Polymer Degradation and Stability 70 (2000) 161±170

www.elsevier.nl/locate/polydegstab

Chemical modi®cation of starch based biodegradable polymeric

blends: e€ects on water uptake, degradation behaviour and
mechanical properties
DoÈne DemirgoÈz a,b, Carlos Elvira a,*, JoaÄo F. Mano a,
Antonio M. Cunha a, Erhan Piskin b, Rui L. Reis a
a
Department of Polymer Engineering, University of Minho, Campus AzureÂm, 4810-058 GuimaraÄes, Portugal
b
Department of Chemical Engineering, Hacettepe University, Beytepe Campus, 06532 Ankara, Turkey

Received 13 April 2000; accepted 13 June 2000

Abstract
The main disadvantages of biodegradable polymers obtained from renewable sources are their dominant hydrophilic character,
fast degradation rate and, in some cases, unsatisfactory mechanical properties particularly under wet environments. One possible
solution to this problem is to reduce the water-uptake ability of these materials and to enhance the respective mechanical behaviour
by chemical modi®cation. In this work, three based starch blends with: (i) a copolymer of ethylene and vinyl alcohol (SEVA-C), (ii)
cellulose acetate (SCA), and (iii) poly-e-caprolactone (SPCL); were chemically modi®ed by chain crosslinking. This modi®cation is
based on the reaction between the starch hydroxyl groups and tri-sodium tri-meta phosphate. The obtained compounds were
characterized by FTIR and the respective properties were assessed and compared to the original materials by means of the hydra-
tion degree, the degradation behaviour, contact angle measurements and mechanical testing. The results show that the water-uptake
of these blends could be reduced up to 15% and that simultaneously sti€er materials with a less pronounced degradation rate can
be obtained. # 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction available in large quantities [1,5]. Furthermore, starch-

