J Polym Environ
DOI 10.1007/s10924-017-1032-3
ORIGINAL PAPER
Soybean Oil Based Polylactic Acid Membranes: Synthesis
and Degradation Characteristics
R. Seda Tığlı Aydın1 · Elvan Akyol2 · Baki Hazer2
© Springer Science+Business Media New York 2017
Abstract Controlling the degradation parameters is one
of the main challenges of preparing appropriate biomateri-
als for biomedical applications. In this study, the effect of
soybean oil inclusion on hydrolytic degradation of polylac-
tic acid (PLA) was investigated both in vitro and in vivo.
PLA/oil membranes were prepared by using polymeric
soybean oil (PSO), epoxidized soybean oil and soybean
oil (SOYA) with their varied concentrations. Degradation
of membranes was performed in vitro for 8 weeks period
and in vivo for 4 weeks period. Weight loss, changes in
molecular weight, thermal properties and morphological
changes were studied during degradation. SOYA blended
PLA membranes show the lowest degradation rates by bulk
degradation after 4 weeks in vitro, followed by surface ero-
sion for the first week. Approximately twofold high per-
centage weight losses of all membranes were obtained after
4 weeks of degradation in vivo in comparison with in vitro
data. The significant weight loss, molecular weight loss and
thermal property change for PSO blended membranes were
determined during in vivo degradation which highlights
the increase of degradation rate by bulk degradation. Dras-
tic morphological changes were observed on surface of
degraded membranes in vivo with large pores, cracks, fis-
sures and large cavities.
Keywords Biodegradable polymers · Polymer blends ·
PLA · Soybean oil · In vitro · In vivo
* R. Seda Tığlı Aydın
rseda.tigli@gmail.com; seda.aydin@beun.edu.tr
1
Department of Biomedical Engineering, Bülent Ecevit
University, 67100 İncivez‑Zonguldak, Turkey
2
Department of Chemistry, Bülent Ecevit University,
67100 İncivez‑Zonguldak, Turkey
Introduction
Polylactic acid (PLA), which is used worldwide as a bio-
material, has long been used for various biomedical appli-
cations since it has gained its reputation of good bio-
compatibility [1, 2]. PLA based biomaterials are used in
applications such as bone fixation, repair of osteochondral
defects, ligament reconstructions and more generally for the
fabrications of stents, sutures and porous scaffolds [2–5].
However, the prediction of biodegradation characteristics
of PLA is a challenge, since several parameters including
molecular structure, crystallinity, L/D ratio, copolymeriza-
tion and physical structure greatly influence degradation
characteristics [6–8]. Studies proved that degradation time
increase with the higher content of L-units and PLA fib-
ers are reported as more resistant to degradation compared
to bulk forms [6, 7]. Moreover, the brittle nature of PLA
limits its applications in some biomedical area [9, 10].
Thus, researchers tried to tailor the mechanical and physi-
cal properties of PLA to suit the requirements of particular
applications through copolymerization, blending, etc [2, 4,
11–13]. Since polymer blending serves a synergy of differ-
ent materials, desirable degradation profiles as well as tun-
able physical and mechanical properties may be achieved
[10, 13–15].
According to great attention towards polymers pre-
pared from renewable resources due to limited petroleum
reserves, researchers have been pushed to work on vegeta-
ble oil based polymers [16]. Soy bean oil based polymers,
which have some properties like universal availability, low
price and superior compatibility, are being required for suit-
able biomedical applications [17–22]. Aydın et al. reported
polymeric soybean oil-g-polystyrene (PSO-g-PS) mem-
branes as a potential candidate of guided bone regenera-
tion [19]. Miao et al. reported a new class of biocompatible
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polyurethanes prepared from soybean-oil-based polyol for
suitable use in biomedical applications [20]. Successful
studies of in vivo biocompatibility of the autoxidized and
unoxidized unsaturated medium–long chain length (m–lcl)
co-poly-3-hydroxyalkanoates (m-lclPHAs) derived from
soya oily acids have been reported [21]. Biocompatibility
properties of elastomers with epoxidized soybean oil (ESO)
and epoxidized linseed oil have been demonstrated [22].
