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The mechanical behavior of poly(lactic acid) unreinforced and nanocomposite

films subjected to monotonic and fatigue loading conditions

Article  in  Journal of Composite Materials · December 2011

DOI: 10.1177/0021998311410464

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 JOURNAL OF
COMPOSITE
Article M AT E R I A L S
Journal of Composite Materials
45(26) 2717–2726
! The Author(s) 2011
The mechanical behavior of poly(lactic Reprints and permissions:
sagepub.co.uk/journalsPermissions.nav
acid) unreinforced and nanocomposite DOI: 10.1177/0021998311410464
jcm.sagepub.com
films subjected to monotonic and fatigue
loading conditions

Rodney D. Averett1, Mary L. Realff2, Karl Jacob2,

Mukerrem Cakmak3 and Baris Yalcin3

Abstract
The mechanical and fatigue behavior of neat poly(lactic acid) (PLA) films and PLA films reinforced with 5 wt% nanoclay
particles has been examined using various analytical procedures. The results showed that for the films tested in this
study, PLA-5 wt% samples were more susceptible to crazing at the same maximum fatigue stress as the neat PLA samples,
as evidenced by results from light transmission experiments. Optical microscopy results confirmed this observation. In
addition, under fatigue loading conditions, the neat PLA samples displayed almost the same fatigue resistance (number of
cycles to failure) at 3 and 30 Hz, while the PLA-5 wt% samples showed a shift in the number of cycles to failure to higher
values at a frequency of 30 Hz. Using the linear regression curves from the S–N data (stress vs. number of cycles to
failure), time-to-failure curves were generated to show the difference between the neat PLA and PLA-5 wt% samples
when tested at frequencies of 3 and 30 Hz. Based on these results, it is known that the nanoclay particles served to
increase the fatigue resistance at the higher frequency of 30 Hz, when compared to the neat PLA sample.

