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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 stier materials with a less pronounced degradation rate can
be obtained. # 2000 Elsevier Science Ltd. All rights reserved.
In order to improve this kind of behaviour, chemical The reaction was initially performed using the blends in
modi®cations based on well-known organic reactions the powder form. However, some studies were also
were used in this work. Nevertheless, it is worth developed on the obtained ®lms and on the ASTM speci-
mentioning that such type of modi®cations have never mens. All the tensile samples were previously immersed in
been tried before on the types of blends studied in this a water solution at room temperature for 3 days in order to
work. Special attention was devoted to the surface remove the processing aids contained in the blends.
modi®cation as material surface properties are determi-
nant in biomedical applications (bioactivity, cell adhe- 2.3. Characterization by Fourier transformed infra-red
sion and proliferation, protein interactions, etc.). In spectroscopy (FTIR)
fact, it is the surface of the material that interacts with
proteins and cells and, consequently, the implant beha- FTIR spectra were recorded on a Perkin-Elmer 1600
viour will deeply depend on its properties [26]. Series spectrometer. Spectra were taken with a resolution
So, the present work is an attempt to ®nd an adequate of 2 cmÿ1 and were averaged over 32 scans. Samples were
method to reduce the water sensitivity and the degra- thoroughly grounded with exhaustively dried KBr and
dation rate of starch-based formulations by crosslinking pellets were prepared by compression under vacuum.
some of the hydroxyl groups present in the blends.
These chemical modi®cations are expected to have also 2.4. Hydration degree and degradation behaviour
a direct impact over surface and mechanical properties
of the modi®ed compounds. 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
2. Experimental being immersed in 100 ml of a simulated physiological
isotonic solution (0.154 M NaCl aqueous solution at pH
2.1. Materials 7.4). The specimens were removed at regular intervals of
3, 7, 14, 30, 60 and 90 days, being taken out of the
The studied starch-based thermoplastic blends, kindly solution, blotted on ®lter paper to remove surface solu-
supplied by Novamont, Novara, Italy, were: (i) a corn tion and further rinsed with distilled water and weighed.
starch/ethylene-vinyl alcohol (SEVA-C); (ii) a corn After being removed from the solution, the specimens
starch/cellulose acetate (SCA); and (iii) a corn starch/e- were dried, in an oven at 60 C, to constant weight in
caprolactone, (SPCL). order to determine the eventual weight loss (an average
Powders, ®lms (prepared by compression moulding at of value of two readings was used). Equilibrium hydra-
120±130 C) and ASTM dumbell tensile test specimens tion degree was considered when no weight change (
(prepared by injection moulding using a previously 0.001 g) was observed, after 2±3 days of immersion. The
described procedure 4, with a cross-section of 24 mm) hydration degree of the blends was also determined in
were used in this work. crosslinked ®lms with thickness between 90 and 220 mm,
considering the equilibrium hydration degree obtained
when no weight change was observed.
2.2. Crosslinking reaction
2.5. Mechanical properties
The crosslinking reactions were carried out, as
described in the literature for native starch 28, using tri- The tensile tests were performed on an Instron 4505
sodium tri-meta phosphate, Na3P3O9 (Aldrich-Ger- machine, ®tted with resistive extensometer (gauge length 10
many) as a crosslinking reagent in the following con- mm) in a controlled environment (23 C, 55% RH). The
centrations (relatively to the weight of the blend): 15.7, crosshead velocity was 5 mm/min (8.3 10ÿ5 m/s) until
7.8 and 3.9%. These concentrations were used on 1% strain (to determine the secant modulus with higher
preliminary tests aimed at choosing the ideal Na3P3O9 precision) and then increased to 50 mm/min (8.310ÿ4 m/s)
concentration to use on all subsequent studies. This until fracture. The samples were stored under controlled
ideal concentration was found to be 15.7% (see temperature and moisture conditions until testing, and
Results). at least six specimens were used. The fracture surfaces
First, the Na3P3O9 was dissolved in an aqueous solu- were examined by scanning electron microscopy (SEM).