Inspiring from these studies, several forms of soybean oil
(i.e., conjugated soybean oil, ESO, hydrogenated forms-
polyols, auto-oxidized soy bean oil) have been used by
the scientists for the production of soybean oil-based PLA
polymers [23–27]. Robertson et al. reported the compatibi-
lization and toughening effect of conjugated soya oil on the
PLA [23]. Chieng et al. [24], Emad et al. [25], and Fathilah
et al. [26] reported mechanical and thermal properties of
ESO based PLA. Hazer studied the autoxidized soya oil
polymer and hydroxylated soya oil polymer by means of
mechanical properties, fracture surface analysis and anti-
bacterial properties [27]. Nevertheless, to the best of our
knowledge, biodegradation properties of soybean-oil based
PLA polymers have not been reported before.
A closer look at the degradation of PLA based bioma-
terials has revealed that PLA degrades by hydrolysis up
to lactic acid monomers, resorbed biologically and there
is no enzymatic degradation of PLA polymers in human
[28]. Hydrolytic degradation is of crucial importance for
its successful implementation in applications such as surgi-
cal sutures, drug delivery systems, and tissue engineering
scaffolds and the rate of degradation has been attributed to
a number of polymer characteristics [29]. Thus, the objec-
tive of this study is to evaluate hydrolytic degradability of
appropriate amounts of auto-oxidized soybean oil (poly-
meric soybean oil), ESO and soybean oil based PLA mem-
branes since the composition, structure and/or miscibility
of the blended components are known to be key factors
influencing the resulting degradation rate [13]. Moreover,
surface and bulk properties of degraded soybean-oil based
PLA membranes have been evaluated by assessing the
effects of oil blending on weight loss, molecular weight,
thermal and morphological changes during degradation
period both in vitro and in vivo.
Materials and Methods
Soybean oil (SOYA) (MW: 3.2 kDa) and ESO (MW:
3.0 kDa) were locally purchased from (Çotanak, Turkey)
and antioxidant adduct inside the commercial soya oil was
removed by leaching. Lactic acid monomer (d,l-Laktid)
was obtained from Sigma-Aldrich (Germany) and all the
other chemicals (Sigma-Aldrich, Germany) were analytical
grade and used without further purification.
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J Polym Environ
Ring Opening Polymerization of PLA
Lactic acid monomer (d,l-Laktid) was polymerized via ring
opening polymerization (ROP) according to the procedure
written below. Briefly, the catalyst, 0.03 g of tin(II) octo-
ate and the initiator, 0.2 mg 1-dodecanol were charged into
a flame-dried Schlenk flask and argon gas was introduced
through a needle into the tube for about 3 min to expel the
air. Then, 2 g of d,l-Laktid and toluene was introduced and
the flask was placed in an oil bath preheated at 110 °C for
24 h and the reaction was finalized by adding cold chloro-
form and the catalyst was filtered out. The crude polymer
was dissolved in dichloromethane and poured into excess
methanol to precipitate the polymer. Then, the precipitated
polymer (PLA) was dried under a vacuum for 24 h (MW:
138.1 kDa, Mn: 78.3 kDa, PDI: 1.8).
Auto‑oxidation of Polymeric Soybean Oil (PSO)
The polymeric soybean oil (PSO) was prepared due the
auto-oxidation according to previously reported procedure
in the literature [20]. In brief, soybean oil (50 g), spread
out in a Petri dish (Ø = 16 cm), was exposed to sunlight in
the air at room temperature. After 8 weeks, a gel polymer
film associated with a waxy and viscous liquid was formed.
Chloroform extraction of the crude polymeric oil for 24 h
at room temperature allowed separation of the soluble part
of the PSO from the gel. In our previous study, the scheme
of auto-oxidation process and the chemical structures of
PSO, soy bean oil (SOYA) and ESO have been demon-
strated [30].
