Effect of Processing Conditions on Morphology

and Mechanical Properties of Injection-Molded

Poly(L-lactic acid)

S. Ghosh,1,2 J.C. Viana,2,3 R.L. Reis,1,2 J.F. Mano1,2

1
3B’s Research Group – Biomaterials, Biodegradables and Biomimetics, Campus de Gualtar,
4710-057 Braga, Portugal

2
Department of Polymer Engineering, University of Minho, 4800-058 Guimãrães, Portugal

3
IPC – Institute for Polymers and Composites, University of Minho, 4800-058 Guimãrães, Portugal

This work investigates the relationship among the INTRODUCTION

processing, morphology, and the mechanical proper-
ties of injection-molded poly(L-lactic acid) (PLLA). Melt
processing temperature, mold temperature, injection
flow rate, and holding pressure were systematically
changed following a design of experiments array. The
thermomechanical environment imposed during pro-
cessing was estimated by computer simulations for
the mold-filling phase, which allows the calculation of
shear stress, shear rate, and the thickness of frozen
skin layer. The morphology was characterized by differ-
ential scanning calorimetry and hot recoverable strain
measurements. The analysis of variance results of
influence of processing factors on the morphology are
in good agreement with the analysis of thermomechan-
ical parameters on the morphology. The primary factor
for inducing the crystallinity in PLLA product was the
stress-induced crystallization, whereas the thermal
induced crystallization had a little effect. The morphol-
ogy–mechanical property relationships were estab-
lished. The crystallinity developed during processing
has little effect on elastic modulus, increases the yield
strength, and severely decreases the elongation at
break. The level of molecular orientation developed
during processing has little effect on elastic modulus,
but increases both the yield strength and the elonga-
tion at break. POLYM. ENG. SCI., 47:1141–1147, 2007.
ª 2007 Society of Plastics Engineers
Correspondence to: J.F. Mano; e-mail: jmano@dep.uminho.pt
Contract grant sponsor: Portuguese Foundation for Science and Technol-
ogy, FCT, Government of Portugal; contract grant number: SFRH/BD/
12657/2003; contract grant sponsor: FCT (POCTI, FEDER programes);
contract grant number: POCTI/FIS/61621/2004; contract grant sponsor: Eu-
ropean Union funded STREP Project HIPPOCRATES; contract grant num-
ber: NMP3-CT-2003-505758.
DOI 10.1002/pen.20799
Published online in Wiley InterScience (www.interscience.wiley.com).
C 2007 Society of Plastics Engineers
V made, e.g., branching is typically introduced to obtain
Poly(lactic acid) (PLA) is a biodegradable aliphatic
polyester derived from 100% renewable resources [1]. PLA
offers a wide range of properties depending on its stereo-
chemical make up [2]. It exists in two optical isomeric
forms, poly(L-lactic acid) (PLLA) and poly(D-lactic acid)
(PDLA) and a copolymer of the two as poly(D,L-lactic acid)
(PDLLA). Optically pure PLLA and PDLA are semicrystal-
line polymers, whereas with the incorporation of
15%
meso-lactide, the polymer (PDLLA) becomes amorphous.
PLLA is currently used in a number biomedical appli-
cations, such as sutures, internal fixation rods, fixation
tacks, and drug delivery devices, and it is also been used
for tissue engineering applications [3–5]. Typically, amor-
phous PLLA products are suitable for biomedical applica-
tions, for uniform degradation, and resorption in physio-
logical conditions [6]. Being biodegradable, it is also used
to replace the petroleum-derived plastics in loose-fill
packaging, compost bags, food packaging, and agricul-
tural applications [7–9]. For most of these commodity
applications, PLA is often compared with other thermo-
plastics, mainly with polystyrene. The lower glass transi-
tion temperature of PLLA
608C compared with polysty-
rene of
1008C limits its usage for many such applica-
tions. Moreover, these applications require higher flexural
properties, heat distortion temperature, and impact
strength, where crystallinity is a key parameter, because it
increases the stiffness and heat distortion temperature of
the product but reduces the impact properties.
For different applications, PLA can be easily processed
using conventional polymer processing techniques like
injection molding, sheet extrusion, blow molding, thermo-
forming, and fiber spinning [2, 10, 11]. However, for dif-
ferent processing techniques, PLA resins need to be tailor

POLYMER ENGINEERING AND SCIENCE—-2007

 TABLE 1. Injection molding processing parameters (Tm, Tw, Qinj, Ph) and simulated thermomechanical variables (Tb, g_ , tw, Sa) of PLLA.