Natural origin and synthetic polymers (and the
respective composites) are currently extensively used as
biomaterials and in biodegradable applications, because
they are available in a wide variety of compositions and
their properties can be tailored to meet speci®c
demands. Furthermore, the stability of the majority of
the polymers obtained from the petrochemical industry
can cause disposal problems. Within this scope, it has
been noticeable in the last few years an increasing
interest in biodegradable polymers derived from
annually renewable feedstock such as starch and starch-
based materials [1±4].
Starch-based blends present an enormous potential to
be widely used in the biomedical and the environmental
®elds, as they are totally biodegradable, inexpensive
(when compared to other biodegradable polymers) and
* Corresponding author.
E-mail address: celvira@eng.uminho.pt (C. Elvira).
0141-3910/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(00)00102-6
based polymers can also be converted into complex
geometries using standard equipment developed for the
processing of synthetic polymers. The properties, appli-
cations and the processing procedures of biodegradable
starch-based thermoplastic blends, like starch/poly-
caprolactone, starch/cellulose acetate and starch/(ethyl-
ene-vinyl alcohol copolymer), as been already reported
in literature [4,6±8,11]. However, new areas are emer-
ging including drug delivery systems, hydrogels, bone
cements and bone replacement/®xation devices [6±14].
All these developments require the possibility of
accurately control the polymer water sensitivity, degra-
dation rate and, consequently, the mechanical perfor-
mance. In the orthopaedic ®eld, the aim is to develop
systems that will be able to sustain their integrity and
mechanical performance in the presence of aqueous
media in the ®rst implantation stages and start to
degrade thereafter. This performance has to be achieved
keeping the materials able to degrade under controlled
kinetics [15±25].
162 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170
In order to improve this kind of behaviour, chemical
modi®cations based on well-known organic reactions
were used in this work. Nevertheless, it is worth
mentioning that such type of modi®cations have never
been tried before on the types of blends studied in this
work. Special attention was devoted to the surface
modi®cation as material surface properties are determi-
nant in biomedical applications (bioactivity, cell adhe-
sion and proliferation, protein interactions, etc.). In
fact, it is the surface of the material that interacts with
proteins and cells and, consequently, the implant beha-
viour will deeply depend on its properties [26].
So, the present work is an attempt to ®nd an adequate
method to reduce the water sensitivity and the degra-
dation rate of starch-based formulations by crosslinking
some of the hydroxyl groups present in the blends.
These chemical modi®cations are expected to have also
a direct impact over surface and mechanical properties
of the modi®ed compounds.
2. Experimental
2.1. Materials
The studied starch-based thermoplastic blends, kindly
supplied by Novamont, Novara, Italy, were: (i) a corn
starch/ethylene-vinyl alcohol (SEVA-C); (ii) a corn
starch/cellulose acetate (SCA); and (iii) a corn starch/e-
caprolactone, (SPCL).
Powders, ®lms (prepared by compression moulding at
120±130 C) and ASTM dumbell tensile test specimens
(prepared by injection moulding using a previously
described procedure 4, with a cross-section of 24 mm)
were used in this work.
2.2. Crosslinking reaction
The crosslinking reactions were carried out, as
described in the literature for native starch 28, using tri-
sodium tri-meta phosphate, Na3P3O9 (Aldrich-Ger-
many) as a crosslinking reagent in the following con-
centrations (relatively to the weight of the blend): 15.7,
7.8 and 3.9%. These concentrations were used on
preliminary tests aimed at choosing the ideal Na3P3O9
concentration to use on all subsequent studies. This
ideal concentration was found to be 15.7% (see
Results).
First, the Na3P3O9 was dissolved in an aqueous solu-
tion being the pH value adjusted to 10±11 by using
Na2CO3 (CO) or NaOH (NA), both from Aldrich-Ger-
many. The starch-based blend was then added (2 g) to
the solution (20 ml) and the reaction was carried out at
50 C for 5 h under continuous stirring.
The reaction was initially performed using the blends in
the powder form. However, some studies were also
developed on the obtained ®lms and on the ASTM speci-
mens. All the tensile samples were previously immersed in
a water solution at room temperature for 3 days in order to
remove the processing aids contained in the blends.
2.3. Characterization by Fourier transformed infra-red
spectroscopy (FTIR)
FTIR spectra were recorded on a Perkin-Elmer 1600
Series spectrometer. Spectra were taken with a resolution
of 2 cmÿ1 and were averaged over 32 scans. Samples were
thoroughly grounded with exhaustively dried KBr and
pellets were prepared by compression under vacuum.
2.4. Hydration degree and degradation behaviour
The water-uptake and the degradation of the materi-
als (in the form of tensile specimens) was studied over a
period of 90 days. Materials were conditioned to mini-
mum weight at 37 C in an oven with desiccant prior to
being immersed in 100 ml of a simulated physiological
isotonic solution (0.154 M NaCl aqueous solution at pH
7.4). The specimens were removed at regular intervals of
3, 7, 14, 30, 60 and 90 days, being taken out of the
solution, blotted on ®lter paper to remove surface solu-
tion and further rinsed with distilled water and weighed.
After being removed from the solution, the specimens
were dried, in an oven at 60 C, to constant weight in
order to determine the eventual weight loss (an average
of value of two readings was used). Equilibrium hydra-