Keywords
Films, nanocomposite, fatigue, poly(lactic acid), nanoclay

molecular architecture. The films possess defined

Introduction
Poly(lactic acid) or polylactide (PLA) is a biodegrad-
able, thermoplastic, aliphatic polyester derived from
renewable resources. As a biodegradable polymer,
PLA is becoming increasingly popular. PLA has high
mechanical strength, thermal plasticity, fabricability,
biodegradability, and biocompatibility. It has been pro-
posed as a renewable, degradable plastic for uses in
service ware, grocery, waste and composting bags,
mulch films, and controlled-release matrices for fertil-
izers, pesticides, and herbicides.1 PLA is currently used
in a number of biomedical applications, such as sutures,
stints, dialysis media, and drug delivery devices, but it is
also evaluated as a material for tissue engineering. In
addition, films composed of PLA have been employed
in the medical industry as a means to reduce the for-
mation of postoperative cardiac adhesions2 and intra-
abdominal adhesions, inflammation, and fibrosis.3 In
these biomedical applications, the PLA system is
selected because of its specific composition and
mechanical strength, flexibility, rate of resorption, and
biocompatibility. Thus, it can be avowed that PLA is a
multi-purposed material that can be utilized due to its
superior mechanical strength and biodegradability
attributes.
Combining PLA with nanoclay particles for increa-
sed barrier and mechanical performance has also
become popular.4–6 Because of the increased interest
1
The Wallace H. Coulter Department of Biomedical Engineering, Georgia
Institute of Technology and Emory University School of Medicine, 313
Ferst Drive, Atlanta, GA 30332, USA.
2
The School of Materials Science and Engineering, Georgia Institute of
Technology, 801 Ferst Drive, Atlanta, GA 30332, USA.
3
Department of Polymer Engineering, Polymer Engineering Academic
Center, The University of Akron, Akron, OH 44325-0301, USA.
Corresponding author:
The School of Materials Science and Engineering, Georgia Institute of
Technology, 801 Ferst Drive, Atlanta, GA 30332, USA
Email: marylynn.realff@mse.gatech.edu
2718
in PLA as a viable engineering and packaging material,
there should be more studies directed at the mechanical
and fatigue behavior of the materials. This study seeks
to mitigate this research gap by identifying the modes
and mechanisms of failure for PLA and PLA-5 wt%
samples with nanoparticle loaded under uniaxial ten-
sion and uniaxial fatigue loading.
Experimental
Materials and film preparation
PLA 2002D (LMW) was provided in pure and filled
(5 wt% Cloisite 30B organoclay) pellet form from
NatureWorksÕ company. Cloisite 30B (C30B) is an
organically modified montmorillonite (MMT) with
alkyl ammonium as the clay modifier. Before the cast-
ing took place, the pellets were dried in a vacuum oven
overnight at a temperature of 80 C. A 1.500 Prodex
single screw extruder with a chill roll casting unit was
used to cast amorphous films of neat and filled PLA
2002D (LMW). The casting conditions are presented in
Table 1. Cast films were prepared with the single screw
extruder (melt temperature 200 C, L/D 32:1), which
was equipped with a 200 mm wide T-die and a take-
up system. The films were cast onto a chilled roll (tem-
perature 30 C) using the screw extruder. After process-
ing, a gel permeation chromatograph machine was used
to measure the molecular weights of PLA. The weight–
average molecular weight (MW) of the 2002D film
grade was determined to be 137,000 g/mol.
Mechanical testing
The sample specimen size used for the fatigue tests
was 9.5 mm wide and 30 mm long. The thickness of the
neat PLA and PLA-5 wt% samples was 0.26  0.02 and
0.30  0.04 mm, respectively. The BOSEÕ ELectroForceÕ
(ELFÕ ) 3200 testing machine (Enduratec)) was used to
conduct the mechanical experiments in uniaxial fatigue.
Table 1. Processing conditions used to fabricate PLA nano-
composite film specimens
Feed temperature (zone 1) 180 C
Compression section temperature (zone 2) 190 C
Metering temperature (zone 3) 200 C
Adapter temperature 200 C
Die temperature 200 C
Chill roll temperature 52 C
Screw speed 33 rpm
Take-up speed 70 rpm
Die gap thickness 0.4 mm
Journal of Composite Materials 45(26)
The uniaxial tensile tests for characterization were per-
formed at an elongation rate of 5 mm/min on a standard
Instron machine and the fatigue tests at frequencies of
3 and 30 Hz. The Enduratec has a maximum load of
225 N and a maximum frequency of 400 Hz. A set of low
mass grips, Model GRP-TC-DMA450N from BOSE
ELectroForceÕ (Eden Prairie, MN, USA), were used to
conduct the fatigue tests. The ELF 3200 measures dis-
placements via a Capacitec 100 mm displacement trans-
ducer (Model HPC-40/4101) used as a feedback for the
control loop. The Q800 dynamic mechanical analysis
(DMA) machine from TA Instruments (New Castle,
DE, USA) was used to evaluate and characterize the
dynamic behavior of the samples as a function of
frequency and temperature. The specimen size used for
the DMA tests was 10 mm wide and 25 mm long. All
experiments were conducted at room temperature, labo-
ratory air. The typical humidity of the laboratory air was
about 50%.
Light transmission experiments
Light transmission experiments were conducted in
the visible wavelength spectrum (360–750 nm) on the
UltraScan XE spectrophotometer from HunterLab
(Reston, VA). Due to the small specimen width, an
aperture size of 0.37500 was attached to the instrument
to conduct the experiments. Light transmission experi-
ments were conducted in the visible wavelength
spectrum (360–750 nm) to determine the effects of
mechanical loading on the opacity (reduction in trans-
parency) of the PLA and PLA-5 wt% nanocomposite
samples. The samples were loaded into the machine
as close to the fracture surface as possible, so as to
capture the effects of stress whitening close to the fail-
ure region.
The equation that appositely describes the amount
of light that is transmitted through the sample can be
determined by considering the Beer–Lambert Law,7, 8
considering that the fractional intensity that is lost can
be represented as:
dI
¼ aT dh ð1Þ
I
where dI is the fractional loss in intensity, I the intensity
of light, aT the extinction coefficient, and dh the infin-
itesimal thickness of the sample. If this equation is inte-
grated, one obtains the following for the general form
of the Beer–Lambert Law:
Z h Z h
dI
¼ aT dh ð2Þ
0 I 0
Averett et al. 2719