Run Tm (8C) Tw (8C) Qinj (cm3 s1) Ph (MPa) Tb (8C) ġ (s1) tw (MPa) Sa (%)

I 165 24 7 7 171.7 2594 0.61 4.4

II 165 60 7 29 172.0 2592 0.61 2.8
III 165 24 28 29 177.8 21,550 0.82 2.7
IV 165 60 28 7 178.1 18,845 0.79 1.5
V 220 24 7 29 224.3 2505 0.46 4.4
VI 220 60 7 7 224.3 2510 0.46 2.8
VII 220 24 28 7 227.0 10,304 0.63 2.8
VIII 220 60 28 29 227.1 10,339 0.64 1.5
Variation (%) 32 760 78 193

Tm, melt processing temperature; Tw, mold temperature; Qinj, injection flow rate; Ph, holding pressure; Tb, average bulk temperature; ġ, maximum
shear rate; tw, maximum shear stress; Sa, thickness of frozen layer.

high melt strength, which is suitable for processing like
extrusion, coating, blow molding, and foaming. For ther-
moforming, 4–8% D-isomer is introduced to avoid crystal-
lization during stretching of the polymer below melting
point [12].
The development of different microstructures because of
the applied thermomechanical conditions during injection
molding depends upon the operative parameters involving
melt processing temperature, mold temperature, the injec-
tion flow rate, and holding pressure [13, 14]. For the particu-
lar case of high L-lactide content linear PLA, most of the
injection-molded specimens exhibits low degree of crystal-
linity because of its slow crystallization rate and the high
cooling rates imposed during processing [15, 16]. Typically,
a nucleating agent is added to enhance the rate of crystalli-
zation and to obtain higher crystallinity. In this regard, a
recent review highlights the demanding technological im-
portance and complexity of crystallinity development of
stressed melt under intense flow field [17]. However, the
effect of shear stress and shear rate on molecular orientation
and crystallinity development of injection-molded PLLA
products were not properly addressed so far.
In this context, it would be desirable to investigate the
thermomechanical conditions that regulate the final me-
chanical performance of PLLA products. A suitable way
to accomplish this task is to perform a design of experi-
ments (DOE) plan that could allow investigating the fac-
tors and interaction between them that contribute more
significantly to the final product’s characteristics. The aim
of this study was to investigate the effect of injection
molding processing parameters on the microstructure and
mechanical properties of PLLA products, adopting a sta-
tistical technique (DOE and ANOVA) and to establish the
correlations among processing conditions, morphological
parameters, and mechanical properties.
MATERIALS AND METHODS
measured in chloroform at a concentration of 1 g dl1
and 258C (AA-1000 Polarimeter). PLLA was estimated to
have an L-lactide content of 99.6% by assuming [a]D25 of
poly(L-lactic acid) and poly(D-lactic acid) to be 156 and
þ156, respectively [18]. The PLLA had Mn ¼ 69,000 and
polydispersity of 1.73 as determined by gel permeation
chromatography (Shimadzu LC,10A, Japan) in chloroform
with the standard of polystyrene.
Molding Program
The pellets were predried at 508C for 4 h in a vacuum
oven. They were injection-molded in an ENGEL T 45
machine (ES-200/45 H L-V). The injection-molded speci-
mens were dumbbell shaped with 60 mm length, a con-
stant rectangular cross-section of 4  2 mm2, and 20 mm
of reference length. The molding program followed a
DOE plan, see Table 1, selecting the following process
parameters: melt processing temperature, Tm; mold tem-
perature, Tw; injection flow rate, Qinj; and holding pres-
sure, Ph. The low and high level of Tm (165 and 2208C),
Tw (24 and 608C), Qinj (7 and 28 cm3 s1), and Ph (7 and
29 MPa) were a compromise among machine limits, melt
viscosities, and mold filling characteristics. The barrel
was always flashed before every injection to avoid incor-
poration of possible degraded material.
Simulation of Thermomechanical Environment
The thermomechanical environment of processing was
characterized by computer simulations for the mold filling
stage (in Moldflow software package). The rheological
behavior of the material was described by a Cross-WLF
model. From the simulations the bulk temperature, Tb; the
maximum shear rate, ġ; the maximum shear stress, tw;
and the frozen layer ratio, Sa, were computed locally
along the calibrated region of the tensile specimen and
the average values were calculated. The effect of holding
pressure was not considered in the simulation.