tion degree was considered when no weight change (
0.001 g) was observed, after 2±3 days of immersion. The
hydration degree of the blends was also determined in
crosslinked ®lms with thickness between 90 and 220 mm,
considering the equilibrium hydration degree obtained
when no weight change was observed.
2.5. Mechanical properties
The tensile tests were performed on an Instron 4505
machine, ®tted with resistive extensometer (gauge length 10
mm) in a controlled environment (23 C, 55% RH). The
crosshead velocity was 5 mm/min (8.3  10ÿ5 m/s) until
1% strain (to determine the secant modulus with higher
precision) and then increased to 50 mm/min (8.310ÿ4 m/s)
until fracture. The samples were stored under controlled
temperature and moisture conditions until testing, and
at least six specimens were used. The fracture surfaces
were examined by scanning electron microscopy (SEM).
2.6. DMA analysis
Dynamic mechanical analysis (DMA) was also used
to characterize the mechanical behaviour of the mod-
 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170
i®ed blends. The tests were carried out using a tensile
loading scheme, by means of scanning the temperature
from ÿ20 to 160 C, in a Perkin-Elmer 7 series Thermal
Analysis System (specimen size 2053 mm). A fre-
quency of 1 Hz and a constant heating rate of 4 C minÿ1
were used. A static stress of 0.12 MPa was applied to the
specimens over a dynamic stress of 0.1 MPa.
2.7. Contact angle measurements
The contact angle between a liquid and the surface of
the ASTM specimens was measured at room tempera-
ture by means of a Contact Angle Measuring System
G10 by depositing a drop of distilled water and meth-
ylene iodide (CH2I2) on the material to study. The aim
was to evaluate the polar and dispersive components of
the surface energy. The quantity of liquid was measured
with a syringe monitored by a micrometric screw. The
results correspond to the average value of at least ten
measurements.
3. Results and discussion
3.1. Crosslinking reaction
Non-modi®ed SEVA-C, SCA and SPCL blends are
completely soluble in dimethylsulfoxide (DMSO).
However, after the reaction only a partial solubilization
was observed in all blends, which is a clear indication of
the high percentages of crosslinking obtained. Con-
centrations of Na3P3O9 (7.8 and 3.9%) were only used
in terms of ®nding the most optimal conditions to
achieve a relatively high crosslinking density. As the
amount of crosslinker was increased, the crosslinking
mass percentages were found to be higher, using the
highest concentration of Na3P3O9 (15.7%) in all the
experiments and performed studies. Consequently, this
concentration was used for preparing samples for all
other tests. Table 1 presents the amount of crosslinked
material for the three blends under study, following the
reactions performed with NaOH or Na2CO3, disclosing
percentages higher then 90% for SCA and SPCL
blends, and of about 50% for SEVA-C.
The high percentage of crosslinked mass obtained
with the described experimental conditions for SCA and
Table 1
Crosslinked mass percentage of the starch based blends after reacting
with 15.7% of Na3P3O9 (w/w) with respect to the blend, at 50 C for 5
h in the presence of NaOH (NA) or Na2CO3 (CO)
Sample SEVA-C- SEVA-C- SCA- SCA- SPCL-
NA CO NA CO NA
Crosslinked 62 50 91 63 96
mass (%)
163
SPCL can be attributed to: (i) the partial hydrolysis in
basic media of the corresponding ester groups (acetate
and lactone, respectively); and (ii) the hydroxyl groups
which can react with Na3P3O9 and also be involved in
the crosslinking reaction (see Fig. 1). On the other hand,
the low crosslinked mass percentage in the case of
SEVA-C blend can be attributed to the compatibility of
the blend in which starch and the ethylene-vinyl alcohol
are forming an interpenetrating network, and con-
seqently both hydroxyl groups from starch and vinyl
alcohol can be involved in the crosslinking reaction with
more diculty. The presence of the non-reactive ethyl-
ene units also reduced the crosslinked mass percentage,
as less accessible hydroxyl groups are present in the
blend. It was also observed in all cases that the cross-
linked mass percentage is higher when NaOH is used to
catalyse and to adjust the pH of the reaction [27].
3.2. Characterization by FTIR
The crosslinking reaction (Fig. 1) was charaterized by
comparing the FTIR spectra of both reacted and non-
reacted samples as the original material does not con-
tain any phosphate group in its structure. The typical
stretching vibrations of PˆO and P±O (at about 1200±
1100 cmÿ1) were observed in the spectra of all the
crosslinked samples. It was also noticeable that the
bands assigned to the starch hydroxyl stretching vibra-
tions (at 3400 cmÿ1) were decreased in intensity after the
crosslinking treatment as a consequence of the reaction
involving two starch hydroxyl groups per one phos-
phate. This can be observed in the spectra of non-treated
and crosslinked SPCL exhibited in Fig. 2.
The most important signals assigned to the corre-
sponding stretching vibrations (±OH, PˆO and P±O) of
SEVA-C, SCA and SPCL samples are summarised in
Table 2. No remarkable di€erences were observed in the
bands assigned to the carbonyl stretching vibration (at
about 1700 cmÿ1) in SCA (of acetate groups) and SPCL
(from poly-caprolactone), with respect to the corre-
sponding crosslinked blends.
3.3. Hydration degree and degradation behaviour
Both the hydration degree and the degradation beha-
viour are the most important properties of these mate-
rials when they are aimed to be used in biomedical or
environmental applications, as their life time will be
SPCL-
CO
94 Fig. 1. Crosslinking reaction of starch with tn-sodium tri-meta phos-
phate through the hydroxyl starch groups in sodium carbonate or
sodium hydroxide aqueous solution.
164 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170