The intensity as a function of the extinction coefficient
and thickness of the sample is expressed as the Beer–
Lambert Law:7
I ¼ I0 eaT h
The transmission of light through the sample can be
expressed as:
I P
T¼  ð4Þ
I0 P0
where I and I0 represent the transmitted intensity and
the incident intensity, respectively, and P and P0 the
transmitted power and incident power, respectively.
Optical microscopy experiments
Optical microscopy of the unfilled and filled samples
was performed on a Leitz Laborlux 12 Pol S micro-
scope in unpolarized light configuration. Optical pic-
tures were taken by a digital camera, Micropublisher
5.0 RTV, from Qimaging connected to the microscope
and collected using Image Pro plus 6.2 software.
Results and discussion
Uniaxial tensile test results
The results from the uniaxial tensile tests indicate that
the neat PLA and PLA-5 wt% films exhibited similar
mechanical properties. The results for these experi-
ments are presented in Tables 2 and 3. The modulus
of the neat film (3.1 GPa) was very close to that of the
PLA-5 wt% nanocomposite film (3.2 GPa). On aver-
age, the maximum strain of the neat film sample was
very close to that of the nanocomposite sample (0.081
compared to 0.10). The tensile energy of the PLA-5
wt% sample was approximately 5% more than the
neat PLA sample. Finally, the maximum stress of
the neat PLA sample was actually 18% higher than
the 5 wt% sample. These results are not in accordance
ð3Þ with similar studies that have evaluated the mechanical
behavior of PLA with the inclusion of clay nanoparti-
cles. Jiang et al.5 noted an increase in the tensile
strength of the PLA nanocomposites up to 5 wt%,
whereas in this study, a decrease in the tensile strength
was observed.
These results are somewhat counterintuitive, since
one would envision that the addition of rigid platelet
clay nanoparticles would significantly enhance all the
mechanical properties of the PLA samples. However,
the intimacy of the bonding between the matrix and
nanoparticle was low, since the addition of functional
groups or other bonding agents was not incorporated
into the fabrication process. This led to a lower inter-
facial strength of the nanocomposite specimens. Due to
the low interfacial adhesion between the nanoparticles
and PLA matrix, debonding occurred at the site of the
interface, leading to lower fracture strengths and higher
strains at break under uniaxial conditions. In fact, it
has been observed in literature that systems with low
interfacial adhesion between the matrix and polymer
exhibit debonding at a stress lower than that of the
neat matrix,5 leading to lower yield strengths and
higher strains at break (due to massive crazing) with
increasing nanoparticle concentration. Also, due to
the platelet shape of the nanoparticles, stress concen-
tration sites were engendered, causing the debonding to
occur more easily. Argon and Cohen9 have illustrated
how the yield stress in a polymeric sample decreases
with the addition of rigid platelet CaCO3 nanoparticles
(Figure 1). In essence, they9 explained that the reduc-
tion in yield strength was due to the fact that the par-
ticles debonded from the matrix before overall yield.
Based on these results, it is believed that under uniaxial

Table 2. Uniaxial tensile test results for neat PLA films

Thickness (mm) E (GPa)  max (MPa)  f (MPa) emax Energy (kJ/m3)

Average (10 samples) 0.26 3.1 58 50 0.081 3.7

Standard deviation 0.02 0.21 1.0 1.2 0.032 1.6

Table 3. Uniaxial tensile test results for PLA films with 5 wt% nanoclay particles

Thickness (mm) E (GPa)  max (MPa)  f (MPa) emax Energy (kJ/m3)

Average (10 samples) 0.30 3.2 49 41 0.10 3.9

Standard deviation 0.040 0.20 2.7 2.5 0.020 0.94
2720 Journal of Composite Materials 45(26)

0.3 9000
tan delta
Storage modulus 8000
0.25
5 wt% sample 7000

Storage Modulus (MPa)

0.2 6000

tan delta
5000
0.15
4000
0.1 3000
Neat
sample 2000
0.05
1000
0 0
0 50 100 150 200 250
frequency (Hz)

Figure 3. Tan  and storage modulus vs. frequency for neat PLA
and PLA-5 wt% samples.