tion being the pH value adjusted to 10±11 by using
Na2CO3 (CO) or NaOH (NA), both from Aldrich-Ger- 2.6. DMA analysis
many. The starch-based blend was then added (2 g) to
the solution (20 ml) and the reaction was carried out at Dynamic mechanical analysis (DMA) was also used
50 C for 5 h under continuous stirring. to characterize the mechanical behaviour of the mod-
D. DemirgoÈz et al. / Polymer Degradation and Stability 70 (2000) 161±170 163
i®ed blends. The tests were carried out using a tensile SPCL can be attributed to: (i) the partial hydrolysis in
loading scheme, by means of scanning the temperature basic media of the corresponding ester groups (acetate
from ÿ20 to 160 C, in a Perkin-Elmer 7 series Thermal and lactone, respectively); and (ii) the hydroxyl groups
Analysis System (specimen size 2053 mm). A fre- which can react with Na3P3O9 and also be involved in
quency of 1 Hz and a constant heating rate of 4 C minÿ1 the crosslinking reaction (see Fig. 1). On the other hand,
were used. A static stress of 0.12 MPa was applied to the the low crosslinked mass percentage in the case of
specimens over a dynamic stress of 0.1 MPa. SEVA-C blend can be attributed to the compatibility of
the blend in which starch and the ethylene-vinyl alcohol
2.7. Contact angle measurements are forming an interpenetrating network, and con-
seqently both hydroxyl groups from starch and vinyl
The contact angle between a liquid and the surface of alcohol can be involved in the crosslinking reaction with
the ASTM specimens was measured at room tempera- more diculty. The presence of the non-reactive ethyl-
ture by means of a Contact Angle Measuring System ene units also reduced the crosslinked mass percentage,
G10 by depositing a drop of distilled water and meth- as less accessible hydroxyl groups are present in the
ylene iodide (CH2I2) on the material to study. The aim blend. It was also observed in all cases that the cross-
was to evaluate the polar and dispersive components of linked mass percentage is higher when NaOH is used to
the surface energy. The quantity of liquid was measured catalyse and to adjust the pH of the reaction [27].
with a syringe monitored by a micrometric screw. The
results correspond to the average value of at least ten 3.2. Characterization by FTIR
measurements.
The crosslinking reaction (Fig. 1) was charaterized by
comparing the FTIR spectra of both reacted and non-
3. Results and discussion reacted samples as the original material does not con-
tain any phosphate group in its structure. The typical
3.1. Crosslinking reaction stretching vibrations of PO and P±O (at about 1200±
1100 cmÿ1) were observed in the spectra of all the
Non-modi®ed SEVA-C, SCA and SPCL blends are crosslinked samples. It was also noticeable that the
completely soluble in dimethylsulfoxide (DMSO). bands assigned to the starch hydroxyl stretching vibra-
However, after the reaction only a partial solubilization tions (at 3400 cmÿ1) were decreased in intensity after the
was observed in all blends, which is a clear indication of crosslinking treatment as a consequence of the reaction
the high percentages of crosslinking obtained. Con- involving two starch hydroxyl groups per one phos-
centrations of Na3P3O9 (7.8 and 3.9%) were only used phate. This can be observed in the spectra of non-treated
in terms of ®nding the most optimal conditions to and crosslinked SPCL exhibited in Fig. 2.
achieve a relatively high crosslinking density. As the The most important signals assigned to the corre-
amount of crosslinker was increased, the crosslinking sponding stretching vibrations (±OH, PO and P±O) of
mass percentages were found to be higher, using the SEVA-C, SCA and SPCL samples are summarised in
highest concentration of Na3P3O9 (15.7%) in all the Table 2. No remarkable dierences were observed in the
experiments and performed studies. Consequently, this bands assigned to the carbonyl stretching vibration (at
concentration was used for preparing samples for all about 1700 cmÿ1) in SCA (of acetate groups) and SPCL
other tests. Table 1 presents the amount of crosslinked (from poly-caprolactone), with respect to the corre-
material for the three blends under study, following the sponding crosslinked blends.
reactions performed with NaOH or Na2CO3, disclosing
percentages higher then 90% for SCA and SPCL 3.3. Hydration degree and degradation behaviour
blends, and of about 50% for SEVA-C.
