J Polym Environ (2010) 18:532538

DOI 10.1007/s10924-010-0251-7

Effect of Hydrothermal Polylactic Acid Degradation

on Polymer Molecular Weight and Surface Properties
E. L. Sambhaa A. Lallam A. Jada

Published online: 7 October 2010

 Springer Science+Business Media, LLC 2010

Abstract In the present work, polylactic acid, PLA,

samples were degraded by hydrothermal treatment, and
then their molecular weights, crystallinity, surface charges
and compositions, were determined, respectively, by using
viscometry, 1H NMR, Differential Scanning Calorimetry
(DSC), microelectrophoresis and Infra Red spectroscopy
methods. The viscometry and 1H NMR data indicate that
the molecular weight, of the polymer, decreases after the
hydrothermal treatment. However, the crystalline fractions
of the PLA samples, as obtained from the DSC and X-ray
data, were not altered after the hydrothermal treatment.
Furthermore, the zeta potential data, as determined by
microelectrophoresis, show for both non-degraded and
degraded PLA, an increase of the polymer surface charge
density with the pH of the aqueous phase. However, at
acidic pH values, the surface charge density for the
degraded PLA was higher as compared to the non degraded
one. These differences in surface charge densities of the
PLA samples were conrmed by Infrared study, according
to which the spectra of degraded polymer show the
appearance of carboxyl groups occurring at 1,600 cm-1 at
the polymer surface.
Keywords PLA  Hydrothermal degradation 
Microelectrophoresis  Infrared spectroscopy 
Zeta potential
E. L. Sambhaa  A. Lallam
LPMT Laboratoire Physique et Mecanique Textiles, UMR 7189
CNRS-UHA, 11, rue Alfred Werner, 68093 Mulhouse cedex,
France
A. Jada (&)
IS2M CNRS LRC 7228, 15 rue Jean Starcky, B.P. 2488,
68057 Mulhouse cedex, France
e-mail: A.Jada@uha.fr

123

Introduction
The production of biodegradable materials has been
increased three times over the last ten decade. The main
reasons for this development are due to the protection of
environment and to the medical uses of biopolymers.
Polylactic acid, PLA, which belongs to this class of biomaterials, is of prime importance nowadays. This polymer
is biodegradable aliphatic polyester. It is prepared from
resources 100% renewable such as beetroots, potato or all
other products rich in starch [1]. The starch is readily
extracted from plant matter and converted to a fermentable
sugar (e.g. glucose) by enzymatic hydrolysis. The carbon
and other elements in these natural sugars are then converted to lactic acid through fermentation. A high molecular weight polylactide is prepared by ring opening
polymerization from lactide [2], which is a cyclic product
of condensation of two lactic acid molecules [3]. Owing to
the presence of two asymmetric carbon atoms in its
structure, lactide has three stereo isomeric forms: (ss), (rr)
and (rs).
Over the past few years, PLA polymer was used for
packaging and ber applications. However, it is important
that PLA is used broadly in textile applications, since
polyesters such as poly(ethyleneterephthalate) (PET), are
currently used for apparel and related ber applications,
and their use is constantly increasing. The low resistance of
the PLA to the hydrothermal degradation limits its capacities of use in applications similar to those of aromatic
polyesters such as the PET.
Developing PLA biodegradable having small particle
sizes is of a great interest, since they offer a suitable means
of delivering small molecular weights drugs, proteins, or
genes by either localized or targeted delivering to the tissue
of interest. Further, the physical and the mechanical

J Polym Environ (2010) 18:532538

properties of PLA, allow it to be used in a very large

variety of domains among which, the biomedical, the textile clothing etc. On the other hand, thermal stability of the
aliphatic polyesters remains limited. Hence, under the
effect of temperature, the macromolecular chains may
undergo ruptures, which lead to the formation of more
stable products [4]. Thus, at high temperatures, the thermal
stability of the PLA is poor. Gupta and Deshmukh [5]
showed that the CO bond of carbonyl group can break
under the heating effect and the numbers of ends of chain
characterized by COOH, which are formed during the
process degradation, are larger than the OH groups. This
thermal degradation was found to increase in the presence
of moisture [68]. Moreover, the change of pH of the
aqueous PLA dispersions led to important mass and surface
structural modications of the polymer.
In the present work, we propose to study the combined
effects of the temperature, the moisture and the pH of the
aqueous phase, on the molecular weight, the crystallinity,
and the surface structure of PLA samples.