Materials Intrinsic Viscosity Measurement

A high stereoregular PLLA was used in this study. The The viscosity characterization was performed in bulk
specific optical rotation, [a]D25 of this PLLA was 154.7 as specimens cut from the central part of the rectangular

1142 POLYMER ENGINEERING AND SCIENCE—-2007 DOI 10.1002/pen

cross-section of the specimens. The intrinsic viscosity was
measured on one specimen from each molding condition.
The chosen concentrations of PLLA in chloroform were
0.1, 0.2, 0.3, and 0.4 g dl1. The viscometer was placed
into a controlled water temperature bath at 258C. Each run
was repeated for seven times to obtain the constant efflux
time. The intrinsic viscosity (Z) (expressed as dl g1) was
calculated by extrapolating to zero concentration.
Morphological Characterization
Hot Recoverable Strain Test. The level of amorphous
molecular orientation resultant from processing can relax
upon thermal treatment at a temperature higher than the
glass transition temperature of the material. This effect
was observed in injection-molded poly(ethylene terephtha-
late) specimens with the variations of cooling indices
[13]. This results in variations on the sample dimensions.
The difference between the dimension before and after
thermal treatment is described as the hot recoverable
strain (HR). The higher the HR, i.e., the more is the re-
covery, the higher is expected to be the initial level of
molecular orientation in the molded specimen. Five speci-
mens of each condition were marked with a grid spaced
18 mm along the constant cross-section zone. The speci-
mens were then placed on a fine talc layer in an oven at
1208C for an hour. Thereafter, the oven was turned off
and allowed to cool to room temperature. In each speci-
men, the distance between grid marks were measured
again. The HR was defined as the average percentage
reduction on the distance between the grid marks.
Differential Scanning Calorimetry. The thermal
behavior of the molded specimens was assessed by differ-
ential scanning calorimetry (DSC) in a Perkin Elmer
DSC-7 system at 208C min1 using nitrogen as purge gas.
Calibrations of temperature and energy scale were carried
out using pure indium standard. The DSC scans were per-
formed in bulk specimens (one from each condition) cut
from the central part of the rectangular cross-section of
the specimens. The glass transition temperature, Tg, cold
crystallization onset, Tc, and total enthalpy, DH were
identified. The degree of crystallinity was calculated by
DHc þ DHm
wc ¼  100 (1)
DHo
where DHc and DHm are the enthalpy of cold crystalliza-
tion and the enthalpy of melting, respectively. DHo ¼ 93
J g1 was assumed as enthalpy for 100% crystalline
PLLA [19].
Mechanical Characterization. The dumbbell-like
specimens were tested in a computerized Universal testing
machine, INSTRON 4505, in tensile mode. The deforma-
tion of the specimens was measured using an extensome-
ter. The tests were performed at a controlled room tem-
DOI 10.1002/pen
perature of 238C at a test velocity of 5 mm min1. A
minimum number of five specimens from each condition
were tested. The mechanical properties envisaged were
the elastic modulus (taken as the initial slope of the
stress–strain curve), E; the maximum stress, smax; and the
strain percentage at break, eb.
Statistical Data Treatment. Analysis of variance
(ANOVA) was performed on all assessed morphological
parameters. Level 1 and level 2 were considered as the
low and high-level settings, respectively. Results pre-
sented were significant upon 95% of confidence limit.
The F-ratio values were the determinant for significance
of the factors. The percentage contributions of the proc-
essing factors were calculated.
RESULTS AND DISCUSSION
Processing and Thermomechanical Environment
Table 1 shows the variations of the thermomechanical
parameters with different processing conditions. The bulk
temperature, Tb, is mainly controlled by melt processing
temperature, Tm. The evolution of the thermomechanical
parameters from different injection molding processing
conditions were explained in detail by Viana et al. [20].
The increment of bulk temperature over Tm was 7–138C
at low Tm and 4–78C at high Tm. The higher increment of
bulk temperature was because of higher viscous dissipa-
tion generated by high viscosity melt at low Tm. More-
over, at low Tm, the bulk temperature increased by
68C
with high Qinj compared with low Qinj. Therefore, high
flow rate generates more viscous dissipation during proc-
essing.
Figure 1a shows the variations of the shear-rate with
the injection flow rate and melt processing temperature. ġ
increases with the former, especially for low Tm setting,
and decreases with the latter, mainly for high settings of
Qinj. An interaction between both these processing varia-
bles does occur. The variations of the shear stress with
the injection flow rate and melt processing temperature
present a similar trend (see Fig. 1b). The shear stress, tw,
decreases with increasing Tm and increases with increas-
ing Qinj.
The thicknesses of the frozen layers were limited
within 1.5–4.4% (see Table 1). As expected, for the low
mold temperature, Tw, the frozen layer thicknesses were
higher compared with the high Tw because of the faster
cooling rate at low Tw.
Hot Recoverable Strain
HR is an important parameter directly related to
thermo-mechanical environment applied during process-
ing. Figure 2 shows the variations of HR with maximum
shear rate and maximum shear stress. HR increases stead-
POLYMER ENGINEERING AND SCIENCE—-2007 1143
 FIG. 2. Hot recoverable strain, HR, versus maximum shear rate, ġ and
maximum shear stress, tw of injection-molded PLLA.