The high percentage of crosslinked mass obtained Both the hydration degree and the degradation beha-
with the described experimental conditions for SCA and 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
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)
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)
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±170 167
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 ples, namely in SPCL specimens (see Fig. 10c) that, as
increase of the modulus (E1% and E0 ). It should be commented previously, were more eectively cross-
reminded that the modulus is being measured for 1% linked. These results are expected to be associated to the
strain, for which the morphological change is, of course, higher crosslinking density that prevents the liberation
not yet clear. of new degrees of translational/rotational freedom dur-
ing heating.
3.5. DMA analysis The values of E 0 at room temperature are also pre-
sented in Table 4. The stiness measured by dynamic
Dynamic mechanical experiments are a valuable experiments is, as expected, very dierent from that
technique to investigate the mechanical behaviour of obtained on quasi-static tensile measurements. How-
materials subjected to cyclic loads and to obtain infor- ever, it may be concluded that the variation of the
mation about the relaxation mechanisms that may be values between dierent samples is consistent for the
correlated with the dynamics and the microstructure of two techniques used. In fact, as in the quasi-static
the material. results, it is clear for SEVA-C and SPCL samples an
Fig. 10 shows the DMA results for the studied sam- increasing of stiness after the crosslinking reactions
ples. Storage modulus, E 0 , and loss factor, tan , are that is higher when NaOH is used. For the SCA blend
presented for each blend. The ®rst parameter is related this eect is not so evident.
with the mechanical energy stored during each load The tan curves may also provide complementary
cycled and per volume unit. The loss factor is sensitive information. SEVA-C exhibits two relaxation processes
to the viscoelastic behaviour and is useful to detect in this temperature range, also observed in ¯exural
mechanical relaxations. experiments [32,33]. The low temperature relaxation, at
For all specimens E 0 decreases with the increasing of 30 C is more noticeable in a loss modulus plot (not
the temperature, re¯ecting a stiness loss. It is interest- shown) and was attributed to molecular mobility where
ing to note that this eect (i.e. the variation of the slope the copolymer intervenes. As seen in Fig. 10a the pro-
of E 0 curve) is less pronounced for the crosslinked sam- 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 media are also important in predicting interactions of
involved polymeric chains. The peak at 80 C was this kind of materials with the surrounding tissues when
attributed to the molecular motions within the starch considering applications in the biomedical ®eld [34,35].
fraction. A very interesting result is that within the stu- The contribution of the dispersive and of the polar
died temperature range, this peak disappears in the interactions can be calculated considering that the
treated samples, indicating that the crosslinking points intermolecular attraction that causes surface energy,
are in the starch fraction, obstructing the conforma- results from a variety of intermolecular forces according
tional mobility of the corresponding polymeric seg- to an additive rule. Most of these forces are functions of
ments. This behaviour was also clearly found for the the speci®c chemical nature of a particular material.
case of the SCA blend: the ascending side of the peak The surface energy can be expressed as:
almost vanishes with the crosslinking process. It must
be noted that for SCA and SPCL systems the experi-
d
p
ments were interrupted before the peak at 80 C
appeared because of the excessive strain amplitude. where
d is the dispersive contribution (dispersive for-
However, the existence of this process in SCA is well ces), and
p the polar contribution (polar interactions),
visible in ¯exural experiment [33]. For the case of SPCL to the total surface energy.
this process seems also to exist as it can be conclude by In this work, it was used the well-known Fowkes [36]
the tail of the tan curve at the high temperature. and Young±Dupre [37] equations, and the contact
angles of the blends were measured at room tempera-
3.6. Contact angle measurements ture with water and methylene iodide. The total surface
energy and the respective components were calculated
The contact angle measurements, carried out on the following the Owens and Wendt method [38].
modi®ed samples, indicate how the materials change in Table 5 exhibits the surface energy values of non-
terms of surface energy and the respective importance of treated and crosslinked samples. It can be observed that
the polar and dispersive contributions. Interfacial prop- in all modi®cations there is an increase in the total energy
erties of the crosslinked blends in contact with hydrated 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
4. Conclusions