Author’s Accepted Manuscript

The mechanical, thermal and morphological

properties of γ-irradiated PLA/TAIC and
PLA/OvPOSS

Mehmet Kodal, Abdulmounem Alchekh Wis,

Guralp Ozkoc
www.elsevier.com/locate/radphyschem

PII: S0969-806X(18)30531-0
DOI: https://doi.org/10.1016/j.radphyschem.2018.10.018
Reference: RPC8034
To appear in: Radiation Physics and Chemistry
Received date: 3 June 2018
Revised date: 14 October 2018
Accepted date: 19 October 2018
Cite this article as: Mehmet Kodal, Abdulmounem Alchekh Wis and Guralp
Ozkoc, The mechanical, thermal and morphological properties of γ-irradiated
PLA/TAIC and PLA/OvPOSS, Radiation Physics and Chemistry,
https://doi.org/10.1016/j.radphyschem.2018.10.018
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 The mechanical, thermal and morphological properties of γ-irradiated
PLA/TAIC and PLA/OvPOSS
Mehmet Kodal*, Abdulmounem Alchekh Wis and Guralp Ozkoc
Department of Chemical Engineering, Kocaeli University, 41380 Kocaeli/Turkey
*Corresponding author: Dr. Mehmet Kodal TEL: +902623732802 (KOCAELI/TURKEY)
FAX: +902623732719, E-mail: mehmet.kodal@kocaeli.edu.tr
Abstract

In the present work, various blend ratios of poly (lactic acid) (PLA), triallylisocyanurate (TAIC)
and octavinyl-POSS (OvPOSS) were prepared by melt compounding in an Xplore
microcompounder and molded by an Xplore microinjection molding device. POSS is a new
generation organic/inorganic hybrid nanoparticle having possibility to improve the performance
of polymers without sacrificing mechanical and thermal properties. TAIC and OvPOSS were
used as crosslinking agents. After the compounding process, PLA, PLA/TAIC and
PLA/OvPOSS composites were exposed to a gamma irradiation at various adsorbed doses
ranging from 0 to 100 kGy. The properties of neat PLA, PLA/TAIC and PLA/OvPOSS
composites were investigated using scanning electron microscopy (SEM), Fourier transform
infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermal gravimetric
analysis (TGA) and tensile testing. Results showed that both chain scission reactions and
formation of network structure occurred simultaneously after gamma irradiation. The highest gel
formation was obtained from PLA composites including 3 wt% OvPOSS at the dose of 100 kGy.
DSC results indicated that a sharp decrease in the degree of crystallinity (Xc%) of PLA in the
presence of TAIC and OvPOSS was obtained after gamma irradiation process. All irradiated
composites exhibited lower elongation at break and higher E-Modulus values at any irradiation
doses. TGA results showed that irradiated samples were more thermally stable than the
unirradiated ones. Moreover, the heat deflection temperature (HDT) of PLA in the presence of
TAIC and OvPOSS was found higher than that of neat PLA. Brittle surface morphology of
composites after gamma irradiation process was obtained from SEM analysis.

Graphical Abstract:

1
Keywords:
PLA; gamma irradiation; crosslinking; TAIC; POSS

1 INTRODUCTION
Recently, poly(lactic acid) (PLA) has been extensively considered by researchers as a suitable
candidate for replacing some synthetic polymers, because of its good mechanical properties, ease
of processability, lower environmental impact and its renewable resources [1-3]. PLA is a high
potent material since it combines attractive mechanical properties, high transparency,
biocompatibility and reasonable price. Thus, PLA is considered as an ideal candidate to be used
as an alternative to non-biodegradable polymeric materials in several applications [4]. Moreover,
PLA can be processed in conventional machines that are commonly used for non-degradable
polymers. On the other hand, its poor heat stability, thermal resistance and low crystallization
ability limit applications of PLA. The modulus of PLA decreases instantly above its glass
transition temperature (Tg) of between 50 to 65˚C. Therefore, thermo-mechanical stability of
PLA has to be improved in order to widen its commercial exploitation [5].
Recently, researchers from both industry and academia have focused on to improve the
negative aspects of PLA through different chemical and physical methods, such as blending with
other polymers, introducing stereocomplex crystals and nanoparticles or crosslinking [6-9]. PLA
can be cross-linked either by irradiation or by chemical reactions [10]. The radiation types such
as electron beam and gamma-irradiation are generally used to crosslink PLA together with small
amounts of chemical agents such as trimethylopropane triacrylate (TMPTA), triallyl