Experimental Part
PLA Characteristics
The degradation experiments were carried out on PLA
sample provided by Cargill. It is composed of 98% L-isomer and 2% of isomer D. The PLA sample has a knitted
morphology made of multi-lament thread and having
circular cross section. The thread characteristics are the
following:

the title is 21 tex (the tex is the unit of titling the thread,
one tex is the weight in gram, of a thread having a
length of 1,000 m).
the density is 1.24 g/cm3.
the water content at room temperature is in the range
0.40.6 wt%.
the fracture toughness is in the range 0.320.36 N/tex.

Degradation Mode of PLA Samples

Three PLA samples weighing 3.00 g each were immersed
in an aqueous solution of pH = 6, then agitated by using
a bath-samples unit whose temperature was maintained
constant at 90 C, during 1 h. Thereafter, the samples
were withdrawn from the aqueous dispersions, dried at
room temperature during 24 h, and weighed until constant
weights were obtained. These different steps constitute
one complete cycle of polymer treatment, and 15 cycles
were systematically used to degrade each PLA sample.
Finally, several experimental techniques, as described

533

below were used to characterize the resulting degraded

PLA samples.
It should be noted that the procedure (constant values
of pH and temperature) used to degrade the PLA sample,
as described above, is due to the conditions of the polymer use and maintenance in various applications, such as
the biomedical eld. Recall that the PLA is aliphatic
polyester, which is sensitive to moisture, high temperature, and pH. Thus, the degradation of PLA in water
should be function of both the pH of the medium and the
treatment cycle temperature. In the present work, the pH
of the hydrothermal treatment, namely pH = 6, is chosen
so that the hydrolysis of the polymer is as low as possible. Further, the temperatures of dyeing and use of PLA
in various application areas, range between 90 and
100 C. Consequently, in our work the PLA treatment
temperature was choused to be 90 C, since a temperature
above 100 C will enhance the mechanical properties loss
of PLA bers. The decrease of the PLA molecular weight
and thus the loose of the polymer mechanical properties
under temperature treatment increase were observed in
various studies dealing with the effects of hydrothermal
conditions on the PLA degradation [9 and references cited
therein]. These works have shown morphology modication and/or enhancement of the polymer degradation as
resulting from the increase of temperature treatment
(70180 C) or the pH of the aqueous phase (water-0.6 M
NaOH).
Nuclear Magnetic Resonance (1H NMR)
The treated and untreated samples were dissolved in deuterated chloroform at 25 C, then their spectra 1H NMR
were carried out using a Bruker spectrometer operating at a
frequency of 400.17 MHz, and with a time of data acquisition equal to 8 s. These experiments aim to determine the
tacticity of polymer xed during polymerization and
deduce the arrangement of monomers according to their
conguration L or D. The analysis of the results obtained,
makes it possible to follow the evolution of the degradation
of the PLA under the previously denite operating
conditions.
Differential Scanning Calorimetry (DSC)
The study in differential scanning calorimetry was carried
out using DSC standard equipment STAR SW.8.10. In
these experiments, 25 mg of sample are introduced into an
aluminum cell of 30 ll. The sample is then heated in
temperature range situated between 100 and 250 C, under
nitrogen ow. All the DSC measurements were made at a
program ramp rate of 10 C/min and the analysis were
performed on the rst up heat of the sample.

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J Polym Environ (2010) 18:532538

This technique allows studying the variations of the

enthalpy of polymer versus time. From experimental
results, it is possible to obtain the values of glass transition,
Tg, the melting temperature, Tm, and the crystallinity
fraction, Xc.
Diffraction of X-rays
Diffraction of X-ray were carried out by a powder Philips
X Pert Diffractometer. The wavelength (Ka) of the copper and the scanning rate were respectively equal to
, and 0.025 degree per second, for angles
1.54 A
3 B 2h B 70. The applied voltage was xed at 40 kV
and the intensity of electrical current 40 mA, 1,090 points
were necessary to plot the curves of DRX. The expected
results will inform us about the crystalline structure of
polymer.
Viscometry
Measurements were carried out in Ubbelohde viscometer,
immersed in a bath maintained at 25 C. The samples to be
characterized are dissolved in chloroform in order to obtain
a concentration of 1 g/dL. Thus, the viscometric average
molecular weight of polymer, Mv, can be calculated
according to Mark Houwinks law:
g 5:45  104 M0:73
v