shear stress led to higher level of molecular orientation.

The effect was a strong dependence of HR on Tm. As
explained before, the increase in shear rate at low Tm led
to higher viscous dissipation, showing an increase in bulk
temperature. This could facilitate the relaxation of molec-
ular orientation and thereby reduces HR, as revealed from
the Tm  Qinj interaction. The high Tw facilitates the
relaxation compared with low Tw, thereby reducing the
HR, as also revealed in the Tm  Tw interaction.

Differential Scanning Calorimetry

The DSC scans of processed PLLA specimens showed
FIG. 1. (a) Relationship among maximum shear rate, ġ, on the injec- characteristic peaks of exothermic cold crystallization and
tion flow rate, Qinj, and melt processing temperature, Tm. (b) endothermic melting apart from the signal of glass transi-
Relationship among maximum shear stress, tw, on the injection
flow rate, Qinj, and melt processing temperature, Tm. tion (see Fig. 4). The glass transition temperature of pro-
cessed PLLA, assessed from the mid-point of DSC scans
varies from 58.1 to 60.98C (a variation of 4.8%). The in-
ily with increasing shear stress. This reflects the increased crement of heat capacity because of the relaxation process
molecular orientation with increasing stress level. The
effect of shear rate on HR is low and shows a tendency
to decrease with increasing shear rate. The higher viscous
dissipation with increase in shear rate could enhance the
relaxation of molecular orientation and resulting in a
decrease in HR.
The maximum and minimum values of HR were 11.6
and 5.7, respectively. The minimum value was observed
in Run V; this could be probably because of the very low
molecular orientation induced by low shear stress and low
shear rate (refer Table 1). The statistical analysis allowed
us to conclude that Tm is the most important processing
parameter for the variations of HR with an individual rel-
ative contribution of 53% (see Fig. 3). The relative contri-
butions of Qinj and Tw were 7 and 5%, respectively. The
significant interactions are Tm  Tw and Tm  Qinj with
FIG. 3. Relative contributions of injection molding processing variables
relative contributions of 15 and 12%, respectively. on hot recoverable strain, HR, of PLLA specimens calculated from sta-
Figure 3 also presents the dependences of HR upon the tistical analysis. The inset graph shows the effect of individual factors
significant factor and interactions. At low Tm, the high and interactions on HR.