This is shown in Figure 3, where an example result of

the tan  and storage modulus vs. frequency has been
plotted for the samples.
Figure 1. Yield stress vs. particle volume fraction for polymer It is believed that the broader transition in tan  for
system with rigid CaCO3 particles displaying the decrease as a the nanocomposite samples is the result of the nanopar-
function of particle volume fraction.9 ticles that interacted with the matrix and caused the
strain in the samples to lag the stress for a larger fre-
quency window than the neat samples. A similar result
70 has been obtained by another group,10 where studies of
60 the viscoelastic behavior of PLA systems reinforced
PLA Neat Sample
with organoclay nanoparticles has been obtained.
50 They confirmed results showing that the tan  function
Stress (MPa)

40
PLA 5wt% Sample increased as a function of the nanoclay content for
all frequencies. In this study, for both the neat PLA
30 and the PLA-5 wt% samples, the critical frequency at
which the tan  function displayed its maximum
20
peak was approximately 100 Hz. The results from the
10 storage modulus vs. temperature show a similar result
(Figure 4), where the mechanical behavior of the films
0
0 0.02 0.04 0.06 0.08 0.1 0.12 from room temperature up to 120 C was virtually iden-
strain tical. The results (Figure 5) show that for PLA-5 wt%
PLA Neat Sample PLA 5wt% sample
samples, the glass transition temperature was slightly
Figure 2. Example stress–strain curves of neat PLA and PLA-5 shifted to a lower temperature. The Tg of the neat
wt% samples under uniaxial tensile loading conditions. PLA samples was 77.1 C while that of the PLA-5
wt% samples was 74.7 C.

conditions, the debonding caused a lower yield and

fracture strength of the PLA-5 wt% sample, as shown
in Figure 2.
Results from DMA
The results from the DMA experiments revealed a dif-
ference in behavior for the neat PLA and PLA-5 wt%
samples. For DMA tests conducted on the mechanical
properties as a function of frequency, the results
showed that the nanocomposite 5 wt% samples
showed a broader transition in tan  and storage mod-
ulus from lower frequencies up to higher frequencies.
Results from light transmission experiments
The results indicate that samples loaded in uniaxial ten-
sion displayed a significant reduction in transparency
reduction due to the formation of craze zone that sur-
rounded the crack tip region and spread to a larger
portion of the film. It was visually observed from the
experiments and from Figure 6 that displays the results
from a PLA-5 wt% film that the light transmission
behavior changed with loading condition and wave-
length. At around 420 nm, the maximum difference
between the undeformed PLA-5 wt% and the uniaxi-
ally loaded sample occurs. For the uniaxially tested
Averett et al. 2721

10000
Storage modulus PLA neat
PLA 5wt%
1000
Loss modulus
100

Modulus (MPa)
10

1
0 20 40 60 80 100 120 140

0.1

0.01
Temperature (deg C)

Figure 4. Storage and loss modulus vs. temperature for neat PLA and PLA-5 wt% samples.

3.5
rigid particles were responsible for preventing light
from passing through the film.
3
PLA Neat The light transmission of PLA-5 wt% vs. neat PLA
PLA 5wt% samples can be seen more clearly from Figure 8, where
2.5
the light transmission at 420 nm (critical wavelength) of
tan delta