Fig. 3. Swelling isotherms in isotonic saline solutions at 37 C of ®lms

of ^, SEVA; &, SEVA-NA; ~, SEVA-CO.

observe that the respective swelling kinetics are very

Fig. 2. FTIR spectra of SPCL and crosslinked SPCL.
governed by these two processes which are intimately
correlated.
The water-uptake percentage of the blends was deter-
mined by using the following equation [28]:
WW ÿ Wi
%Water-uptake ˆ  100%
Wi
where Wi is the initial weight of the sample and Ww is
the weight of the wet sample at di€erent times.
Table 3 presents the equilibrium hydration degree of
both tensile specimens and ®lms of SEVA-C, SCA and
SPCL and of the corresponding crosslinked blends
using NaOH or Na2CO3 in the reaction. No remarkable
di€erences are noticeable between the hydration degrees
of the ASTM specimens and of the ®lms, following the
same tendency in all cases.
When NaOH is used in the reaction a reduction in the
equilibrium hydration degree is observed for all the
blends, especially in the case of SCA going from 49.5 to
33.5% (in tensile specimens) as a result of the higher
crosslinked mass when NaOH was used.
When sodium carbonate was added to the reaction
media, the equilibrium hydration degrees were in the
same range than those found for the untreated materials.
Fig. 3 shows the swelling isotherms of the ®lms of
untreated and crosslinked SEVA-C. It is possible to
di€erent, being much faster in the case of the cross-
linked samples. However, the equilibrium hydration
degree is slightly lower in both cases. This should be
associated to the presence of the ionic phosphate groups
on the surface, which leads initially to a fast water-up-
take, but is later limited by the crosslinked nature of the
blends. The phosphate groups (shown in the ionic form
in Fig. 1) have, as the hydroxyl ones, a hydrophilic
character, being capable to be associated to water
molecules by hydrogen bonding or ionic solvating. As
the crosslinked mass percentage is increased the water
molecules di€usion and the consequent accessibility to
the polymeric chains becomes more dicult and the
¯exibility of the polymer chains is reduced.
The percentage weight loss of the material was deter-
mined by the equation:
Wi ÿ Wf
%Weight loss ˆ  100%
Wi
where Wf is the ®nal weight of the dry sample and Wi is
the initial weight of the specimen at di€erent immersion
times.
It has been reported [29] that the degradation of
SEVA-C is composed by: (i) an initial step of leaching
of the plasticisers (necessary to enable the material pro-
cessing); (ii) the elimination of the low molecular weight
chains resulting from the thermo-oxidative degradation
occurred during the processing stages; and (iii) the
chemical degradation of the starch phase. So, it is
expected the considerable decrease of the weight loss

Table 2
Most signi®cant FTIR signals of the starch based blends and crosslinked starch blends SEVA-C, SCA and SPCL

Stretching vibration SEVA-C signals (cmÿ1) SCA signals (cmÿ1) SPCL signals (cmÿ1)

Non-treated Crosslinked Non-treated Crosslinked Non-treated Crosslinked

O±H st 3423 3350 3444 3423 3391 3391

Sharp Less intense Sharp Less intense Sharp Less intense
C±H st 2959 2949 2959 2959 2949 2927
P±O st and No signals 1283 No signals 1256 No signals 1046
PˆO st 1288 1079
CˆO st No signal No signal 1720 1720 1740 1740
 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170 165