1144 POLYMER ENGINEERING AND SCIENCE—-2007 DOI 10.1002/pen

FIG. 4. Representative DSC thermogram of injection-molded PLLA FIG. 5. Degree of crystallinity, wc, versus maximum shear rate, ġ, and
specimen. maximum shear stress, tw of injection-molded PLLA.

ing [22]. Therefore, it can be concluded that the process-

of the mobile amorphous fraction at Tg is termed as DCp. ing conditions did not significantly change the molecular
The DCp values vary from 0.525 to 0.366 J K1 g1 weight of the material and the changes in the properties
(a variation of 43%). were affected mainly by the morphological changes
In the experimental conditions used in this work, the induced by the different processing conditions.
crystallinity of the processed PLLA specimens is low
because of slow crystallization kinetics of this polymer
and fast cooling rates [15]. This was clearly confirmed Mechanical Properties
from the DSC scans, where the degree of crystallinity var-
The elastic modulus, E, scattered from 2.02 to 1.89
ied between 1.5 and 6.2%.
GPa under the present experimental set-up (see Table 2).
The crystallinity development of a polymer during
Thus, the variation is 7% whereas the average experimen-
injection molding process is a complex phenomenon
tal error was 4%. The degree of crystallinity and level of
involving thermomechanical stress, shear rate, and cooling
molecular orientation developed during injection molding
rate [17]. Figure 5 shows that the degree of crystallinity
process have little effect on initial modulus. The yield
is steadily increasing with increasing shear stress. The
strain scattered from 4.0 to 4.4%.
effect of shear rate on crystallinity is low and shows a
tendency to decrease with increasing shear rate.
The statistical analysis enabled to accomplish that the Elongation at Break
relevant processing factors and interactions influencing wc
The maximum and minimum values of elongation at
were Tm and Tm  Tw and their relative contributions
break, eb, were 18.2 and 6.3, respectively. The percentage
were 79 and 10%, respectively (refer Fig. 6). The results
of variation was 189%. The elongation values are lower
of statistical analysis are consistent with the findings from
at low Tm and higher at high Tm (refer Table 2). More-
thermomechanical indices that the shear rate had little
influence on wc (as the contribution of Qinj did not appear
on statistical analysis). The inset graph in Fig. 6 shows
that the wc was high at low Tm and low at high Tm. The
high shear stress levels at low Tm imposed more con-
straints to molecular chains during processing, leading to
stress induced crystallization. Moreover, the slow cooling
rate at low Tm could have facilitated an increased crystal-
linity development.
The degradation of lactic acid based polymers by
injection molding was always a debate [16, 21, 22]. How-
ever, in the present experimental set up, the observed
change on the intrinsic viscosity was very low. The meas-
ured Z of processed PLLA varies from 1.37–1.48 dl g1,
whereas Z for the PLLA pellets was of 1.45 dl g1. The
degradation was minimum because injection-molding bar-
FIG. 6. Relative contributions of injection molding processing variables
rel was always flashed before each shot. An independent on the degree of crystallinity, wc, of PLLA specimens, calculated from
study by Dow chemical company on Cargill PDLLA statistical analysis. The inset graph showed that the low Tm induced
showed no molecular degradation during injection mold- more crystallinity.

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—-2007 1145

TABLE 2. Morphological parameters (HR, wc) and mechanical
properties (E, s, eb) of injection-molded PLLA specimens
produced different thermomechanical environment.

Run HR wc (%) E (GPa) s (MPa) eb (%)

I 11.6 6 0.6 6.1 1.94 6 0.04 67.3 6 0.3 11.4 6 1.3

II 10.6 6 0.4 6.2 2.02 6 0.11 70.6 6 2.2 10.1 6 1.4
III 10.6 6 0.5 5.9 1.93 6 0.12 62.4 6 1.6 6.3 6 2.2
IV 6.2 6 0.4 4.9 1.98 6 0.05 63.8 6 0.7 10.3 6 2.3
V 5.7 6 0.4 2.3 1.96 6 0.05 62.8 6 2.8 11.3 6 2.4
VI 7.0 6 0.3 2.8 1.95 6 0.03 64.9 6 2.7 14.9 6 4.3
VII 6.6 6 0.3 1.5 1.89 6 0.02 60.9 6 1.0 18.2 6 3.2
VIII 6.8 6 0.3 4.3 1.89 6 0.07 61.3 6 2.1 9.2 6 1.1
Variation 103 313 7 74 189 FIG. 8. Relationship among the maximum yield stress, smax, on hot
(%) recoverable strain, HR, and the crystallinity developed during processing,
wc, on injection-molded PLLA specimens produced from different proc-
HR, hot recoverable strain; wc, degree of crystallinity; E, tensile mod- essing conditions. (The 3D plane is a fit of the data s ¼ 57.52 þ
ulus; s, maximum yield stress; eb, elongation at break. 0.57HR þ 0.49wc). R2 ¼ 0.43.