Preparation and Characterization of PLA/Oil (PLA/
PSO, PLA/SOYA, PLA/ESO) Membranes
PLA/oil polymeric blends were prepared by stirring appro-
priate portions (w/w) of PLA and oil (PSO, SOYA and
ESO) overnight at room temperature. PLA/oil blends were
prepared in chloroform in order to achieve 2, 7, 14, and
20% (w/w) oil in blends. Blends were assigned as PLA/
oil2, PLA/oil7, PLA/oil14, and PLA/oil20 which represents
oil composition in blends. Then, solvent-casting technique
was used in order to maintain PLA/oil membranes with
approximately 0.2 mm thickness (measured from SEM
image, data not shown). Briefly, 0.04 g/mL blend solution
(10 mL) poured in a Petri dish (Ø = 16 cm), then a transpar-
ent, smooth polymer film was obtained in 1–2 days of sol-
vent evaporation. Then, the film was easily peeled off from
Petri dish by adding some water on it. The film was subse-
quently dried under vacuum for a week at room tempera-
ture. The molecular weights of prepared membranes were
determined by gel permeation chromatography (GPC),
Viscotek GPCmax Auto sampler system (G2000H HR,
J Polym Environ
G3000H HR and G4000H HR), and a Viscotek differential
refractive index detector (THF flow rate of 1.0 mL/min). A
calibration curve was generated with PS standards having
narrow molecular weight distribution. Data were analyzed
using Viscotek OmniSEC Omni–01 software. Molecular
weight loss (%) was calculated form data maintained from
GPC results. The morphology and surface topography of
PLA/oil membranes were visualized by using a SEM (FEI
Quanta 200 FEG, USA) after coating with a thin gold–pal-
ladium alloy layer under vacuum. In order to evaluate ther-
mal characteristics of PLA/oil membranes, thermal gravi-
metric analysis (TGA) of the membranes was assessed by
(TA Q50, TGA) instrument in inert gas to determine ther-
mal maximum degradation ­(Tmax) and decomposition tem-
peratures ­[Td50(°C)] between 0 and 700 °C.
In Vitro Biodegradation
In vitro degradation studies of PLA/oil membranes were
carried out by hydrolysis in the presence of phosphate
buffer solution (PBS) (pH 7.4). Dry membranes (10 mm
diameter) were weighed and immersed in capped bottles
containing 5 mL phosphate buffer solution (PBS) (pH 7.4)
containing 0.02% sodium azide ­(NaN3) as the bacteriostatic
agent. Samples were incubated at 37 °C and the buffer was
refreshed for every week (8 weeks period). Three parallel
samples were withdrawn from the degradation medium at
1st, 4th, and 8th weeks, rinsed with distilled water three
times and then dried to constant weight in a vacuum at
room temperature. Weight loss was determined gravimet-
rically as the percentage of weight loss (­WL) according to
Eq. (1):
(1)
[( ) ]
WL (%) = W0 − W ∕W0 × 100
where, (W) is the dry weight remaining at a specific time
and ­(W0) is the initial weight.
After gravimetrical tests, biodegradation were also char-
acterized by GPC, thermal analysis and SEM methods as
described before.
In Vivo Biodegradation
In vivo biodegradation studies were performed on the
selected membranes (PLA, PLA-PSO14, PLA-SOYA14,
PLA-ESO14) due to the animal experiments proto-
col approved by TÜBİTAK Animal Experiments Ethic
Committee (Number: 16563500-111-85). Additionally,
ISO 10993-2:2006 “Animal Welfare requirements” and
ISO10993-12:2012 “Sample preparation and reference
materials” standards were taken into account. Briefly,
sterilized membranes [70% ethanol for 1 h, equilibrated in
sterile Dulbecco’s PBS (pH 7.4)] were implanted into dor-
sal subcutaneous tissue of three Sprague Dawley rabbits
(3–4 months, female). After 4 weeks of incubation, sam-
ples were withdrawn from the animals. The assessment of
the biodegradability after 4 weeks implantation of prepared
membranes was evaluated by gravimetrically according to
the Eq. 1 as described before. Additionally, samples were
also characterized by SEM, GPC and thermal analysis.
Statistical Analysis
All data are expressed as means ± standard deviations.
Three similar experiments were done which were carried
out in triplicate.
Results and Discussion
Biodegradation is one of the main challenges of the prepa-
ration of biomaterials for appropriate biomedical applica-
tions. Thus, tailoring biomaterial performance is required
which could be achieved by controlling the degradation
parameters. Several studies showed that degradation pro-
cess of PLA occurs by hydrolytic cleavage of ester bonds
which lead to decrease in the macromolecule average
length [31, 32]. In this study, a series of oil inclusion [2,
7, 14, and 20% (w/w) oil] in blends is evaluated in terms
of degradability of PLA/oil membranes. It has been previ-
ously reported that the miscibility was not accomplished
above 20% (w/w) of the oil content according to the physi-
cal observations [30].