Table 3 weight loss of 2.5% after 90 days, whereas SEVA-C-CO

Equilibrium hydration degree (H equil.%) of tensile samples and ®lms approaches the SEVA-C percentages for similar times
of starch blends and crosslinked starch based blends
(about 10%, after 90 days of immersion). For SCA (Fig.
H equil. (%) 5) the weight loss after 14 days is about 11.5%, and
13% after 90 days, whereas in the case of the cross-
Samples ASTM specimens Films
linked samples the values are 5.8 and 7.4% (14 days)
SEVA-C 25.7 30.1 and 8.4 and 10% (90 days), respectively, for SCA-NA
SEVA-C-NA 23.8 27.7 and SCA-CO. SPCL (Fig. 6) samples show the clearest
SEVA-C-CO 26.2 28.7
di€erences in terms of weight loss varying from 14% in
SCA 49.5 51.2 the untreated samples to 6.2 and 9.2% for SPCL-NA
SCA-NA 33.5 41.7 and SPCL-CO, respectively (results for 90 days).
SCA-CO 37.7 50.1
These results are in accordance with the crosslinked
SPCL 11.2 8.1 mass percentages data (Table 1) being the slowest
SPCL-NA 10.8 7.7
degradation rate observed for samples treated in NaOH
SPCL-CO 10.6 13.6
media, as a result of the higher crosslinked mass than in
the case of Na2CO3 media. The reduction of the degra-
percentages observed when the three di€erent blends dation rate and of the weight loss percentage is also
were crosslinked. in¯uenced by the water-up take ability of these materi-
Figs. 4±6 show the degradation diagrams in terms of als, which are reduced as the crosslinked mass increases.
weight loss versus time for all the non- and crosslinked In fact, this should inhibit the chains with low molecular
blends in the presence of sodium hydroxide or sodium weight and the small molecules to di€use out from the
carbonate. In all cases the degradation kinetics patterns macromolecular domains. Furthermore, the onset of
evidence signi®cant di€erences between the non-reacted chemical degradation will appear at longer degradation
samples and the crosslinked ones. times also as a consequence of the crosslinked structure.
In the case of SEVA-C (see Fig. 4) there is an initial On the other hand, a similar e€ect is observed in all the
weight loss of 10% which is reduced to 1.1 and 5.6% non-treated starch based blends after 14 days of
when samples are crosslinked in the presence of NaOH immersion time at which a decrease in weight loss
or Na2CO3 respectively. SEVA-C-NA has a small clearly appears. The same e€ect can be observed in
some crosslinked samples at longer immersion times as
in the case of SCA-CO and SEVA-C-CO. This fact has
been also observed in other molecules of carbohydrate
nature [29].

3.4. Mechanical properties

The mechanical results exhibit an improvement in the

Fig. 4. Weight loss of ^, SEVA-C; &, crosslinked SEVA-NA; ~,
SEVA-CO as a function of immersion time on an isotonic saline solu-
tion at 37 C.
secant modulus of the crosslinked blends with respect to
the non-reacted ones. Table 4 shows the obtained data
for all the tested samples, being the ultimate tensile
strength (UTS) values in the same range for crosslinked
and non-treated blends (higher in some cases such as in
SCA-NA and SCA-CO). The secant modulus was

Fig. 6. Weight loss of ^, SPCL; &, crosslinked SPCL-NA; ~, SPCL-

Fig. 5. Weight loss of ^, SCA; &, crosslinked SCA-NA; ~, SCA-CO CO as a function of immersion time on an isotonic saline solution at
as a function of immersion time on an isotonic saline solution at 37 C. 37 C.
166 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170

Table 4 The SEM micrographs presented in Figs. 7 (SEVA-

Tensile mechanical properties of untreated and crosslinked starch C), 8 (SCA) and 9 (SPCL) should be analysed together
based blends, as obtained on quasi-static and dynamical±mechanical
with the data of Table 4. It is clear from this table that
tests
the most signi®cant variations on the modulus (as eval-
Material UTSa E1%b DMA 1 Hz uated by both quasi-static and dynamical experiments)
(MPa) (GPa) E 0 c (GPa) were found for the most ductile blend, SPCL. The
SEVA-C 36.4 5.5 2.160.47 0.99 crosslinking e€ect on the texture of the fracture surface
SEVA-NA 35.80.8 2.770.30 1.04 is clear when comparing Fig. 9a and b with Fig. 9c and
SEVA-CO 38.00.5 2.310.48 1.12 d. The later one evidences a much more brittle fracture
SCA 37.71.2 2.390.16 0.93 as a result of the successful crosslinking attained. In fact
SCA-NA 57.21.5 4.590.17 1.30 the fracture surface in Fig. 9c becomes much more
SCA-CO 46.913.2 3.400.25 1.12 similar to that of SEVA-C (Fig. 7a), as already reported
SPCL 23.75.7 0.570.08 0.36 [8,30,31], presenting a brittle nature.
SPCL-NA 22.90.9 2.440.09 0.58 On SCA blends, especially by comparing Fig. 8a and
SPCL-CO 23.40.5 1.660.03 0.47 c, it is also possible to note a small decrease of ductility
a
UTS, ultimate tensile strength. (fracture seems more brittle) that may be associated to
b
E1%, secant modulus at 1% strain. the crosslinking modi®cation.
c
E0 , storage modulus as determined in DMA experiments at 1 Hz Finally, on what concerns to SEVA-C, for which the
frequency. reactions did not seem to be so e€ective, it appears to be
possible a morphological change (compare Fig. 7b and
increased in all cases when the crosslinked mass per- d) that leads to a more ductile behaviour, and to the
centage increases, being the highest values obtained formation of a neck during deformation. As the reac-
when NaOH was used in the reaction media. The high- tion was not very e€ective the observed di€erences on
est increment was observed in the crosslinked SPCL SEM fracture surfaces are not as clear as those observed
where the secant modulus is about 4 times higher in the for SPCL materials. The balance between some cross-
case of SPCL-NA and 3 times for SPCL-CO. linking and this morphological change, is responsible