2
isocyanurate (TAIC) and dicumyl peroxide (DCP), etc. [5, 9, 10-12]. In other words, the
radiation itself only drops the molecular weight of the PLA that results in the deterioration of the
properties. On the other hand, the radiation of PLA using ionizing radiation in the presence of
multifunctional compounds, so called crosslinking agents, is advantageous since they result in
the formation of crosslinking, which promotes its thermal stability and mechanical properties.
One should also note that the crosslinking occurs together with degradation processes in
amorphous regions of PLA. This may result in formation of various radical structures, which
leads to recombination, dissociation, disproportionation, etc. reactions [13].
One of the frequently used agents for crosslinking PLA is TAIC. The radiation cross-linked
PLA with TAIC shows low crystallinity and exhibits relatively lower melting point; whereas, it
enhances the thermal stability [14]. It was reported in the literature that TAIC content of 8% and
radiation dose of 30 kGy were found as optimum conditions to perform crosslinking in PLA
[14].
In addition to that, polyhedral oligomeric silsesquioxane (POSS)-based nanomaterials have
attracted great attention over the past decade because of their unique structure [15] providing
new and potentially valuable applications that make them attractive as an additive for many
polymers [16]. POSS organic/inorganic hybrid materials are nominated as alternative nanofillers
having the ability of reinforcement and high temperature stabilization of the polymers [17-19].
POSS having chemical formula of (RSiO1.5)n (n is generally 8) has a -Si-O- cage-like skeleton
with organic side groups. These side groups can be reactive and/or non-reactive groups. The type
of these side groups are very important since they reveal the compatibility of POSS types with
polymers. Besides, the silicone-rich skeletal structure can enhance the mechanical properties and
flame-retardancy of polymers [17-21]. POSS can also be utilized as a crosslinking agent for
many polymers. Choi et al. prepared polypropylene (PP)/multifunctional acrylo POSS
nanocomposites via melt blending method. The samples were subjected to γ-ray irradiation by
using 60Co source at various absorption doses till 100 kGy. They stated that the tensile strength
of PP/POSS nanocomposites improved up to 5 wt% POSS as the absorption dose increased up to
50 kGy [22]. Wu et al. reported a new methodology to prepare crosslinked low density
polyethylene (LDPE) by using POSS particles as crosslinking agents. They found that the
crosslinking degree increased with POSS content [23].

3
 To best of our knowledge, a limited number of researches have been reported for the use of
POSS in crosslinked biodegradable polymers, which is the motivation for the present research.
Jung and coworkers prepared e-beam radiated PLA/poly(ethylene glycol)-functionalized POSS
(PEG-POSS) nanocomposites with/without TAIC as a crosslinking agent to improve the
flexibility of PLA. In this study, PEG-POSS used as a plasticizing agent. They reported that in
the presence of TAIC the degree of crosslinking reached up to 80%. PEG-POSS content of 15%
was found to be the most flexible composition. In addition, 44.5 MPa strength was obtained at
the 100kGy radiation dose [24].
In the present study, preparation of PLA/TAIC and PLA/POSS composites and radiation-
induced crosslinking were investigated to enhance the thermal stability of PLA. Octavinyl-POSS
(OvPOSS) including double bonds was used for the first time as a crosslinking agent for PLA.
The criterion in the selection of the POSS type is the presence of multiple double bonds that
provides the grafting of POSS to the PLA molecules during radiation. The properties of
PLA/TAIC was also investigated to make a comparison with PLA/OvPOSS system. The
mixtures was irradiated at different doses, ranging from 0 to 100 kGy. The OvPOSS content was
1 and 3%, while the TAIC content was 3% and 7% by weight in PLA. The molecular structures,
mechanical properties, thermal behavior, and morphology were investigated as a function of
irradiation doses.

2 EXPERIMENTAL
2.1 Materials
Poly(lactic acid) (PLI005) with an MFI of 16 g/10 min at 190°C/2.16 kg was obtained from
NaturePlast, France. The number average molecular weight of PLA was measured as 106000
Daltons using gel permeation chromatography (GPC). The heterogeneity index was 1.97.
Octavinyl-POSS (OvPOSS) and TAIC, as crosslinkers, were purchased from Hybrid Plastics
Company and Sigma Aldrich, respectively. Their chemical structures are shown in Table 1.
OvPOSS, a white crystalline solid at ambient conditions, can be dissolved in tetrahydrofuran
(THF), chloroform and hexane. PLA also dissolves in these solvents that points out a possible
compatibility.

4
 Table 1. Chemical structure of OvPOSS and TAIC used in this study
Material Chemical Structure

Octavinyl-POSS (OvPOSS)

Triallyl isocyanurate (TAIC)

2.2 Sample preparation by microcompounding and injection molding

Prior to processing, PLA was dried at 50°C for 12 h under vacuum. PLA/TAIC and
PLA/OvPOSS at two different concentrations were prepared via melt blending in a twin-screw
microcompounder (MC15, Xplore Instruments, The Netherlands) at a screw speed of 100 rpm.
The barrel temperature of microcompounder was set to 180°C. The mixing time was kept
constant at 3 min. At the end of mixing, the molten extrudate was directly transferred to the
injection-molding machine (IM12, Xplore Instruments, The Netherlands). The molten
compound was subsequently injection molded. The injection and holding pressures were set to
10 bars. Melt temperature and mold temperature were 180°C and 25C, respectively. A
schematic showing of the processing is given in Figure 1.