2 unfatigued and fatigued neat PLA and PLA-5 wt%

1.5
1 PLA, the percentage of light transmitted through the
0.5
0
0 20 40 60 80
Temperature (deg C)
Figure 5. Tan  vs. temperature for neat PLA and PLA-5 wt%
samples.
samples, craze zones formed perpendicular to the load-
ing direction. Craze zone formation with the creation of
a nubilous film surface is a highly established in litera-
ture.11,12 This crazing process is known to create micro-
void sites and stress whitening in the vicinity of
deformation for PLA samples with and without the
reinforcement of clay nanoparticles.5 From the light
transmission experiments, it was determined that the
wavelength at which the largest deviation in light trans-
mission between the undeformed and deformed sam-
ples was approximately 420 nm.
The light transmission results from the fatigue exper-
iments are shown in Figure 7. These results indicated a
similar pattern to that of the uniaxially tested samples.
There was a critical wavelength around 420 nm that
existed for the samples, where the largest deviation
was observed between the undeformed sample and
deformed samples. It should also be noted that the
PLA-5 wt% samples displayed lower light transmission
values in the visible spectrum than the neat PLA sam-
ples. This is expected, due to the fact that the platelet
samples has been plotted as a function of the maximum
fatigue stress. The results show that for unfatigued
sample was approximately 83%, while the PLA-5 wt%
unfatigued sample exhibited a light transmission value
of 75%. In addition, the PLA-5 wt% samples exhibited
100 120 140 a larger decrease in the light transmission as a function
of maximum stress with respect to the neat PLA sam-
ples. Stress whitening due to crazing was observed visu-
ally on both neat PLA and PLA-5 wt% samples.
However, based on the light transmission results from
Figure 8, it is seen that the 5 wt% samples exhibited
increasing turbidity as a function of maximum fatigue
stress. This is in contrast to that of neat PLA samples,
indicating that the PLA-5 wt% samples were more sen-
sitive to crazing than the neat PLA samples. This can be
explained by considering results from literature that
explain that an increase in the loading of nanoclay par-
ticles induces a phenomenon that promotes debonding
and localized yielding, leading to significant crazing.5
Jiang et al.5 have noted that neat PLA tested under
uniaxial tension showed fairly smooth fracture surfaces,
when viewed using the scanning electron microscope.
This was due to the lack of large-scale plastic deforma-
tion in neat PLA. However, the fracture surfaces of
PLA reinforced with nanosized precipitated calcium
carbonate showed more yielding features because of
larger plastic deformation caused by more crazes. In
addition, they observed that the fracture morphology
of PLA reinforced with 2.5 wt% MMT clay exhibited
stress whitening and necking during tension. The results
from Figures 6–8 in this study are directly in synchro-
nization with the results from literature, where more
2722
Figure 6. Uniaxial tensile test results: example light transmission vs. wavelength in the visible spectrum (360–750 nm) for PLA-5 wt%
sample tested under uniaxial loading to failure.
Figure 7. Fatigue results: light transmission vs. wavelength for neat PLA and PLA-5 wt% nanocomposite samples.
opacity due to stress whitening was observed for the
PLA-5 wt% nanoclay films.
Results from fatigue
Fatigue tests were conducted on the PLA and PLA-5
wt% samples at various levels of maximum stress to
determine the fatigue resistance at frequencies of 3
and 30 Hz. Maximum stress vs. number of cycles to
failure (S–N) curves were generated for these samples
to determine their resistance to a repeated cyclic load-
ing for a fixed maximum stress. Maximum fatigue stress
values in the range of approximately 25% to 75% of
the maximum uniaxial stress were used to conduct the
fatigue experiments. Approximately 54 samples were
Journal of Composite Materials 45(26)
tested in the study (both neat and 5 wt% nanocompo-
site). The experiments conducted below the critical
glass transition frequency (below 100 Hz) at a fre-
quency of 3 Hz indicate a result that is concomitant
with the results from the uniaxial tensile tests. At
3 Hz, the unreinforced PLA samples exhibited a
higher fatigue resistance than the PLA samples rein-
forced with 5 wt% nanoclay particles, as shown in
Figure 9. However, at 30 Hz, the neat PLA and PLA-
5 wt% samples exhibited almost the same fatigue
behavior. This indicates that the nanoclay particles
served to enhance the fatigue resistance of the samples
at 30 Hz. Based on the regression results shown in
Figure 9, it is known that both neat PLA and PLA-5
wt% samples displayed a linear semi-log behavior with
Averett et al. 2723

a functional form that relates the maximum fatigue where  max represents the maximum fatigue stress, m
stress to the number of cycles to failure as: the slope of the regression curve, Nf the number of
cycles to failure, and b the y-intercept. Equation (5),
which relates the maximum stress to the number of
cycles to failure can be rewritten in a modified form,
expressing the maximum stress as a function of time to
max ¼ m lnðNf Þ þ b ð5Þ
failure, tf, and frequency, f, as:

max ¼ m lnðtf  fÞ þ b ð6Þ

90
Light Transmission Data
λ = 420nm Equation (6) was algebraically modified to derive an
85
empirical relationship for the time to failure that was
PLA neat samples expected for the neat PLA and PLA-5wt% samples, as
80 a function of maximum stress and frequency, as:
% Transmission