where, [g] is the intrinsic viscosity of polymer,

5.45 9 10-4 and 0.73 are constants of Mark Houwink,
considered at 25 C [10, 11]. The intrinsic viscosity [g] of
the PLA sample was obtained from the intercept of the plot
(g - g0)/g0 C vs. C, where (g - g0)/g0 is the reduced
viscosity and C is the polymer concentration; g and g0, are
the measured viscosities of, respectively, the PLA-chloroform solution and the pure chloroform. Finally, the calculated viscometric molecular weights, Mv were compared to
number average molecular weights, Mn, obtained from 1H
NMR data.
Microelectrophoresis
zeta potential of aqueous dispersions was measured by
microelectrophoresis at 25 C, as described elsewhere [12].
Equipment used transforms the electrophoretic mobility of
the particles, in zeta potential according to Henrys law:
l 2=3ef=gfja

where, g and e are respectively the viscosity and the

dielectric constant of the aqueous solution; ja is a factor
which corresponds to the relationship between the thickness of the ionic double-layer and the diameter of particles.
The pH of dispersions studied ranging between 3 and 10,

123

are adjusted by addition of minor amounts of NaOH or

HCl.
Infra-red Spectroscopy
Few milligrams of PLA samples were mixed and pressed
with KBr powder in order to obtain a solid pallet, which
have to be introduced in the infrared BRUKER spectrometer to be analyzed.

Results and Discussion

Number Average Molecular Weight Determination
from 1H NMR Data
The PLA is obtained starting from polymerization of the
lactide under various cyclic isomeric forms: D-lactide,
L-lactide, or the meso form [13]. L and D are being optically active [14]. Polymerization of isomers D and L, allow
obtaining mainly the isotactic polymer whereas, the meso
form leads to the syndiotactic polymer [15]. Works
undertaken by Kricheldorf et al. [3] and Zell et al. [16]
allow establishing references spectra according to the
Bernoulli calculations. According to these authors, a mixture or racemic D, L-lactide will lead mainly to a large 1H
NMR peak, corresponding to isotactic, whereas, meso D,
L-lactide will give a large 1H NMR peak corresponding to
syndiotactic, PLA microstructures. Furthermore, the
intensities and resolution of peaks are depending, respectively, on the D/L fraction, and on the concentration on the
polymeric solution in the CDCL3 [17].
The PLA is a very sensitive polymer to the hydrolysis in
aqueous mediums. Any heat treatment carried out under
these conditions leads to loss of its molecular weight. In
addition, this molecular weight reduction weakens the
mechanical properties of the polymer and leads to limitation in its applications.
The 1H NMR spectra of the PLA, before and after
treatment, were carried out, and Fig. 1 shows an example
of the experimental 1H NMR spectrum of non-degraded
PLA. As can be seen in Fig. 1, two types of protons for CH
groups are present: CH groups (2) belonging to the
repeating PLA unit, and CH groups (1) belonging to the
PLA chain ends. Further, as expected, Fig. 1 shows that
CH groups (2) give the highest peak intensity, whereas the
CH groups (1) give the lowest peak intensity. It is noteworthy that in all instances, the CH peak intensities of the
PLA samples, before and after treatment, were not the
same. Hence, the non-treated PLA gives higher intensities
as compared to the treated one. These differences in 1H
NMR intensities result from differences in molecular
weights of degraded and non-degraded PLA.

535

5,198
5,181
5,163
5,146

J Polym Environ (2010) 18:532538

Polylactic acid

2
CH3

HO

O
O

CH3

HO
n

1
OH

6,0

5,5

5,0

4,5

4,0

ppm

1,000

311,314

6,5

Finally, from the integration of the peaks, corresponding

to CH groups (1) and CH groups (2), we calculate the value
of the repeating unit number, n and then the number PLA
average molecular weight (Mn) according to Eq. 3:
Mn = 72 n + 90

where, the numbers 72 and 90 g/mol correspond to the

molecular weights of, respectively, the repeating unit and the
ends of PLA chain. Calculations give, Mn = 22,500 g/mol
and Mn = 15,420 g/mol, respectively, before and after PLA
hydrothermal treatment.
Figure 2 shows the variation of the reduced viscosity,
(g - g0)/g0 C, as function of the PLA concentration C, for
the non-degraded and degraded sample. As can be seen on
this gure the viscosity data are scattered, resulting hence
in higher experimental errors of 11% for the intrinsic
viscosity [g] and 15% for the viscometric molecular
weight Mv.
In Table 1 are presented the molecular weights of
degraded and non-degraded PLA samples. As can be seen
in Table 1, a good correlation is found between the two
methods, viscometry and 1H NMR, used in the present
work, for determining the PLA molecular weights. The two
methods give nearly the same PLA weight loss, which is
about 30%, as resulting from PLA degradation (Table 1.)