5
 Figure 1. Schematic showing of the sample preparation steps

2.3 Gamma irradiation

Pure PLA, PLA/TAIC and PLA/OvPOSS composites were irradiated using a 60Co-γ source,
at 25°C (JS 9600 MDS NORDION) in Gamma Pak Company (Tekirdag, Turkey). According to
the data supplied by the company, the radiation dose rate was 2.5 kGy/h and the activity of the
source was 1.2 Mci. Target doses of 0, 25, 50, and 100 kGy were applied. The samples were
located in double layered 25 microns HDPE bag and vacuumed prior to irradiation. When the
irradiation equipment is in off-position, the source panel is in a water-filled pool of 8 m by 6 m.
In order to put the equipment in the irradiation position, the source panel is brought towards the
Al-boxes containing samples using a pneumatic piston. Then the boxes move around the source
as “go-stop” and are beamed up at 53 different positions. At the end of the time, they are
automatically taken outside by the conveyor system. The irradiation equipment and the conveyor
system are commanded in full automatically by computer.
The samples were abbreviated with respect to the loading level of OvPOSS or TAIC and the
irradiation dose. For instance, “PLA/OvPOSS1 - 25” represents the sample containing 1 wt%
octavinyl-POSS, which was irradiated at a dose of 25 kGy.

6
2.4 Characterization
The mechanical properties of samples were obtained by using Instron 3345 model universal
testing machine according to ISO 527(5a). The sample thickness was 2 mm, and the width of the
narrow section is 4 mm. The overall length of the sample was 75 mm. The crosshead speed was
10 mm/min. In order to obtain a significant value, 10 samples were tested from each batch.
In order to obtain heat deflection temperature (HDT) according to ASTM D648, a constant
load of 0.46 MPa was applied at the center of 3-point bending flexural bars having dimensions of
5" x ½" x ¼". The samples were heated from 25 to 200°C at a heating rate of 2°C/min and
sample deflection was recorded as a function of temperature. Five samples from each batch were
tested to obtain an average value.
The infrared spectra (FTIR) were obtained at room temperature using Perkin Elmer spectrum
100 FTIR instrument equipped with a diamond ATR crystal. The samples were analyzed in the
range of 4000–600 cm−1.
The differential scanning calorimetry (DSC) of samples was performed using a Mettler
Toledo DSC1 Star instrument under nitrogen atmosphere. Samples were heated from 25 to
200°C at a heating rate of 10°C/min. Glass transition temperature (Tg), cold crystallization
temperature (Tcc), melting temperature (Tm) and enthalpies of melting (ΔHm) and cold
crystallization (ΔHc) of PLA, PLA/TAIC and PLA/OvPOSS were determined via DSC
thermograms. The percent crystallinity (%XC) of the samples was calculated according to Eq. 1:

) x 100

(1)

where ΔHm is the melting enthalpy (J/g), ΔHc is the cold crystallization enthalpy (J/g) and ΔHm*
is the melting enthalpy of 100% crystalline PLA (93 J/g, [25]) and ϕ is the fraction of PLA in the
composites.
Thermal gravimetric analysis (TGA) was conducted to determine the thermal stability of the
composites under nitrogen atmosphere. A TA Q50 model TGA instrument was used. Test
samples were heated from room temperature to 600°C at a heating rate of 20°C/min.

7
 The microstructure of the tensile-fractured samples were investigated by performing scanning
electron microscopy (SEM) using a JEOL JSM 6060 model scanning electron microscope. The
samples were gold coated before observations to prevent arching.
Samples of 0.5 g for gel extraction were cut from the tensile specimens. Eq. 2 was used to
determine the gel fraction measured by the amount of insoluble materials in chloroform:

Gel fraction (%) = (Wg / W0) * 100 (2)

where W0 is the dry-weigth of the sample and the Wg is the remaining weight (dry gel
component) of the sample after dissolving in chloroform at room temperature for 24 h [9].
Degree of swelling (DS) that is the volume ratio of absorbed solvent to dry gel sample was
calculated with respect to Eq. 3 [9]:

DS = [( Ws – Wg ) / ( Wg )] ( ρp / ρS ) (3)

where Wg is the weight of dry gel component in the crosslinked sample, Ws is the weight of gel
component swollen at room temperature for 48 h in chloroform. ρp and ρS are densities of
polymer and solvent, respectively [9].

3 RESULTS AND DISCUSSION

3.1 Degree of swelling and gel fraction of PA/TAIC and PLA/OvPOSS
Gel fraction of the gamma irradiated samples are shown in Figure 2A as a function of
radiation dose and composition. The relevant results concerning PLA were not presented,
because there is no gel formed for PLA, it completely dissolved in chloroform. This indicated
that when PLA subjected to the irradiation, it did not show crosslinking, but exhibited chain
scission. The addition of TAIC to PLA increased the gel fraction regardless of radiation doses.
As the TAIC content increased from 3 to 7 wt%, the gel content increased for any given radiation
dose. The difference in gel content at 25 and 50 kGy doses was very close to each other with

