle to the analyzer.
Recent measurements of l for 14 polymers have yielded an
average value of about 35.3 Å.[33,34] The estimated
thickness of the analyzed depth as a function of angle is Figure 5. Estimated sampling depth into polymer layer as a
shown in Figure 5. X-ray diffraction data have shown that function of take-off angle.
876 L. J. Matienzo, S. K. Winnacker

affect the wettability of the surface. At higher angles, the

photoelectrons come from several layers of the copolymer
and the surface stoichiometry may be influenced by the
contribution of other signals that yield spectral intensity. In
addition, the repetitive nature of the chains is not well
defined.[3]
Figure 6 presents the results for advancing contact angle
measurements with water for films treated in oxygen plasma
conditions including the RIE mode, non-RIE mode (Plasma
Etcher) and films exposed to UV/ozone reactions. The
initially highly hydrophobic surface with a contact angle of
1008 is made quite hydrophilic by treatment in either
plasma or UV/ozone oxidation reactions, and reaches an
equilibrium contact angle of about 188. Both plasma sys-
tems result in comparable rates of modification, but the
treatment in the plasma barrel etcher does not alter the
surface roughness of the polymer as much as the RIE
process does. The surface morphologies of irradiated films
under oxygen plasma (reduced RIE mode, 60 s) are affected
more than those subjected to UV/ozone irradiation (60 s of
exposure). AFM surface profiles of these samples reveal
that oxygen plasma contributes to film roughness while the
UV/ozone modified films show smoother films and very
comparable to the untreated films (see Figure 7).
Figure 8a and 8b display isometric views of the sequential
transformation of the C1s region of chitosan as a function of
plasma reactor type and treatment times. The modification
leads to oxidized segments with a preferred enhancement of
carbonyl-containing species. The oxidation rate in UV/
ozone is slower but still resembles the changes seen in the
oxygen plasma results. Figure 9 presents the XPS C1s
curve-resolved spectrum of a treated film in UV/ozone for
4 min. The high binding energy signal associated with Figure 7. AFM surface profiles for (a) UV/ozone treated
carbonyl groups has increased in intensity. The O1s region chitosan film for 1 min and (b) oxygen plasma treated film in
of the same sample shows the growth of the oxygen asso- barrel etcher for 1 min.
ciated with the carbonyl group while the nitrogen region
does not appear to change at all. Infrared spectra
(see Figure 10) of the untreated films also show that the
films do not undergo any bulk changes with irradiation. This
effect, in the case of UV/ozone modification appears to be
restricted to very shallow depths without any surface
roughness change.
The role of hydroxyl groups in the modification reactions
can be determined by using a reaction that is able to measure
the density of existing groups on the polymer surface.
Alkoxysilanes are known to react efficiently with hydroxyl
groups to yield Si–O-surface bonds.[35] This transformation
is accomplished by hydrolysis of the alkoxy groups and the
displacement of volatile alcohol byproducts. If 3,3,3-
trifluoromethylproyltrimethoxysilane is used, the incor-
poration of the silicon atom and the foreign group –CF3 can
be used to monitor the abundance of hydroxyl groups pre-
Figure 6. Advancing water contact angles for chitosan films
modified in RIE oxygen plasma reactor, barrel etcher oxygen sent after any time of modification. The results summarized
plasma reactor and UV/ozone irradiation as a function of treatment in Table 1 indicate that incorporation of fluorinated groups
time. for surface modified films and non-treated films is similar.
Dry Processes for Surface Modification of a Biopolymer: Chitosan 877

Figure 9. High resolution C1s XPS envelope for a chitosan film

treated for 4 min in UV/ozone.

Figure 8. Changes in C1s XPS band shapes as a function of

treatment times for film modified: (a) in barrel etcher and (b) UV/
ozone reactor. The third axes represent the sequential display of Figure 10. Reflectance FTIR spectra (grazing angle of 458) of
signals as a function of treatment time (identified on each chitosan films before and after 4 min of exposure to UV/ozone
spectrum). irradiation.

Table 1. Surface compositions (atomic %) of chitosan films following exposure to fluorosilane and to UV/ozone treatments.

