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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.
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 L. J. Matienzo, S. K. Winnacker
for these materials are less commonly used. In fact, a single ganic origin.[21] XPS analysis of chitosan films has not been
reference exists on this type of modification approach for well documented in the literature and in most cases, the
chitosan. Shin et al. have recently reported improved emphasis has been limited to the results of ion complexation
chitosan absorption on cotton and poly(ethylene terephtha- or the reactivity of chitosan in other polymer blends.[22,23]
late) using UV irradiation and air plasmas.[9] In addition to this, the XPS spectra of cellulose like ma-
Chitosan is the second largest supply of natural biopoly- terials has not been well defined and band assignments of
mers after cellulose.[10] For this reason, this polymer has the C1s environments are still in debate.[24–26] The reason
found a tremendous variety of real and potential industrial for this is the rather broad nature of the signals and the lack
applications in the past years.[11–14] Chitin is typically of adequate reference materials. This study has attempted to
found in the exoskeleton of marine animals, fungi and some evaluate the high resolution XPS spectra of the C1s, N1s
living plants.[2,15] Cellulose and chitin are polymers that and O1s regions of chitosan in order to follow spectral
have similar structures, however, chitin is quite insoluble changes with treatment times.
for direct applications. Chitin can be made soluble by che- This work describes the effects induced by oxidation of
mical extraction from its source and then through a series of chitosan films, deposited on aluminium-coated silicon sub-
chemical reactions, chitosan, a soluble material in acetic strates, in both oxygen plasma environments as well as
acid/water solutions can be produced.[16] Chitosan, as defin- under UV/ozone irradiation conditions. Additional infor-
ed here, is a polymeric material that contains some level of mation is presented to propose the degradation mechanism
deacetylated groups when compared to the initial chitin of the surfaces of these films under the experimental
structure (see Figure 1). conditions outlined below.
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 Experimental Part
and their resulting changes have been described else-
where.[17–19] The modified surfaces can contain chemical Chitosan with a degree of deacetylation of 70% (measured
groups amenable to reactions as well as different degrees by infrared spectroscopy) and an average molecular weight of
of surface energies. These changes are necessary to 250 000 D (measured by intrinsic viscosity) was prepared by
standard procedures by the transformation of chitin.[27] The
induce compatibility between dissimilar materials as well
source of chitosan was shrimp shells of the species Penaeus
as strong chemical interactions for adhesion purposes. In
vannamei. Self standing films were prepared by dilution of the
other cases, the modification in oxidative environments is deacetylated material in a 2% aqueous acetic acid solution and
an initial step to create diffusion barriers in organic films by casting onto polystyrene Petri dishes under a nitrogen
that can compete with more costly standard sputter deposi- atmosphere. Films of chitosan were also deposited onto silicon
tion methods.[20] wafers (orientation (111)) sputter-coated with 1 000 Å of
A typical approach to the surface modification of mate- Al. Aqueous solutions of chitosan with a concentration of 0.4%
rials requires the use of complementary techniques such as (w/v) in 1% aqueous acetic acid solution were placed in an
X-ray photoelectron spectroscopy (XPS), contact angle ultrasonic bath for about 0.5 h. The Al surfaces were pre-
measurements, surface morphology, and the chemical cleaned in a UV/ozone reactor for 10 min prior to contact with
characteristics of the surface modified layer. Because the the chitosan solution. The solution was allowed to evaporate
slowly on the Al surface and when the films appeared to be dry,
material chosen for this work is a biopolymer, special
they were placed in a vacuum oven at 120 8C for 50 min.
care must be made to minimize its decomposition under the
The resulting films had an approximate thickness of 5 000 to
experimental conditions chosen for characterization. The 5 500 Å as measured by Nomarski interferometry and also
reported results have been obtained on chitosan films depo- using a stylus profilometer.
sited on aluminium-coated silicon wafers. A modified Physical Electronics 5500 Multiprobe spectro-
XPS spectroscopy is a powerful technique for the charac- meter (base pressure of 1 1010 Torr) was used for XPS
terization of insulators and conductors of organic or inor- measurements. An Al Ka monochromatized source (11 keV
and 350 W) was used to produce photoelectron emission function of irradiation time, solutions of the polymer were
from the samples and a flood gun eliminated any charging exposed to the effects of UV/ozone treatment. After each
of the surfaces under study (sampling spot size of 800 mm). experiment, the viscosity of the solutions was measured using a
Most spectra were collected with an angle of 658 to the calibrated viscosimeter.
analyzer. This condition provides, the deepest sampling (ca. A Plasma reactor (Yorktown T Design) was used for pre-
100 Å) into the films. Variable angle XPS spectroscopy at liminary experiments. A full description of this reactor has
angles between 65 and 108 was used to monitor spectral been given elsewhere.[28] Since this system contains a higher
changes on the C1s region of the spectra as a function of tilting dosage of ion bombardment (reactive ion etching mode, RIE),
angle. Survey spectra were taken with a pass energy of 185 eV it produces high etching rates of organic materials. The initial
over the range of 1 200 and 0 eV. High resolution spectra on the evaluations indicated that the rate of modification was extre-
regions of interest were taken in a 20 eV window with a pass mely high in this reactor. A second system with a minimal
energy of 5.85 eV. The envelopes from high resolution spectra contribution from ion bombardment was then selected for
were curve-fitted using standard fitting routines with Gaussian- plasma modification. A SPI Plasma PREP II, barrel etcher type
Lorentzian bands and by selecting a linear background. The reactor met these specifications. The typical operating pressure
binding energies where initially measured before and after range was maintained at 400 mTorr to obtain an oxygen plasma.