8
respect to increasing TAIC content, whereas much higher differences obtained at 100 kGy
depending on the amount of TAIC. The highest gel content of 76% was obtained at 7 wt% TAIC
at 100 kGy radiation dose for PLA/TAIC system.
As PLA/OvPOSS system was considered, higher gel contents were obtained for the entire
radiation doses as compared to the 1 and 7% TAIC containing PLA samples. The increasing
OvPOSS in the PLA from 1% to 3 wt% yielded a drastic increase in the gel content for
especially higher radiation doses such as 50 kGy and 100 kGy. Among these irradiated
composites, the highest gel content of 86% is obtained in the presence of 3 wt% Ov-POSS at the
dose of 100 kGy, which indicates the formation of highly crosslinked PLA. The results of gel-
fraction experiments indicated that OvPOSS is a very efficient crosslinker for PLA in radiation
crosslinking system. Even at very low contents such as 1 wt%, the higher degree of crosslinking
can be achieved for PLA/OvPOSS in comparison to the conventional PLA/TAIC system.
The other indication of the degree of crosslinking is the degree of swelling. As in the case of
gel fraction measurement, since the neat PLA did not undergo crosslinking but showed chain
scission when exposed to gamma radiation, it was completely dissolved in chloroform, therefore
degree of swelling could not be obtained for PLA. Degree of swelling of the gamma irradiated of
samples are shown in Figure 2B as a function of radiation dose and composition. The increasing
radiation dose resulted in a decrease in the swelling degree of PLA/TAIC system. Larger
radiation doses increased the degree of crosslinking besides the chain scission of PLA, which
created hindrance to the solvent sorption by the polymer and, consequently, degree of swelling
decreased; but from a certain level, the increasing radiation dose did not influence the
crosslinking degree. This can be attributed to the possibility that at higher radiation doses, the
PLA chain scission reactions may overcome the PLA crosslinking reactions [13]. In contrast, a
gradual declining trend was obtained for PLA/TAIC7 sample with the increasing radiation dose.
The swelling test results were well correlated with gel fraction results for PLA/TAIC samples,
which implies that the crosslinking hindered the molecular expansion during swelling. The
degree of swelling for PLA/OvPOSS was found to be lower than that of PLA/TAIC for any
given radiation dose and concentration. This means that the degree of crosslinking for
PLA/OvPOSS was higher than that of PLA/TAIC The degree of swelling reduced from 25 kGy
to 50 kGy for both PLA/OvPOSS1 and PLA/OvPOSS3, then stayed the same with increasing

9
radiation dose to 100 kGy. The degree of swelling was smaller for the entire dose range for 3%
OvPOSS, which means that the amount of crosslinking was higher.

Figure 2. A) Gel fraction, B) Degree of swelling of PLA/TAIC and PLA/OvPOSS composites

at different radiation doses

3.2 FT-IR analysis

The chemical changes in the structure of irradiated samples of neat PLA, PLA/TAIC, and
PLA/OvPOSS composites were analyzed by FTIR. The gamma radiation of polymers can result
in the formation of various radicals, intermediates, which lead the formation of different
chemical structures as a result of disproportion, hydrogen abstraction and the formation of new
bonds that could induce varying extent of degradation and/or crosslinking reactions in polymers
[26].
Figure 3 shows the FTIR spectra of pure PLA after irradiation at various doses (25, 50, and
100 kGy). The absorption band located at 3506 cm−1 can be attributed to -OH groups in alcohols,
hydro-peroxides or carboxylic acids [27]. The intensity of this band increased and broadened in
the samples with doses of 50 and 100 kGy. The band at 1756 cm−1 confirmed the presence of the
ester via the carbonyl stretch (C=O), which increased absorbance as the irradiation dose
increased [27, 28]. The changes in the peaks seen in FTIR spectra for PLA could be associated
to the chain scission occurred simultaneously with oxidation reactions due to the irradiation
treatment, which resulted in change of the height of the absorption bands in FTIR spectra [27]. In

10
addition, due to the chain scission reactions, the –OH number increases since the number of
chain ends increased, which result in a higher intensity of –OH absorption band in FTIR spectra.

Figure 3. FTIR spectra of gamma irradiated PLA

TAIC is well-known since it is one of the most effective crosslinking agents for polyesters,
also for PLA [29]. Monomer radicals can easily form due to the breaking of the double bonds of
the TAIC and then combine with the polymer radicals to generate the crosslinked network [12].
The reflective FTIR spectra of PLA/TAIC composites are shown in Figure 4 and Figure 5,
respectively. The spectra of PLA/TAIC composites showed particular bands located at
3506 cm−1. New hydroxyl (-OH) and vinyl (-CH=CH2) groups were formed because of gamma
irradiation. The reason for hydroxyl group formation could be due to the surface oxidation as a
result of irradiation or from the thermal degradation of the polymer during melt processing [30].
The absorption band at 3506 cm−1 attributed to the hydroxyl groups was higher for PLA/TAIC7
than PLA/TAIC3 composites. Three bands observed at 2995, 2945 and 2875 cm−1 were
associated to the saturated CH3 stretching bands and symmetric/asymmetric deformation bands
of –CH of PLA/TAIC, respectively [27, 31]. After γ-irradiation exposure, the bands became
stronger in intensity as the absorbed doses increased. As can be seen in Figure 4 and Figure 5,
the spectra region between 1800 cm−1 and 850 cm−1 shows strong peaks at about 1180 cm−1 and
1756 cm−1, which belongs to the C–O–C stretching and C=O stretching of PLA/TAIC,