In Vitro Degradation Behaviour of PLA/Oil
Membranes
Weight Loss and Molecular Weight Analysis
In vitro biodegradability of PLA/oil membranes were quan-
titatively assessed by gravimetrical analysis and percentage
weight loss of membranes after 1st, 4th, and 8th weeks of
incubation were shown in Table 1. According to Table 1,
oil inclusion greatly decrease degradation rate of mem-
branes compared to neat PLA. PLA membranes showed
4.6% weight loss for the first week although 1.1–3.6% of
PLA/oil membranes were degraded at the end of first week.
Since hydrolysis mechanism depends on the water attack
of the polymer chain, the interaction and location of water
molecules with polymer chain greatly influence the deg-
radation behavior [33]. Results showed that water can not
properly penetrate PLA/oil membranes during incubation
period. However, weight loss of PLA/ESO membranes
except PLA/ESO2 showed approximate values (3.0–3.6%)
compared to PLA (4.6%). After 4 weeks, PLA/PSO, PLA/
ESO and PLA/SOYA membranes showed 4.7–6.2%,
4.8–6.7%, and 3.9–4.7% weight loss, respectively while
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 J Polym Environ

Table 1  Percentage weight loss data during in vitro degradation peroxide and epoxide groups. Thus, large water uptake
period increase hydrolysis rate by ester groups on surface.
Membrane 1st week (%) 4th week (%) 8th week (%) Table 2 demonstrates percentage molecular weight loss
of membranes after 1st, 4th, and 8th weeks of incubation
PLA 4.6 ± 0.7 7.3 ± 1.2 7.8 ± 0.7
according to GPC results. After 1 week of degradation,
PLA-PSO2 2.0 ± 0.6 4.7 ± 0.2 4.9 ± 0.7
PLA, PLA/PSO, PLA/SOYA and PLA/ESO membranes
PLA-PSO7 1.1 ± 0.1 4.6 ± 0.5 5.9 ± 0.6
show 1.0%, 10.5–17.0%, 1.0-4.6%, and 1.9–8.8% molecu-
PLA-PSO14 2.4 ± 1.1 6.1 ± 0.5 6.6 ± 0.5
lar weight loss, respectively. Results can be related to sur-
PLA-PSO20 2.1 ± 0.7 6.2 ± 0.5 7.3 ± 0.4
face degradation of PLA membranes. Despite weight loss,
PLA-SOYA2 1.3 ± 0.7 3.9 ± 0.5 5.1 ± 0.3
degradation occurs at surface which leads thinning effect
PLA-SOYA7 2.0 ± 0.7 3.5 ± 0.1 5.0 ± 0.7
occurs molecular weight remains intact [33]. Figure 1
PLA-SOYA14 2.0 ± 0.6 4.7 ± 0.6 5.0 ± 0.4
represents the changes in molecular weight distribution
PLA-SOYA20 1.9 ± 0.8 3.9 ± 1.7 5.4 ± 0.5
for membranes during degradation period. It is observed
PLA-ESO2 1.0 ± 0.9 4.8 ± 0.2 4.8 ± 0.6
that molecular weight distribution of PLA membrane not
PLA-ESO7 3.6 ± 0.1 6.3 ± 0.8 5.9 ± 0.6
significantly lowers with time until 4 weeks and then the
PLA-ESO14 3.4 ± 0.2 6.8 ± 0.4 7.2 ± 0.4
molecular weight distribution is seen to move towards
PLA-ESO20 3.0 ± 0.2 6.7 ± 0.3 7.3 ± 0.3
lower values at the end of 4 weeks. Similar results were
observed for PLA/ESO and PLA/SOYA membranes
(Fig. 1). Results conclude that the degradation behavior of
PLA degraded 7.3% (Table 2). Surprisingly, results showed PLA, PLA/ESO and PLA/SOYA membranes occur at the
that the increase of oil content in PLA/PSO and PLA/ESO surface by erosion during 1 week. After 4 weeks, bulk deg-
membranes greatly increase weight loss which may be due radation occurs where medium is able to penetrate entire
to the fact that oil began to move away from the structure. polymer and random hydrolytic chain scission takes place
Higher water interaction results in an increased hydrolysis [29]. However, PLA/PSO membranes show bulk degrada-
rate as more water penetrates the samples. At the end of tion behaviour starting from first week (Fig. 1). Significant