over, the minimum eb was observed at Run III, which

was with low Tm, high shear stress, and high shear rate.
Tensile Strength
The maximum and minimum values of tensile stress,
smax, were 70.6 and 60.9 MPa, respectively (refer Table
2). The percentage of variation was 16%. The overall ten-
sile strength was high at low Tm compared with high Tm.
Moreover, at low Tm, there was a decrease in smax with
increasing shear rate.
Morphology–Mechanical Property Relationship
There are interactions between yield stress, elongation
at break, and the morphology parameters like the HR and
the degree of crystallinity; so none of these factors should
be considered in isolation. The morphology–mechanical
properties relationships could be established with the aid
of polynomial fit in a three-dimensional experimental
FIG. 7. Relationship among the elongation at break, eb, on hot recover-
able strain, HR, and the crystallinity developed during processing, wc, of
injection-molded PLLA specimens produced from different processing
conditions. (The 3D plane is a fit of the data eb ¼ 14.54 þ 0.82HR þ
2.28wc). R2 ¼ 0.66.
area, where the individual morphology parameters can be
applied over mechanical properties.
Figure 7 shows the evolution of elongation at break, eb
with HR and wc fitted by a simple polynomial equation: eb
¼ 14.54 þ 0.82HR þ 2.28wc. Elongation at break
increases with increasing HR and decreases with increas-
ing wc. The similar result was reported by drawing
PDLLA, where the increase in orientation increases the
elongation at break [20]. However, the crystallinity devel-
opment has severely reduced the eb of PLLA moldings.
Figure 8 shows the resulting fit for the variation of
yield stress, smax with HR and wc by the equation: smax ¼
57.52 þ 0.57HR þ 0.49wc. The maximum stress increases
with increasing HR, i.e., as the level of molecular orienta-
tion increases, the yield stress increases [20]. Moreover,
the yield stress was also increasing with increasing crys-
tallinity [21]. The level of molecular orientation contrib-
uted slightly more than the crystallinity in the increment
of yield stress.
CONCLUSIONS
This study provided an overview among processing
conditions, morphology, and mechanical property relation-
ship of conventional injection-molded PLLA. The proc-
essing conditions were systematically varied following a
DOE array. The thermomechanical indices, i.e., maximum
shear stress and maximum shear rate were estimated by
computer simulations. The two morphological parameters,
the HR, and the degree of crystallinity were interpreted
by the thermomechanical indices. The relationships
between the morphology and mechanical properties were
then established.
The maximum shear stress and maximum shear rate were
mainly controlled by melt processing temperature and injec-
tion flow rate, respectively. With an increase in injection
flow rate, the shear stress and increment of bulk temperature
were increased more at low melt processing temperature
compared with high melt processing temperature.

1146 POLYMER ENGINEERING AND SCIENCE—-2007 DOI 10.1002/pen

 The two morphological parameters analyzed HR,
related to the level of molecular orientation, and wc, the
degree of crystallinity, were interpreted by thermome-
chanical indices and statistical analysis. The shear stress
predominantly controlled both the morphological parame-
ters. The HR and the degree of crystallinity increased
with increasing shear stress. The statistical analysis
allowed us to accomplish that the low melt processing
temperature facilitates to attain high level of molecular
orientation and high degree of crystallinity.
The structure–property relationships between the mor-
phological parameters and mechanical properties were
established. The elongation at break increases with
increasing the level of molecular orientation and
decreases with increasing crystallinity. Although the
degree of crystallinity of these injection-molded speci-
mens was limited to only 6.2%, but the elongation at
break decreases sharply with increase in shear induced
crystallinity.
Both the level of molecular orientation and crystallinity
contributed to the maximum tensile strength of the injected
specimens. The tensile strength increased with an increase
in molecular orientation and degree of crystallinity.
From the application point of view, these results may be
useful to optimize and tailor morphological features of
PLLA devices that will determine relevant properties
including mechanical performance and degradation profile.
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