max b
e ð m Þ
75 tf ¼ ð7Þ
f
PLA 5 wt% samples
70
For the neat PLA and PLA-5 wt% samples con-
ducted at 3 and 30 Hz, one would expect a similar
65 shift in the number of cycles that yields an equivalent
time to failure shift, since (1) the results from DMA
60 indicate that the storage modulus and tan  functions
0 10 20 30 40 50
σmax(MPa)
were virtually constant in this frequency range and (2)
the uniaxial characterization results indicate that the
Figure 8. Percentage light transmission vs. maximum stress for neat PLA sample is superior to that of the PLA-5
neat PLA and PLA-5 wt% samples as a function of maximum wt% sample in terms of yield strength and fracture
fatigue stress. strength. However, the neat PLA and PLA-5 wt%

45
PLA neat
sample
40
PLA neat sample
f =30Hz

35 y = -8.1Ln(x) + 101.6
PLA 5wt%
sample
30 f = 30Hz
Maximum Stress (MPa)

PLA 5wt% y = -5.0Ln(x) + 74.9

sample
25 f = 3Hz
y = -5.7Ln(x) + 71.7
runout
y = -1.8Ln(x) + 39.8
20

y = -0.9Ln(x) + 26.4
15

runout
y = -1.1Ln(x) + 26.6
10
y = -6.0Ln(x) + 80.7

0
100 1000 10000 100000 1000000
# Cycles to Failure

Figure 9. Maximum stress vs. number of cycles to failure (S–N curve) for neat PLA and PLA-5 wt% samples conducted at 3 and
30 Hz.
2724
nanocomposite samples behaved differently in terms of
the time to failure due to fatigue loading as a function
of maximum stress and frequency. In an effort to quan-
tify the difference in behavior of the two samples (neat
vs. 5 wt%) as a function of frequency, time-to-failure
curves were generated based on the empirical expres-
sions and are shown in Figure 10. The time-to-failure
curves for the neat PLA samples at 3 and 30 Hz show a
very wide difference in time to failure than the PLA-5
wt% samples. In terms of time, the neat PLA samples
at 30 Hz failed much sooner than the neat PLA samples
at 3 Hz. At 30 Hz; the PLA-5 wt% samples exhibited
the same behavior as the neat PLA samples, where they
failed sooner than the samples tested at 3 Hz. However,
there is one noticeable difference between the fatigue
behaviors of the two samples. In terms of time, it
must be noted that the PLA-5 wt% samples exhibited
a much smaller time differential between 3 and 30 Hz
than the neat PLA samples. After all, based on the
mechanical characterization results, one would expect
that the fatigue resistance of the PLA-5 wt% samples at
30 Hz would be lower than the neat PLA samples; how-
ever, this was not the case. This observation is interest-
ing, because it indicates that the nanoclay particles
served to enhance the fatigue resistance of the PLA
samples at 30 Hz, where it increased the time necessary
to cause failure. In addition, the neat PLA samples
fatigued at 30 Hz displayed a steeper decline slope in
the semi-log maximum stress vs. number of cycles to
failure behavior. Thus, from the results of the uniaxial
20000
18000
16000
14000
Time to failure (s)
12000
10000
8000
6000
4000
PLA 5wt%, f=30Hz
2000
PLA Neat, f=30Hz
0
0 5
PLA 5wt%, f=3Hz
Figure 10. Empirical curves of time to failure vs. maximum fatigue stress for neat PLA and PLA-5 wt% samples.
Journal of Composite Materials 45(26)
experiments in ‘Uniaxial tensile test results’ section and
the fatigue results of this section, it can be concluded
that the nanoclay particles engendered two antithetical
mechanical property attributes: (1) decreased maximum
stress (yield stress) and fracture stress under uniaxial
tension conditions and (2) increased time to failure
between the lower frequency of 3 Hz and higher fre-
quency of 30 Hz when compared to the neat PLA
sample (lower time-to-failure differential between 5
wt% sample at 3 and 30 Hz).
Optical microscopy results
The results from the optical microscopy study indicated
that the nanofiller particles may have served to prevent
the formation of cracks in the PLA sample at 30 Hz.
Figure 11 shows the pictures of neat PLA and PLA-5
wt% samples at 30 Hz. This is to show that crack for-
mation in neat PLA samples at 30 Hz was more severe
than the PLA-5 wt% samples. This is evidenced by the