8 weeks, similar values of percentage of weight loss were weight distribution shifting is observed for all membranes
obtained for PLA (7.8%), PLA/PSO (4.9–7.3%) and PLA/ at the end of 8 weeks which is due to the fact that diffusion
ESO (4.8–7.3%) membranes except PLA/SOYA (5.0-5.4%) of water into polymer is faster than degradation of polymer
(Table 2). Results concluded that during in vitro degrada- bonds [29] although weight loss is not significant at the
tion process PSO and ESO stability within highly concen- end of 8 weeks (Table 1). When by-products are removed
trated oil blended PLA membranes is less than SOYA sta- from the polymer matrix in uniform manner, chain scission
bility which may be due to the peroxide and epoxide groups becomes homogeneous; in contrast, if they can not able to
on PSO and ESO, respectively. This is probably because diffuse out, internal autocatalysis occurs which leads to a
of water molecules are entrapped by highly concentrated bimodal molecular weight distribution [34]. During bulk

Table 2  Percentage molecular Membrane Molecular weight (Mw) loss (%) Molecular weight (Mn) loss (%)
weight (Mw, Mn) loss data
during in vitro degradation 1st week 4th week 8th week 1st week 4th week 8th week
period
PLA 1.0 24.7 60.4 0.2 32.7 67.4
PLA-PSO2 10.5 51.0 76.6 8.5 30.1 66.0
PLA-PSO7 14.3 48.9 73.0 10.5 46.8 66.8
PLA-PSO14 17.0 33.6 68.1 28.5 29.8 59.7
PLA-PSO20 15.3 49.4 73.0 31.2 52.2 70.0
PLA-SOYA2 2.5 37.4 55.1 2.2 43.3 71.0
PLA-SOYA7 4.6 33.2 64.5 4.0 43.6 64.2
PLA-SOYA14 2.1 27.8 59.3 1.5 30.4 62.5
PLA-SOYA20 1.0 28.3 58.0 3.4 28.6 56.3
PLA-ESO2 4.8 29.5 51.8 4.9 32.0 47.4
PLA-ESO7 4.7 22.3 44.5 8.9 29.8 41.5
PLA-ESO14 1.9 17.0 39.7 2.4 21.6 37.3
PLA-ESO20 8.8 22.6 45.2 2.0 20.4 40.8

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J Polym Environ
Fig. 1  GPC spectrum of membranes before and after in vitro degradation
degradation double peak distributions are observed for
PLA/SOYA and PLA/PSO after 8 and 4 weeks, respec-
tively (Fig. 1).
SEM Analysis
SEM images of PLA and PLA/oil membranes before and
during degradation period are demonstrated in Figs. 2, 3, 4
and 5. PSO droplets on PLA/PSO membranes were homog-
enously distributed before degradation and the increase
in PSO content results larger oil droplets covered on the
membranes (Fig. 2). After 1 week oil drops became non-
homogenous through polymer film and small pores and
cavities appeared after 4 weeks which is consistent with
bulk degradation [29]. After 8 weeks no PSO droplets
were observed for PLA/PSO2 and PLA/PSO7 membranes,
instead small pores were clearly seen (Fig. 2). No signifi-
cant changes were observed for PLA membranes; however,
after 4 weeks small cracks were observed on PLA surfaces
by SEM analysis under higher magnifications (×5000) (not
shown) which indicates bulk degradation. As seen from
Fig. 3, SOYA was homogenously distributed and embed-
ded through surface of PLA/SOYA membranes without
any oil droplets before degradation. However, starting from
the first week, oil droplets appeared on surface and larger
SOYA droplets are observed regarding to oil content in
membranes (Fig. 3). Small pores and cavities are shown by
SEM images after 4 weeks (Fig. 3) similar to images for
PLA/PSO membranes (Fig. 2). However, after 8 weeks no
oil droplets were seen on the surface of membranes and
pores on the membrane surfaces are attractive (Fig. 3).