Fig. 7. Scanning electron micrographs of tensile fracture surfaces of (a) and (b) SEVA-C and (c) and (d) crosslinked SEVA-NA. Bars correspond to
500 and 50 mm, respectively.
 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170
Fig. 8. Scanning electron micrographs of tensile fracture surfaces of (a) and (b) SCA and (c) and (d) crosslinked SCA-NA. Bars correspond to 500
and 50 mm, respectively.
for the almost invariable values of UTS and the small
increase of the modulus (E1% and E0 ). It should be
reminded that the modulus is being measured for 1%
strain, for which the morphological change is, of course,
not yet clear.
3.5. DMA analysis
Dynamic mechanical experiments are a valuable
technique to investigate the mechanical behaviour of
materials subjected to cyclic loads and to obtain infor-
mation about the relaxation mechanisms that may be
correlated with the dynamics and the microstructure of
the material.
Fig. 10 shows the DMA results for the studied sam-
ples. Storage modulus, E 0 , and loss factor, tan , are
presented for each blend. The ®rst parameter is related
with the mechanical energy stored during each load
cycled and per volume unit. The loss factor is sensitive
to the viscoelastic behaviour and is useful to detect
mechanical relaxations.
For all specimens E 0 decreases with the increasing of
the temperature, re¯ecting a sti€ness loss. It is interest-
ing to note that this e€ect (i.e. the variation of the slope
of E 0 curve) is less pronounced for the crosslinked sam-
167
ples, namely in SPCL specimens (see Fig. 10c) that, as
commented previously, were more e€ectively cross-
linked. These results are expected to be associated to the
higher crosslinking density that prevents the liberation
of new degrees of translational/rotational freedom dur-
ing heating.
The values of E 0 at room temperature are also pre-
sented in Table 4. The sti€ness measured by dynamic
experiments is, as expected, very di€erent from that
obtained on quasi-static tensile measurements. How-
ever, it may be concluded that the variation of the
values between di€erent samples is consistent for the
two techniques used. In fact, as in the quasi-static
results, it is clear for SEVA-C and SPCL samples an
increasing of sti€ness after the crosslinking reactions
that is higher when NaOH is used. For the SCA blend
this e€ect is not so evident.
The tan  curves may also provide complementary
information. SEVA-C exhibits two relaxation processes
in this temperature range, also observed in ¯exural
experiments [32,33]. The low temperature relaxation, at
30 C is more noticeable in a loss modulus plot (not
shown) and was attributed to molecular mobility where
the copolymer intervenes. As seen in Fig. 10a the pro-
cess shifts to higher temperatures when crosslinked
168 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170
Fig. 9. Scanning electron micrographs of tensile fracture surfaces of (a) and (b) SPCL and (c) and (d) crosslinked SPCL-NA. Bars correspond to
500 and 50 mm, respectively.
samples are used due to more hindered mobility of the
involved polymeric chains. The peak at 80 C was
attributed to the molecular motions within the starch
fraction. A very interesting result is that within the stu-
died temperature range, this peak disappears in the
treated samples, indicating that the crosslinking points
are in the starch fraction, obstructing the conforma-
tional mobility of the corresponding polymeric seg-
ments. This behaviour was also clearly found for the
case of the SCA blend: the ascending side of the peak
almost vanishes with the crosslinking process. It must
be noted that for SCA and SPCL systems the experi-
ˆ
d ‡
p
ments were interrupted before the peak at 80 C
appeared because of the excessive strain amplitude.
d is the dispersive contribution (dispersive for-
However, the existence of this process in SCA is well
p the polar contribution (polar interactions),
visible in ¯exural experiment [33]. For the case of SPCL
this process seems also to exist as it can be conclude by
the tail of the tan  curve at the high temperature.
3.6. Contact angle measurements
The contact angle measurements, carried out on the
modi®ed samples, indicate how the materials change in
terms of surface energy and the respective importance of
the polar and dispersive contributions. Interfacial prop-
erties of the crosslinked blends in contact with hydrated
media are also important in predicting interactions of
this kind of materials with the surrounding tissues when
considering applications in the biomedical ®eld [34,35].
The contribution of the dispersive and of the polar
interactions can be calculated considering that the
intermolecular attraction that causes surface energy,
results from a variety of intermolecular forces according
to an additive rule. Most of these forces are functions of
the speci®c chemical nature of a particular material.
The surface energy can be expressed as:
where
ces), and
to the total surface energy.
In this work, it was used the well-known Fowkes [36]
and Young±Dupre [37] equations, and the contact
angles of the blends were measured at room tempera-
ture with water and methylene iodide. The total surface
energy and the respective components were calculated
following the Owens and Wendt method [38].
Table 5 exhibits the surface energy values of non-
treated and crosslinked samples. It can be observed that
in all modi®cations there is an increase in the total energy
value with respect to the original non-reacted blends.
 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170 169