fact that the neat PLA samples showed more severe and
long cracks than the PLA-5 wt% samples parallel to the
loading direction. In comparison, the PLA nanocom-
posite samples did not show a large density of cracks, as
shown in Figure 11.
In contrast, for the PLA-5 wt% samples tested at the
lower frequency of 3 Hz (Figure 12), the samples
appeared to have developed longitudinal cracks along
the direction of loading at a stress ratio lower than that
of the PLA-5 wt% samples tested at 30 Hz. This clearly
PLA Neat, f=3Hz
PLA 5wt%, f=3Hz
10 15 20 25 30 35 40 45
Maximum fatigue stress (MPa)
PLA 5wt%, f=30Hz PLA neat sample, f=3Hz PLA neat sample, f=30Hz
Averett et al.
PLA neat sample
Fatigue frequency = 30 Hz
σmax = 28.9 MPa = 0.50σf
Nf = 7,807 cycles
Figure 11. Optical microscope results of neat PLA and PLA-5 wt% samples at 30 Hz.
Longitudinal
cracks
PLA 5 wt% sample
Fatigue frequency = 3 Hz
σmax = 15.0 MPa = 0.30σf
Nf = 36,932 cycles
Figure 12. Optical microscope results of PLA-5 wt% samples
at 3 Hz.
indicates the frequency dependence of the PLA-5 wt%
samples, showing the susceptibility to longitudinal
crack formation at a lower frequency and perhaps a
different mode of failure for uniaxial fatigue testing
conditions.
Futher discussion
Kim and Lu13 conducted a study on polycarbonate
samples at different frequencies to determine that
cycling at lower frequencies caused a shorter fatigue
life (number of cycles to failure) for a given stress
amplitude. This same effect has been realized for this
study in PLA-5 wt% samples. Based on results of
cycling polycarbonate samples at various frequencies,
they noted two observations: Cycling at higher frequen-
cies may cause (1) a change in the internal nature of
viscous flow to create localized yield-like deformation
and (2) a thermal effect due to viscoelastic hysteresis
induced heating.
2725
PLA 5 wt% sample
Fatigue frequency = 30 Hz
σmax = 27.7 MPa = 0.56σf
Nf = 10,599 cycles
From the current results, it is seen that as the fre-
quency of the test is increased, the PLA-5 wt% nano-
composite samples were less susceptible to fatigue
damage than the neat PLA samples, where at the
higher frequency, the nanoparticles served to toughen
the material. In fact, it is known from the results in
Jiang et al.5 that, although nanoclay particles debond
from the surface, they serve to prevent coalescence
from forming large cracks and leading to premature
failure.
Conclusions
The mechanical behavior of neat PLA and PLA-5 wt%
samples has been evaluated to determine the effect of
nanoclay particles on the fatigue resistance. The yield
and fracture strength of the neat PLA samples was
18% and 22% higher than the PLA-5 wt% samples,
respectively, when tested under uniaxial conditions.
Uniaxially tested PLA-5 wt% samples exhibited stress
whitening due to crazing and fatigued PLA-5 wt% sam-
ples exhibited more stress whitening and crazing than
neat PLA samples, as evidenced by results from light
transmission studies. A fatigue study was conducted on
the samples at 3 and 30 Hz to ascertain whether or not
there was a difference in fatigue behavior between neat
PLA and PLA-5 wt% samples. Based on the literature
results and current results from uniaxial tension, it was
expected that the fatigue resistance (number of cycles to
failure) of the samples would increase with increasing
frequency. This increase in fatigue life from 3 to 30 Hz
was observed for the PLA-5 wt% samples. However,
the neat PLA samples did not exhibit this behavior,
where they experienced almost the same number of
cycles to failure at 3 and 30 Hz. This phenomenon
was further quantified using time-to-failure curves for
the different samples at 3 and 30 Hz, where it was shown
that there was a much larger deviation in time to failure
for the neat PLA samples than the PLA-5 wt% samples
2726
when tested at 3 and 30 Hz cyclic frequencies. Perhaps
the results at 3 Hz are concomitant with the results from
the neat PLA and PLA-5 wt% uniaxial (quasistatic)