Sample Surface composition

atomic %
%C %O %N %Ca %Si %Al %F
a)
Untreated 61 30.4 5.8 0.8 0.4 1.2
þF silane 43.1 24.1 3.2 0.3 6.3 24
1 min UV/oz þ F silane 41.1 22.5 1.7 0.4 8.3 1.8 24.1
5 min UV/oz þ F silane 43.6 27 3.9 0.2 5.1 20.1
a)
Untreated sample is a film of chitosan on Al/Si.
878
For example, 1 min in UV/ozone yields a comparable result
to the untreated film. At that point, the contact angle of the
surface is about 308. Longer treatment times, up to 5 min,
show a slight decrease in fluorine incorporation indicating
that for all practical purposes, these groups do not actively
participate in the degradation of the film. As a comparison,
1 min of treatment for a film in the barrel etcher (contact
angle of 208 prior to silylation) contains 39.0% C, 24.5% O,
3.3% N, 5.0 % Si, 24.5% F, 0.9 % Al and 2.7% Ca after
reaction with the silane.
The silylation of chitosan can be taken a step further since
a second modification via oxidation of these surfaces can
produce a silica-like oxygen diffusion barrier on the film.
The initially high contact angle is induced by the fluo-
rosilane layer at the polymer surface (F concentration is
24% atomic). Transformation of the surface into a hydro-
philic surface (SiO2-rich) with a lower contact angle can
be accomplished by oxidation. For example, the surface
composition of a film after 5 min of UV/ozone exposure
contains 37.4% C, 42.7% O, 4.1% N, 8.7% F and 7.1% Si.
The contact angle of this film is 358. At longer treatment
times (11 min), the surface composition contains 40.8% C,
44.1% O, 5.4% N, 2.8% F and 6.9% Si and its water contact
angle is 108. Certainly, this transformation is not restricted
to the silane described here but it can be produced using any
other silane material. TGA analyses of unmodified films,
after reaction with the fluorosilane and after oxidation of the
fluorosilane treated film following 11 min of UV/ozone
irradiation yield similar thermal behavior thus confirming
that the bulk regions of the films have not been altered much
by either process. At temperatures greater than 600 8C, the
silane-treated films yield slightly higher levels of residue
than unmodified chitosan films, as expected.
Since it is practically impossible to determine if any chan-
ges in molecular weight distribution occur at the surface of
the films as a function of treatment time, a parallel experi-
ment was conducted by subjecting chitosan solutions of the
as-received film to UV/ozone irradiation. After specified
times, the viscosity of the exposed solution was measured.
The results obtained in this experiment are plotted in
Figure 11. It is apparent that the viscosity of the initial
solution decreases with irradiation time, thus, yielding
lower molecular weight fragments.
Proposed Mechanism of Modification for Chitosan
Films Under Oxygen Plasma or UV/Ozone Irradiation
The results shown in this work indicate that the oxidation of
chitosan films in either plasma or UV/ozone conditions pro-
ceeds in a similar fashion. UV/ozone reactions of chitosan
are advantageous since they produce surface layers that are
hydrophilic and relatively smooth. This process allows for a
better control on molecular weight changes over faster
plasma oxidation reactions. XPS data show that minimal
hydroxyl or amine participation takes place during the
L. J. Matienzo, S. K. Winnacker
Figure 11. Viscosity changes of chitosan solution and water
(reference) as a function of UV/ozone exposure times.
modification. The increased carbonyl formation with treat-
ment time is similar to reports on the effects of UV-only and
ozone-only exposures of cellulose.[36,37] Ultraviolet radia-
tion and ozone-only processes on chitosan have been
reported to yield carbonyl group formation and reduction in
molecular weight at wavelengths lower than 360 nm.[38,39]
The commonality of the oxygen plasma process and the
UV/ozone reaction lies in the activity of VUV and UV
radiation. The effect of VUV radiation in practical plasmas
is well recognized and the radiation involved in ozone
production is well below the 300 nm range.[17,40] Then, the
overall cleavage reaction leading to carbonyl formation
with segments of reduced molecular weights and amine
group preservation more likely follows the scheme shown
in Figure 12 for the glucosamine portion of the structure.
Attack on the N-acetylglucosamine segments would lead to
the loss of methylated carbonyl fragments.[38]
Conclusions
The exposure of chitosan films coated on Al/Si substrates to
oxidative surface reactions results on a surface that is more
hydrophilic, richer in carbonyl containing molecules and
with lower molecular weights than the bulk material. The
deposition of chitosan films onto Al-coated silicon (111)
wafers produces films with the more ordered chitosan struc-
ture (type II). Surface analysis of modified films by XPS
indicates that the hydroxyl groups as well as the amine
segments appear not to participate in surface degradation
reactions by either UV/ozone or oxygen plasma in the
exposure times chosen for these studies. Surface roughness
of the initial films is preserved under UV/ozone modifica-
tion unlike oxygen plasma modification, even under reduc-
ed RIE conditions. Thus, UV/ozone modification results
in a material with shallower surface modification depths.
Bulk analysis of the films before and after treatments
demonstrate that the thermal behavior and chemical
Dry Processes for Surface Modification of a Biopolymer: Chitosan
Figure 12. Proposed mechanism for attack on the chitin-like
segment of partially deacetylated chitosan leading to the
formation of carbonyl groups under irradiation in a UV/ozone
reactor.
composition of the original chitosan film are preserved.
Because silane materials are capable of reaction with
hydroxyl groups in the polymer, the resulting product can
provide an intermediate and a simple way to form silica-
containing layers on the surface of the films. Finally, UV
radiation with wavelengths shorter than 360 nm is
responsible for film modification.
Acknowledgement: The authors are deeply appreciative for the
help and stimulation provided by Prof. J. Nakamatsu, Pontificia
Universidad Catolica del Peru, during the development of this
work. Also, the assistance of Mr. D. Sarno from the State
University of New York at Binghamton with AFM imaging is
acknowledged.
Received: June 28, 2002
Revised: October 9, 2002
Accepted: October 16, 2002
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[2] S. Hirano, Polym. Int. 1999, 48, 732.
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