Reduced viscosity ( - 0 /( 0c) (dL/g))

Fig. 1 1H NMR spectrum of non-degraded PLA (CH groups) sample

1,6

Non-degraded PLA

Degraded PLA

1,4
1,2
1,0
0,8
0,6
0,4
0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

1,1

Polymer concentration (c (g/dL))

Fig. 2 Variation of the reduced viscosity ((g - g0)/g0C) with the

polymer concentration C, for the non-degraded and degraded PLA
samples

Temperature and Moisture Effects on the Structure

of the PLA
The main effect of temperature is to degrade polymer.
Further, it is known that the thermal stability of aliphatic
polyesters is very limited, and those polyesters degrade
easily with several consequences, on the crystalline

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J Polym Environ (2010) 18:532538

Table 1 Molecular weights as determined from viscometry and 1H

NMR methods, and decrease percent in molecular weights, of
degraded and non-degraded PLA samples
Viscometry (Mv (g/mol)

NMR
(Mn (g/mol)

Molecular
weight

(a)

22,880 3,500 16,100 2,400

22,500
(a)

Decrease in
molecular
weight

29.6%

31.4%

(b)

15,420
(b)

0,0
Non degraded PLA
Degraded PLA

Heat Flow (W/g)

-0,2

The various parameters: Xc, Tg, Tm, and peak surface

area, as determined from the DSC Thermograms for nondegraded and degraded PLA, are gathered in Table 2.
The comparison of the data between the non-degraded
and degraded PLA samples indicate clearly that, within
experimental error of 2% for Xc, the hydrothermal
degradation of PLA does not affect its crystallinity. Our
data showing no modication in the crystallinity of PLA
upon its degradation are in good agreements with the
work Yuan et al. [8], dealing with surface degradation of
poly (L-lactic acid) (PLLA) bers in a concentrated
alkaline solution. According to these authors, the crystallinity of PLLA does not change upon its surface
degradation.
Mechanism of PLA Degradation

-0,4
glass transition temperature

-0,6

-0,8

-1,0

-1,2
-100

-50

50

100

150

200

250

T(C)

Fig. 3 Thermograms of non-degraded and degraded PLA samples

structure of polymer and consequently on the rest of

properties. The aliphatic polyesters such as PLA samples
have a relatively limited thermal stability. They degrade
under the combined effect of the temperature and moisture.
This structural evolution leads to alteration of the polymer
mechanical properties and limits its potential of uses.
The DSC Thermograms of non-degraded and degraded
PLA are shown in Fig. 3.
As can be seen in Fig. 3, there are no important differences in the thermal and crystalline properties between the
non-degraded and degraded PLA samples.
Analysis of DSC Thermograms enables the determination of two important parameters: glass transition temperature, Tg, and melting temperature, Tm, i.e. the temperature
at the maximum of the endothermic pic. Further, the
endothermic peak area is proportional to the total enthalpy
change or to the polymer melting enthalpy, DHm. In
addition, the PLA crystallinity ratio, Xc, was calculated
from the DSC Thermograms, and by using the following
formula:
Xc 100  DHm =93

where, 93 J/g is the melting enthalpy of 100% crystalline

PLA [18].

123

Degradation of aliphatic polyesters proceeds in two

stages; the rst one starts with the diffusion of water in
the amorphous zones of polymer, creating random ruptures in the ester bonds [19]. The second stage starts when
the majority of the amorphous zones are degraded. Fisher
et al. [20], have observed this selective degradation. Other
authors [2129] have also emphasized the correlation that
exists between the morphological structure and the degradability of polymer. Almost authors have argued an
increase in the crystallinity ratio of the PLA, as resulting
from its degradation. These ndings indicate that during
the PLA treatment, only are degraded, the amorphous
zones of polymer. These observations mean that PLA
degradation takes place mainly in the amorphous phase.
However, our experimental data indicate that the crystallinity ratio, Xc, remains constant after the PLA
treatment.
Figure 4 represents the X-rays spectra of the nondegraded and degraded PLA. On this gure, the superposition of the two spectra is almost perfect. This means,
qualitatively, that no signicant modication occurs in the
crystalline zones of materials. The XRD results corroborate
those obtained by the DSC technique, in particular on the
crystallinity rate.
Table 2 Crystallinity ratio, glass transition temperature, melting
temperature, and normalized surface area of DSC peak, of degraded
and non-degraded PLA samples
Polymer property