Before degradation, ESO was homogenously distributed
by oil droplets on PLA/ESO2 and PLA/PSO7 surface, and
embedded through the surface of PLA/ESO14 and PLA/
ESO20 (Fig. 4). Similar to PLA/SOYA membranes, oil
droplets are appeared on the PLA/ESO membranes after
1 week (Fig. 4) which indicate surface erosion. However,
after 4 weeks no oil droplets are observed on the mem-
branes and pore became larger and striking after 8 weeks
(Fig. 4).
Thermal Gravimetric Analysis (TGA)
Thermal degradation behaviour of membranes during
degradation period is monitored by TGA thermograms
where thermal stability factors, including temperature
13

Fig. 2  SEM images of PLA and PLA/PSO membranes before and after in vitro degradation, (scale bars on SEM images: 0 week: 100 µm,
1 week: 50 µm, 4 and 8 weeks: 40 µm)
of maximum rate of degradation (­Tmax) and decomposi-
tion temperature at 50% weight loss ­(Td50) of the mem-
branes can be determined. Results obtained from TG
and DTG curves were shown in Table 3. As seen from
Table 3, before degradation maximum degradation tem-
peratures are not changed by oil blending except PLA/
ESO20 membranes. Moreover, oil blending decrease
decomposition temperature which may be due to the
co-existance of the two polymers [35]. During degrada-
tion period, slight decrease in ­Tmax and ­Td50 values are
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J Polym Environ
detected due to the shorter polymer chains occurred by
degradation (Table 3). However, significant decrease of
­Tmax and T ­ d50 values for PLA/ESO membranes (except
ESO2) during degradation period. The reduction can be
related to epoxy groups on membranes. Although studies
have shown the improvement of thermal stability of PLA
with epoxy processing [35], after hydrolysis the interac-
tion of epoxy with lactic acid fragments may probably
makes ESO possible to reorganize on shorter polymer
chains of the membrane which leads higher thermal deg-
radation rates.
J Polym Environ
Fig. 3  SEM images of PLA/SOYA membranes before and after in vitro degradation, (scale bars on SEM images: 0 week: 100 µm, 1 week:
50 µm, 4 and 8 weeks: 40 µm)
In Vivo Degradation Behaviour of PLA/Oil Membranes
Several studies have shown that in vivo degradation behav-
iour is dramatically different from that for in vitro degra-
dation [36, 37]. The difference is due to the biological
compounds and lipids in body which facilitates uptake of
water into polymer or the body responses that contributes
to the faster degradation in vivo [38, 39]. Table 4 demon-
strates in vivo percentage weight loss, percentage molecu-
lar weight loss data and ­Td50 and ­Tmax values of PLA and
PLAoil14 membranes after 4 weeks of degradation. All
membranes show approximately twofold high values of
percentage weight loss data when degraded in vivo after
4 weeks compared to in vitro (Table 4). After 4 weeks of
in vivo degradation, PLA, PLA/PSO14, PLA/SOYA14 and
PLA/ESO14 membranes show 70.3, 72.6, 68.9 and 58.7%
molecular weight loss, respectively (Table 4). Results indi-
cate dramatic increase of molecular weight loss where bulk
degradation occurred for all membranes, confirmed by
molecular weight distributions (data not shown). Moreo-
ver, double peak distribution is observed for PLA/SOYA14
(data not shown) which indicates internal autocatalysis
[34]. Thermal properties of membranes after 4 weeks of
in vivo degradation (Table 4) show similar decrease pro-
files in ­Tmax and ­Td50 values for PLA, PLA/SOYA14 and
PLA/ESO14 membranes compared to 4 weeks of in vitro
degradation results. However, significant decrease of T­ max
and ­Td50 values for PLA/PSO14 membranes were detected
after 4 weeks of in vivo degradation (Table 4) which may
be related to higher weight loss and molecular weight loss
with regard to shorter polymer chains. SEM images of
in vivo degraded membranes were demonstrated in Fig. 5.
Accelerated degradation of membranes could be deduced
from SEM images where cracks, fissures, cavities and pores
on membranes are clear and prominent (Fig. 5). To summa-
rize, our results are in agreement with the previous reports
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Fig. 4  SEM images of PLA and PLA/ESO membranes before and after in vitro degradation, (scale bars on SEM images: 0 week: 100 µm,
1 week: 50 µm, 4 and 8 weeks: 40 µm)
which described that the mechanism for in vivo degrada-
tion is different from that for in vitro degradation [36].