11
respectively [12, 32, 33]. The absorbance intensities of these two peaks increased with
increasing irradiation dose. This was due to the increasing oxidation of PLA during irradiation.
Figure 6 and Figure 7 show the FTIR spectra of PLA/OvPOSS composites after irradiation at
various doses. Strong symmetric peak located at 1120 cm-1 is related to Si-O-Si asymmetric
stretching vibrations of inorganic silsesquioxane cages [34] The peaks appeared at 3070 cm-1 and
1605 cm-1 were the C=C stretching vibrations of vinyl groups of POSS nanoparticles. For
PLA/OvPOSS composites, the disappearance of the bands located at 3070 cm-1and 1605 cm-1
confirmed the chemical crosslinking reactions of PLA chains with OvPOSS.

Figure 4. FTIR spectra of PLA/TAIC3 composites

12
 Figure 5. FTIR spectra of PLA/TAIC7 composites

Figure 6. FTIR spectra of PLA/OvPOSS1 composites

13
 Figure 7. FTIR spectra of PLA/TAIC7 composites

3.3 Mechanical test results

The mechanical properties of PLA, PLA/TAIC and PLA/OvPOSS composites are
investigated through tensile test on both irradiated and unirradiated samples. Irradiation of
polymers usually makes a big impact on the mechanical properties. These effects depend on the
resulting structure of the irradiated polymer, if it is crosslinked or degraded [35]. PLA has high
sensitivity to irradiation [36]. Table 2 shows the mechanical properties of non-crosslinked and
irradiation crosslinked PLA and PLA composites.

14
 Table 2. Mechanical properties of non-crosslinked and irradiation crosslinked PLA and PLA
composites
Sample designation E-Modulus (MPa) Tensile strength (MPa) Elongation at break (%)
PLA-0 3278 ± 264 63.4 ± 6.1 23.9 ± 3.4
PLA-25 2978 ± 361 20.1 ± 2.1 10.5 ±1.2
PLA-50 2728 ± 152 15.9 ± 1.8 8.8 ± 1.4
PLA-100 2228 ± 215 5.0 ± 2.7 2.0 ± 0.1

PLA/TAIC3-0 3219 ± 207 57.3 ± 3.6 26.5 ± 1.8

PLA/TAIC3-25 3544 ± 233 60.1 ± 3.4 14.8 ± 1.4
PLA/TAIC3-50 3668 ± 152 62.0 ± 4.2 11.1 ± 0.2
PLA/TAIC3-100 4261 ± 216 75.9 ± 1.1 5.3 ± 0.1

PLA/TAIC7-0 3151 ± 129 49.6 ± 1.9 27.3 ± 2.1

PLA/TAIC7-25 3643 ± 141 62.0 ± 2.4 12.3 ± 1.2
PLA/TAIC7-50 3755 ± 285 64.9 ± 2.9 10.6 ± 1.7
PLA/TAIC7-100 4279 ± 184 78.5 ± 4.1 4.3 ± 0.3

PLA/OvPOSS1-0 3269 ± 170 56.6 ± 2.4 23.4 ± 3.1

PLA/OvPOSS1-25 3604 ± 123 67.4 ± 3.0 9.6 ± 1.3
PLA/OvPOSS1-50 3710 ± 118 70.8 ± 2.4 8.4 ± 1.2
PLA/OvPOSS1-100 4284 ± 214 80.5 ± 0.9 1.0 ± 0.1

PLA/OvPOSS3-0 3378 ± 217 59.1 ± 1.6 20.9 ± 2.8

PLA/OvPOSS3-25 3783 ± 112 72.3 ± 2.6 9.0 ± 1.4
PLA/OvPOSS3-50 3852 ± 215 81.1 ± 4.3 6.3 ± 1.1
PLA/OvPOSS3-100 4367 ± 210 82.3 ± 3.4 0.5 ± 1.0

It was observed that as the dose increased, tensile strength, E-Modulus and elongation at
break of PLA severely decreased. These reductions in mechanical properties of PLA was due to
the fact that the chain-scission reactions resulted in reducing the molecular weight of PLA and
severely diminishing the intermolecular forces occurred during irradiation process [27]. As can
be seen in Table 2 that both the tensile strength and the E-modulus of the PLA/TAIC and
PLA/OvPOSS composites were significantly higher than that of the pure PLA at the enter
irradiation doses. This was probably due to the increasing in crosslinking density after irradiation
process, which caused PLA to stiffen. Moreover, at 100 kGy irradiation exposure, the highest
tensile strength and E-Modulus values obtained for the PLA composites including 3 wt%
OvPOSS and 7 wt% TAIC. As mentioned from the literature, TAIC forms radicals through the
breakage of the double bonds that interact with polymer macro-radicals to form the crosslinks
[9]. In addition, irradiated PLA/OvPOSS composites exhibited higher mechanical properties as
comparison with PLA/TAIC composites even at 1 wt% OvPOSS loading level. Higher
mechanical properties of PLA/OvPOSS compared to pure PLA and irradiated PLA/TAIC

15
composites at any given irradiation dose could be attributed to the that the double bonds on the
side chains of OvPOSS might provide grafting of POSS onto the PLA molecules during gamma
induced crosslinking. The possible reaction mechanisms of irradiated PLA samples were given
in the following section. Moreover, irradiation of PLA in the presence of TAIC and OvPOSS
caused considerable decreases in the elongation at break. The obtained value of elongation at
break for PLA/OvPOSS3 -100 was below 1%, which resulted from the enhanced crosslinking
density.