Table 5
Contact angle values measured in air at room temperaturea

Sample Contact Contact s sd sp

angle,  angle,  (mN/m) (mN/m) (mN/m)
water (S.D.) CH2I2 (S.D.)

SEVA-C 65.1 (0.5) 53.7 (0.9) 45.1 32.3 12.8

SEVA-NA 49.4 (2.9) 55.4 (3.2) 53.9 31.2 22.7
SEVA-CO 54.5 (2.1) 47.2 (3.7) 53.0 35.8 17.2
SCA 50.2 (1.4) 44.5 (0.9) 58.3 37.9 20.4
SCA-NA 39.9 (3.3) 38.9 (3.5) 64.1 40.2 23.9
SCA-CO 40.3 (3.5) 43.1 (3.2) 62.1 37.1 25.0
SPCL 73.6 (1.8) 54.4 (1.6) 45.5 32.5 13.0
SPCL-NA 62.2 (3.7) 44.2 (2.3) 49.5 37.4 12.1
SPCL-CO 63.6 (1.3) 43.9 (3.4) 49.1 38.0 11.1
a
Surface energy
ÿ
values and the respective polar and dispersive
contributions sp ; sd to the total surface energy of all non-treated and
crosslinked starch blends. S.D.=standard deviation. (CH2I2=methyl-
ene iodide).

materials surface. The dispersive energy component is in

the same range, (with only a small increase in some
cases) of the non-reacted blends.
In the case of the SPCL crosslinked blends the
increase in total surface energy is mainly due to the dis-
persive component, whereas the polar contribution is
lower but in the same order of magnitude than in the
non-reacted ones. This fact can be attributed to the
highest crosslinking mass percentages determined for
SPCL blends, which in¯uences more the dispersive con-
tribution than the polar one.
It can be also pointed out that all blends crosslinked
in the presence of NaOH have a higher increase in the
total surface energy as their crosslinking mass percen-
tages is higher than when Na2CO3 was used in the
reaction.

4. Conclusions

A methodology based on well-known organic reac-

Fig. 10. DMA spectra of (a) SEVA-C, (b) SCA and (c) SPCL and
their respective crosslinked blends with NaOH or Na2CO3: Ð, original
blend; - - --, crosslinked with NaOH and .... crosslinked with Na2CO3.
In the cases of SEVA-C and SCA crosslinked sam-
ples, there is a signi®cant increase in the polar compo-
nent, higher in the case of SEVA-C, as the phosphates
ionisable crosslinking points are incorporated into the
tions was developed for crosslinking three types of
starch based blends. This methodology based on the use
of tri-sodium tri-meta phosphate, is original when
applied on SEVA-C, SCA and SPCL, starch based
thermoplastic blends. The crosslinking of the novel bio-
materials leads to materials with lower water-up take
ability, slower degradation kinetics and improved
mechanical properties. The water sensibility of these
types of systems has been a limitation for their more
extensive application on the medical and environmental
®elds. Furthermore, the chemical modi®cation of the
blends also leads to di€erent surface properties (as
obtained on contact angle measurements) which should
have a direct impact over the materials interaction with
cells and proteins in-vivo.
170 D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170

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