Non-degraded
PLA

Degraded
PLA

Crystallinity ratio, Xc

46%

44%

Glass transition temperature, Tg

54.1 C

52.1 C

Melting temperature, Tm
Normalized surface area
of DSC peak

169.8 C
-42.96 J g-1

170.9 C
-40.60 J g-1

J Polym Environ (2010) 18:532538

537
5

Non-degraded PLA
Degraded PLA

Non degraded PLA

Degraded PLA

0
-5

19.2

Zeta potential (mV)

16.8

-10
-15
-20
-25
-30
-35
-40
2

10

pH

Fig. 4 X-ray diffraction spectra of non-degraded and degraded PLA

samples

Fig. 5 Zeta potential of non degraded and degraded PLA samples

aqueous dispersions

Surface Characterization of PLA Samples

by Microelectrophoresis

The increase in the zeta potential magnitude in the pH

range 37, results from the increase of COO- groups at the
PLA-water interface, i.e. at pH above the pKa which is
about 3.80 of lactic acid, more COOH groups of the PLA
sample are dissociated to COO- groups.
Furthermore, Fig. 5 indicates that the increase in zeta
potential magnitude is more pronounced for the degraded
PLA as compared to the no-degraded one, from pH = 3 to
pH around 7. Such data show clearly that upon PLA degradation, more ionized carboxyl groups are generated in the
water medium, leading to an increase of smaller PLA
fragments and an increase in the magnitude of the zeta
potential. The enhancement of the PLA COOH density,
during the degradation and/or the fragmentation of the
polymer, is then evidenced by the increase of zeta potential
magnitude with the pH of the aqueous phase, and leads to
highly charged PLA in alkaline medium.
The Infrared spectra of non-degraded and degraded PLA
are presented in Fig. 6. The main functional groups of PLA

The microelectrophoresis is a tool suited to characterize the

surface chemical groups of a solid, by measuring its zeta
potential at solidwater interface, provided that such surface groups (COOH, OH, NH3) are ionisable and/or bear
electrical charges [12 and references cited therein].
In the present work, the chemical modication that
occurs on the PLA surface upon its hydrothermal treatment, and leading to concentration enhancement of carboxylic acid groups (COOH) functional groups may be
determined by microelectrophoresis. Thus, measuring the
variation of zeta potential, f, with the pH of the PLAaqueous dispersion, may give evidences for the presence of
such groups at the polymer surface. It is noteworthy to cite
that the magnitude of the measured zeta potential, of the
PLA-aqueous dispersion, is proportional to the nature and
surface concentration of COOH functional groups.
In addition, in order to compare the degraded and the
non-degraded PLA surface properties, we made blank
experiments by measuring the zeta potential in water of the
non-degraded PLA.
Figure 5 shows the variation of the zeta potential versus
the pH, for the non-degraded and degraded PLA particles
aqueous dispersions. The objective of varying the pH was
to analyze the dissociation of COOH groups at the water
PLA interface for substrates having various carboxylic acid
group contents. The negative surface charge at the PLAwater interface results mainly from the ionization of the
COOH acidic surface groups present on the polymer surface. As can be seen in Fig. 5, the increase in the pH of the
aqueous phase from pH = 3 up to pH around 7, leads, in
all instances, to an increase in the magnitude of the zeta
potential, and beyond pH = 7, a plateau level is reached.

Fig. 6 Infra-red spectra of non degraded and degraded PLA samples

123

538

can be seen in this gure. Further, the principal difference

between the non-degraded and degraded PLA spectra is the
appearance of the COO- peak situated at 1,600 cm-1.
Such carboxyl peak results from the hydrolysis of the PLA
ester bond [19].
The Infrared data shown in Fig. 6, indicate clearly that
upon PLA degradation an increased number of carboxylic
acid chain ends are produced as shown also by the zeta
potential data in Fig. 5.

Conclusions
The PLA, aliphatic polyester, may degrade quickly at
temperatures located between glass transition temperature,
Tg, and melting point, Tm. This degradation is enhanced by
the presence of moisture and/or the increase of pH of the
aqueous medium.
Viscometry and 1H NMR measurements indicate signicant decrease of the PLA molecular weight upon degradation. Infrared data show the appearance of COOsurface groups as resulting from the degradation of PLA
sample. Zeta potential results indicate that the density of
COO- surface groups increase with increasing the pH of
the aqueous phase. From the X-ray and DSC measurements, it was concluded that the crystallinity of PLA
sample was not affected by the polymer degradation.
In order to highlight further the mechanism of PLA degradation, works is in progress in our laboratory, to determine
the effect of pH and temperature on the PLA degradation.

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