the addition of a thin layer of C36H74 over a layer of chitosan. Sample modification was produced on supported films for
Since no change of band width or position was detected for the specified times. Contact angle measurements and XPS spectra
lowest binding energy component in the C1s region, it is were collected as described previously.
reasonable to assume that this band has a binding energy of The density of hydroxyl groups on the initial films and after
285.0 eV. Further verification of this evaluation was made by treatment was monitored by reaction of the surfaces (30 min at
measuring the relative position of the –CF2– group in poly- room temperature) with a 1% (v/v) solution of a 80% meth-
tetrafluoroethylene for a film of chitosan and an adjacent film anol-20% water mixture (v/v) of 3,3,3-trifluoropropyltri-
of the fluoropolymer. This –CF2– group has a binding energy of methoxysilane (TFTMSi). The samples were placed in an
292.5 eV versus the binding energy of C37H76 (C1s signal at oven at 80 8C for 30 min to induce and complete the reaction of
285.00 eV). the methoxy groups of the silane with available hydroxyl
Advancing contact angles were measured on the organic groups on a surface.
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- Results and Discussion
tinuum microscope was used for characterization. Because it
was desirable to compare the degree of deacetylation in the In order to determine the changes introduced on chitosan by
incoming films as well as those deposited onto the Al-coated dry surface modification reactions in an oxidizing medium,
substrates, transmission and reflectance measurements were it is necessary to understand the XPS signals on the unmo-
made, respectively. Background and sample spectra were taken dified material, its response to vacuum and stability under
with total of 500 scans and a resolution of 4 cm1. The degree X-ray exposure, and also to deposition onto a substrate.
of deacetylation was measured by standard methods using Figure 1 gives a schematic representation of chitosan co-
the absorbance ratios of the amide and hydroxyl bands in the polymer with some degree of deacetylation. The values of x
molecule.[1] The degree of deacetylation was 70% for either and y are 0.7 and 0.3, respectively. This Figure also includes
type of sample. FTIR spectra were also used to verify that the the appropriate labeling of carbon environments used in the
material had the type II chitin structure.
interpretation of XPS data. A typical XPS survey spectrum
A Nanoscope IIIa instrument (Digital Instruments) was ope-
of the as-received film shows the expected elements, i.e., C,
rated in the atomic force microscopic (AFM) tapping mode.
Samples of silicon coated films were mounted on metallic N, and O but in addition, traces of Ca, Si and Cl can be found
studs and images were obtained on a square pattern of (see Figure 2). These minor components are the result of the
2.2 mm 2.2 mm. processing of exoskeleton components from the source
Thermogravimetric analyses of modified and unmodified material. The theoretical expected atomic composition of
films were performed with a Series 7 Perkin-Elmer Thermal the 70% deacetylated chitosan is 55% C, 36% O and 9% N.
Analysis System. The samples were run as solids in an air Films produced by the described method give results such
atmosphere between temperatures of 30 to 900 8C at a rate of as 61% C, 31% O, 6% N, with the balance being impurities
40 8C/min. The onset of the decomposition of these films was in the film. These results suggest that the film may contain
estimated to be above 320 8C. some contaminating overlayer or that its surface may not
A UVOCS UV/ozone cleaner was used for modifications of necessarily be the same as the expected average stoichio-
supported chitosan films as well as to clean the metallized
metry of a bulk film. This latter effect has been reported for
substrates prior to film deposition. The characteristics of this
system have been fully described elsewhere.[17] Surface some polymers with some long repeating units and block
modification was induced for various lengths of time. Contact copolymers.[29,30] Concerning chitosan, the actual struc-
angle and XPS measurements of equivalent films were taken tural unit arrangement of the material has not been fully
after these experiments. In order to determine if molecular defined and the nature of random vs. block copolymer units
weight changes were induced on the chitosan molecules as a is still under debate.[3]
874 L. J. Matienzo, S. K. Winnacker
Table 1. Surface compositions (atomic %) of chitosan films following exposure to fluorosilane and to UV/ozone treatments.
[32] G. Beamson, D. Briggs, ‘‘High Resolution XPS of Organic [37] H. Sixtra, G. Gotzinger, A. Schrittweiser, P. Hendel, Papier
Polymers’’, John Wiley & Sons, Chichester, UK, 1992, 1991, 45, 610.
Appendix 2. [38] I. R. Mullagaliev, N. N. Kabal’nova, G. G. Galiaskarova, E. I.
[33] S. Tanuma, C. J. Powell, D. R. Penn, Surf. Interface Anal. Pokalo, V. V. Shereshovets, Yu. B. Monakov, Russ. J. Appl.
1993, 21, 165. Chem. 1997, 70, 1625.
[34] R. J. Samuels, J. Polym. Sci., Polym. Phys. Ed. 1981, 19, [39] A. L. Andrady, A. Torikai, T. Kobatake, J. Appl. Polym. Sci.
1081. 1996, 62, 1465.
[35] L. J. Matienzo, J. Adhes. Sci. Technol. 1989, 5, 357. [40] E. M. Liston, ‘‘Proc. ISPC-7’’, Vol. 2, Eindhoven, The
[36] N. S. Hon, J. Macromol. Sci., Chem. 1976, A10, 1175. Netherlands 1985, p. 513.