experiments, where the lower rate of strain application
at that frequency was highly similar to that of uniaxial
tension. However, at the higher frequency of 30 Hz, the
neat PLA samples may have experienced more damage,
since the fatigue life was not increased. Optical micros-
copy results revealed that the clay nanoparticles served
to aid in the retardation of crack formation at a fatigue
frequency of 30 Hz. Based upon the results from litera-
ture and the neat PLA fatigue experiments, it is known
that the nanoclay particles, although not intimately
bonded to the PLA polymer chain architecture, served
to bolster the fatigue resistance of the samples. The
results of this study are important because they indicate
that the mechanical behavior of neat PLA and PLA
nanoclay samples tested under fatigue loading condi-
tions is different for different frequencies. These results
can be used as a quantitative and qualitative measure
for studies such as accelerated life testing and mechan-
ical performance. It would be interesting to ascertain
how these results compare to a study in which the tem-
perature of the samples is decreased (similar to increase
in frequency for this study), and fatigue experiments
conducted to determine if the time–temperature super-
position phenomenon is applicable to these polymer
systems.
Acknowledgments
The authors thank Dr Fred Cook and Murari Gupta at the
Georgia Institute of Technology for their help with the light
transmission experiments and many helpful discussions.
Funding
This research received no specific grant from any funding
agency in the public, commercial, or not-for-profit sectors.
References
1. Chang YN, Yang PC, Jin Z, Chellapa H, Xing C, Mueller
R, Anderson M, Clarke A and Iannotti E. Low molecular
weight polylactic acid for controlled release of active
agents. In: Proceedings of the Corn Utilization Conference
VI. St. Louis, MO, 4–6 June 1996, National Corn
Growers Association and National Corn Development
Association, pp. 1–4.
View publication stats
Journal of Composite Materials 45(26)
2. Okuyama N, Wang CY, Rose EA, Rodgers KE, Pines E,
diZerega GS, et al. Reduction of retrosternal and pericar-
dial adhesions with rapidly resorbable polymer films.
Ann Thorac Surg 1999; 68: 913–918.
3. Ersoy E, Ozlurk V and Yazgan A. Ozdogan M and
Gundogdu H. Effect of polylactic acid film barrier on
intra-abdominal adhesion formation. J Surg Res 2008;
147: 148–152.
4. Strange M, Plackett D, Kaasgaard M and Krebs FC.
Biodegradable polymer solar cells. Degradation and sta-
bility of polymer and organic solar cells. Sol Energy
Mater Sol Cells 2008; 92(7): 805–813.
5. Jiang L, Zhang J and Wolcott MP. Comparison of
polylactide/nano-sized calcium carbonate and poly-
lactide/montmorillonite composites: Reinforcing effects
and toughening mechanisms. Polymer 2007; 48(26):
7632–7644.
6. Lee YH, Lee JH, An I-G, Kim C, Lee DS, Lee YK, et al.
Electrospun dual-porosity structure and biodegrada-
tion morphology of Montmorillonite reinforced PLLA
nanocomposite scaffolds. Biomaterials 2005; 26(16):
3165–3172.
7. Jenkins FA and White HE. Fundamental of Optics. New
York: McGraw-Hill, 1981, p. 231.
8. Coelho JMP, Abreu MA and Rodrigues FC.
Methodologies for determining thermoplastic films opti-
cal parameters at 10.6 mm laser wavelength. Polym Test
2004; 23(3): 307–312.
9. Argon AS and Cohen RE. Toughenability of polymers.
Polymer 2003; 44(19): 6013–6032.
10. Pluta M, Jeszka JK and Boiteux G. Polylactide/montmo-
rillonite nanocomposites: Structure, dielectric, viscoelas-
tic and thermal properties. Eur Polym J 2007; 43(7):
2819–2835.
11. Ward IM. Mechanical behavior of poly(ethylene tere-
phthalate). J Macromol Sci Part B Phys 1967; 1(4):
667–694.
12. Anderson TL. Fracture Mechanics: Fundamentals and
Applications, 2nd ed. Boca Raton, FL: CRC Press,
1995, p. 688.
13. Kim GH and Lu H. Characteristics of accelerated lifetime
behavior of polycarbonate under athermal and high load-
ing frequency conditions. Polym Test 2007; 26(7):
839–845.