3.4 Reaction mechanism

As mentioned in the literature that if PLA is exposed to beam irradiation, active intermediates
such as free radicals and/or peroxyl free radicals, which will then interact with polymeric chains.
This situation result in chain scission through chain transfer and cutting of the polymer chain,
which lowers the molecular weight of PLA [37, 38]. It was mentioned in the literature that the
degradation upon irradiation for the lactide polymers is related to the presence of ester groups.
As the ester content increases, the probability of lactide degradation increases [39]. On the other
hand, a crosslinking agent can react with polymer free radicals, which leads a higher crosslinking
density when they are exposed to irradiation. Thus, it protects the ester bonds from breaking by
retarding the irradiation-induced chain scission [40]. These two reactions compete with each
other. In addition to that, the thermal degradation of the PLA during processing also follows a
radicalic scission path-way [41]. This also resulted in the formation of possible crosslinking in
the presence of a coagent with double bonds.
Hydrogen abstraction from the –CH groups in PLA chains predominantly occurred when
irradiated by beam irradiation to form radical as be seen in Figure 8 and Figure 9 [42, 43]. These
free radicals promote the chain scission in PLA. At the same time, the double bonds of allyl
groups in TAIC are broken and active radicals form. They react with the PLA chains and
crosslinking between PLA molecules is produced as can be seen in Figure 8 [12, 37, 42, 44].
For PLA/OvPOSS system, the double bonds of vinyl groups in OvPOSS are broken and
active radicals form. Then, OvPOSS radicals can also attack to PLA chain, leading the formation
of PLA network structure, which enhances mechanical properties of PLA (Figure 9).
As a general conclusion, both TAIC and OvPOSS used as crosslinking agents in this study
can help to achieve extended three-dimensional networks with gamma-irradiation by promoting

16
the generation of more bridge grafts by radicals as can be seen in Figure 10. One also should
note that the simultaneous chain scission of PLA could also occur.

Figure 8. Reaction mechanism for chemical crosslinking of between TAIC and PLA molecules

17
Figure 9. Reaction mechanism for chemical crosslinking of between OvPOSS and PLA
molecules

18
 Figure 10. Schematic representation of the crosslinking and the chain scission of PLA/TAIC
and PLA/OvPOSS systems

3.5 Thermal properties

The thermal behavior of irradiated and unirradiated PLA, PLA/TAIC and PLA/OvPOSS
composites received from DSC analysis is given in Table 3. The DSC traces of unirradiated
samples and samples irradiated at a dose of 50 kGy can be found in the Supplementary Materials
file (Figure S1- Figure S5). The glass transition temperature (Tg) of pure PLA is app. 56.1°C.
Moreover, a cold crystallization exotherm and a melting endotherm for neat PLA were observed
at 110.1°C and 151.6°C, respectively (Figure S1). As can be seen from Table 3 that cold
crystallization temperature (Tcc) of PLA shifted to lower temperatures as the irradiation dose
increased as compared to unirradiated PLA, indicating a higher crystallization rate in the
irradiated neat PLA samples. Conversely, percent crystallinity (Xc (%)) of irradiated pure PLA
exhibited higher values as the irradiation dose increased from 25 to 100 kGy because PLA chains
shortened upon the irradiation, which lead the formation of more ordered crystalline structures
[13]. Moreover, irradiation did not significantly affect the melting temperature (Tm) of pure PLA
as seen in Table 3 and Figure S1. Irradiation of PLA sharply decreased the Tg of PLA with the
increasing irradiation dose. This was due to the fact that more mobile short chains of PLA
formed because of the chain scission during irradiation. This is due to the fact that the chemistry

19
of irradiated PLA changed in a way that the number of chain ends increased, and they introduced
additional free volume. Therefore, Tg of PLA decreased during the gamma irradiation process.
Table 3. Thermal parameters of PLA, PLA/TAIC and PLA/OvPOSS composites
Tg Tm ΔHc ΔHm Xc
Sample designation Tcc (°C)
(°C) (°C) (J/g) (J/g) (%)
PLA - 0 56.1 110.1 151.6 26.3 33.6 7.8
PLA - 25 52.3 107.4 152.1 26.9 35.2 8.9
PLA - 50 50.6 100.7 154.3 27.6 38.9 12.2
PLA - 100 48.1 96.2 154.6 28.1 43.2 16.2

PLA/TAIC3 - 0 56.9 111.7 152.4 23.4 30.8 8.2

PLA/TAIC3 - 25 59.6 118.2 150.8 22.3 28.6 6.9
PLA/TAIC3 - 50 61.9 119.3 149.3 18.8 24.5 6.3
PLA/TAIC3 - 100 63.1 120.5 145.8 17.6 22.8 5.7