Conclusions
In vitro and in vivo degradation behaviour of PLA and
PLA/oil membranes were monitored by following weight
loss, changes of molecular weight, thermal properties and
morphology. The hydrolytic degradation of membranes
showed different mechanisms according to the varied oil
(PSO, ESO and SOYA) inclusion and amounts during
degradation period in vitro. SOYA inclusion greatly low-
ers degradation rate with mainly bulk degradation mecha-
nisms after 4 weeks in vitro, followed by surface erosion
for the first week. High concentrated PSO and ESO inclu-
sion increase weight loss and significant molecular weight
loss is obtained for PSO blended membranes starting
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from first week which leads bulk degradation behaviour.
No significant change was observed for PSO and SOYA
blended membranes, while ESO inclusion was seen to
decrease thermal degradation rates. During in vitro degra-
dation period, small pores occurred on oil included mem-
branes while no significant change (only small cracks) was
observed on PLA membranes. Compared to in vitro deg-
radation data, significant mass loss and molecular weight
loss were detected for all membranes degraded in vivo by
bulk degradation mechanism. Different from in vitro pro-
file, PSO significantly increase weight loss and molecular
weight loss with high thermal degradation rates. Accord-
ing to visual examination of degraded membranes, con-
siderable degradation on membranes was observed with
clear fissures, pores and cracks. However, it should be
noted that further mechanical testing may be considered
which will support degradability of membranes when with
in vivo applications. Thus, results concluded controllable
J Polym Environ

Fig. 5  SEM images of a PLA, b PLA/PSO, c PLA/SOYA and d PLA/ESO membranes after 4 weeks in vivo degradation, (scale bars on SEM
images: 40 µm)

Table 3  Thermal properties Membrane Td50 (°C) Td50 (°C) Td50 (°C) Td50 (°C) Tmax (°C) Tmax (°C) Tmax (°C) Tmax (°C)
of membranes before and after 1st week 4th week 8th week 1st week 4th week 8th week
in vitro degradation
PLA 364.2 354.7 349.1 344.8 365.6 361.5 359.1 356.3
PLA-PSO2 363.4 348.1 347.0 344.8 366.2 355.9 354.8 349.8
PLA-PSO7 359.2 345.5 343.3 344.6 366.5 355.7 350.3 348.4
PLA-PSO14 359.5 345.0 342.5 342.1 365.6 354.6 350.3 347.6
PLA-PSO20 357.7 344.9 341.5 341.9 366.7 353.5 349.8 348.8
PLA-SOYA2 362.4 355.3 346.4 345.9 366.5 361.4 357.7 352.6
PLA-SOYA7 359.4 353.3 345.5 341.8 366.5 361.4 355.4 350.2
PLA-SOYA14 359.1 348.9 342.9 343.3 366.1 359.4 351.8 349.3
PLA-SOYA20 357.6 348.9 342.9 339.2 367.8 359.1 350.9 345.6
PLA-ESO2 356.9 342.7 340.8 338.8 366.5 355.4 353.6 352.9
PLA-ESO7 335.0 328.7 324.9 316.3 365.1 323.4 320.3 318.4
PLA-ESO14 334.9 324.3 313.9 319.1 364.5 324.6 318.5 318.2
PLA-ESO20 327.7 317.7 312.3 315.7 326.1 319.5 317.6 316.0

Td50: Decomposition temperature at 50% weight loss (TG curve)

Tmax: Temperature at maximum degradation rate (DTG curve)

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Table 4  In vivo degradation Membrane Weight loss (%) Mw loss (%) Mn loss (%) Tmax (°C) Td50 (°C)
data of membranes after
4 weeks PLA 14.1 70.3 68.7 364.1 357.5
PLA-PSO14 17.4 72.6 68.5 308.3 304.4
PLA-SOYA14 10.5 68.9 47.3 358.4 350.0
PLA-ESO14 14.4 58.7 49.1 315.3 317.5

degradation profiles which encourage the use of soy bean
oil based materials as biomaterials for several biomedical
applications.
Acknowledgements The authors would like to thank financial sup-
ports of Turkish Scientific Research Council (TÜBİTAK) (Grant
Number: 213M375) and Bülent Ecevit University Research Fund
(Grant Number: 2014-39971044-02).
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