PLA/TAIC7 - 0 55.0 112.0 152.0 23.6 31.1 8.6

PLA/TAIC7 - 25 60.3 120.1 148.9 23.1 28.4 6.1
PLA/TAIC7 - 50 64.9 121.6 144.3 23.0 27.9 5.6
PLA/TAIC7 - 100 66.1 125.2 133.8 21.0 25.0 4.6

PLA/OvPOSS1 - 0 56.1 108.3 151.2 27.5 35.3 8.5

PLA/OvPOSS1 - 25 64.3 120.2 150.3 24.2 30.2 6.5
PLA/OvPOSS1 - 50 65.2 124.1 148.4 21.6 26.6 5.4
PLA/OvPOSS1 - 100 65.9 126.8 143.6 20.8 24.6 4.1

PLA/OvPOSS3 - 0 57.5 105.3 152.8 29.4 37.5 9.0

PLA/OvPOSS3 - 25 68.8 124.4 148.6 20.9 23.2 2.5
PLA/OvPOSS3 - 50 70.1 127.7 142.3 18.4 20.4 2.2
PLA/OvPOSS3 - 100 70.9 130.6 139.9 15.8 17.1 1.4

Addition of TAIC to the PLA did not influence the thermal transitions of pure PLA before
irradiation (Figure S2 and Figure S3). On the other hand, Tcc of unirradiated PLA including
OvPOSS exhibited lower values than pure PLA (Table 3, Figure S4 and Figure S5). This can be
associated to the nucleating agent role of POSS molecules [17, 45]. It can be seen from Table 3
that all irradiated PLA/TAIC and PLA/OvPOSS composites exhibited higher Tcc and lower Tm
values compared to both unirradiated and irradiated PLA at any given irradiation dose. This
situation could be attributed to the mobility restriction of PLA chains resulted from the formation
of network structure in the presence of TAIC and OvPOSS. Molecular motion necessary for
crystallization and melting was suppressed by three dimensional polymer network with high
crosslinking density [5]. In addition, the shorter PLA chains formed due to the possible chain

20
scission may also be a result of the lowering ot Tcc. The glass transition temperature of
PLA/TAIC composites increased as the irradiation dose and the TAIC loading level increased.
On the other hand, Tg of PLA in the presence of OvPOSS shifted much higher values for all
doses, which showed that crosslinking network between PLA molecules became more
pronounced in the presence of OvPOSS. The ΔHm of for neat PLA was 33.6 J/g, which means a
7.8% degree of crystallinity (Xc%) according to the melting enthalpy of 93 J/g for the fully
crystalline PLA. Xc% of PLA having TAIC and OvPOSS decreased during the irradiation
exposure as a result of the network formation, which lead to decrease of crystallinity degree.
After irradiation process, the semi-crystalline structure of PLA shifted to amorphous one in the
composites. It should be noted that since the crystallinity of PLA is very limited, it did not
influence the mechanical properties.
The temperature of degradation under nitrogen atmosphere for neat PLA, PLA/TAIC and
PLA/OvPOSS composites obtained from TGA curves are presented in Table 4. The thermal
degradation temperatures, including Td,5 and Td,10, defined as the temperature at which 5% and
10% mass loss occurs, respectively, while Td,max represents the temperature at which maximum
weight loss happens. TGA analysis showed that the thermal stability of pure PLA dropped with
irradiation dose, since the molecular weight of PLA was decreased [46, 47].
Compared to unirradiated PLA/TAIC and PLA/OvPOSS composites, Td,5 and Td,10 values of
the gamma irradiated PLA composites increased due to the increasing gel fraction and
crosslinking density, showing enhanced thermal stability for PLA. This situation could be
attributed to the larger three dimensional molecular structure with high crosslinking density
occurred after irradiation process, which retarded much more degradation [12]. Moreover, the
highest values of Td,max were obtained from gamma irradiated PLA/OvPOSS3 composites. In
addition to the formation of the highest crosslinking networks in the presence of 3 wt% OvPOSS,
inorganic silica part of the OvPOSS served as a barrier and prevented further degradation of the
PLA [48].

Table 4. TGA results of PLA, PLA/TAIC and PLA/OvPOSS composites before and after
irradiation
Sample designation Td,5 (°C) Td,10 (°C) Td, max (°C)
PLA - 0 343.2 351.2 378.2
PLA - 25 340.3 345.2 376.6
PLA - 50 332.2 339.9 372.1

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 PLA - 100 325.4 331.5 370.8

PLA/TAIC3 - 0 346.8 358.2 385.9

PLA/TAIC3 - 25 347.6 371.4 393.6
PLA/TAIC3 - 50 349.1 374.0 399.1
PLA/TAIC3 - 100 352.9 375.6 402.8
PLA/TAIC7 - 0 347.2 362.8 386.2
PLA/TAIC7 - 25 356.1 374.5 397.5
PLA/TAIC7 - 50 357.6 377.9 401.5
PLA/TAIC7 - 100 358.6 378.8 403.5

PLA/OvPOSS1 - 0 344.6 356.2 379.4

PLA/OvPOSS1 - 25 352.0 374.9 398.2
PLA/OvPOSS1 - 50 355.7 376.8 401.8
PLA/OvPOSS1 - 100 355.9 377.1 403.8
PLA/OvPOSS3 - 0 345.1 364.8 382.6
PLA/OvPOSS3 - 25 359.1 379.6 405.8
PLA/OvPOSS3 - 50 362.7 385.9 409.2
PLA/OvPOSS3 - 100 366.8 388.8 409.9

The HDTs of PLA, PLA/TAIC and PLA/OvPOSS at different gamma-irradiation doses are
shown in Table 5. As can be seen in Table 5 that the HDT of pure PLA decreased as the
irradiation dose increased due to the breaking of bonds occurred in the basic chain of PLA. On
the other hand, the HDT of PLA increased in the presence of TAIC and OvPOSS due the
formation of network structure under gamma irradiation, which restricted the PLA chain
movements and therefore retarded the distortion to higher temperatures [49]. In a general
conclusion, the enhancement of HDT was consistent with the changes of the both gel fraction
and degree of swelling.

Table 5. The HDTs of PLA, PLA/TAIC and PLA/OvPOSS composites before and after
irradiation
Sample designation HDT (C)
PLA-0 51.9
PLA-25 50.6
PLA-50 48.3
PLA-100 41.1

PLA/TAIC3-0 58.5
PLA/TAIC3-25 61.4
PLA/TAIC3-50 65.4
PLA/TAIC3-100 66.5

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 PLA/TAIC7-0 59.6
PLA/TAIC7-25 63.1
PLA/TAIC7-50 68.2
PLA/TAIC7-100 73.4

PLA/OvPOSS1-0 58.7
PLA/OvPOSS1-25 68.5
PLA/OvPOSS1-50 74.6
PLA/OvPOSS1-100 78.3

PLA/OvPOSS3-0 74.3
PLA/OvPOSS3-25 83.5
PLA/OvPOSS3-50 88.7
PLA/OvPOSS3-100 90.8

3.6 Morphological analysis

The morphology of the PLA, PLA/TAIC and PLA/OvPOSS composites before and after
irradiation was observed by SEM. As can be seen from Figure 11A that fibrillated surface
morphology of PLA was obtained before irradiation process. On the other hand, PLA exhibited a
brittle surface topology after absorption dose of 100 kGy (Figure 11B). These changes on PLA
surface morphology can be attributed to the degradation of PLA after exposure to gamma
irradiation, which might result from the chain scission of PLA. PLA/TAIC and PLA/OvPOSS
composites exhibited much more ductile fractures as a comparison with unirradiated composites.
SEM images of PLA/TAIC and PLA/OvPOSS composites showed rigid broken surfaces after
irradiation, no plastic regions can be observed (Figure 12). Wider and deeper cracks on the
surface were visible as the TAIC and OvPOSS content increased in PLA matrix after irradiation,
which indicate more brittle surface morphology. Moreover, Ov-POSS particles dispersed
uniformly in PLA matrix in both 1 and 3% loading levels.

23
Figure 11. SEM micrograph of tensile fractured surface of A) PLA-0 and B) PLA-100
(Magnification x1000, Scale Bar: 100 mic.)

24
Figure 12. SEM micrographs of tensile fractured surface of irradiated and unirradiated PLA,
PLA/TAIC and PLA/OvPOSS composites (Magnification x1000, Scale Bar: 100 mic.)

25
4 CONCLUSIONS
In the present study, the effects of gamma irradiation on the mechanical, thermal and
morphological properties of PLA/TAIC and PLA/OvPOSS composites were investigated. It was
obtained that mechanical properties of the samples were greatly dependent on the irradiation
dose. One of the drawbacks for PLA that limits its industrial applications is the lower HDT.
After irradiation, the PLA/OvPOSS composites exhibited higher HDT properties. For example,
the HDT value of the 3% OvPOSS composite radiated at 100 kGy approaches to that of PP (90-
95oC), which is a highly used synthetic polymer in automotive industry. Therefore, improving
the HDT of PLA via irradiation contribute the possibility of usage in automotive applications.
After increasing crosslinking degree, cold crystallization of the all composites shifted to higher
values; however, percent crystallinity decreased upon heating. SEM analysis revealed that
gamma irradiation turned PLA based composites to a much more brittle material, which may be
a disadvantage for the applications where toughness is important, such as packaging. On the
other hand, PLA is generally used in biomedical applications where the toxicity is critical. The
usage of TAIC or OvPOSS as a coagent may be a concern, since the unreacted monomeric
residues may be toxic. As a general conclusion of this work, OvPOSS was found to be an
effective crosslinker for PLA where the thermomechanical properties are critical.

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Highlights
 Octavinyl-POSS (OvPOSS) was found as an effective crosslinker for PLA.
 PLA/OvPOSS composites exhibited higher tensile strength at any irradiation doses.
 Irradiated PLA composites were found more thermally stable.

29