Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022

https://doi.org/10.1007/s10904-023-02646-4

RESEARCH

Nanoarchitectonics Based on Ultrasonication‑Assisted Polymerization

for Enhanced Interaction Between Liquid Monomer and LDH
Nanosheets
Hassam Mazhar1 · Wasim Ullah Khan2 · Farrukh Shehzad1 · Sung‑Gil Hong3 · Mamdouh A. Al‑Harthi1,2

Received: 4 March 2023 / Accepted: 3 April 2023 / Published online: 17 April 2023
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
This work reports on the novel ultrasonication-assisted in situ synthesis of ethylene-propylene-1-hexene (EPH)-ZnAl-layered
double hydroxide (LDH) nanocomposites. The ultrasonication treatment exfoliated the LDH in a few layers or thinner
nanosheets, which demonstrated a positive influence over the catalytic activity and formed different active sites. Moreover, the
highly dispersed ZnAl sheet in the EPH polymer matrices greatly enhanced its thermomechanical properties, as demonstrated
by thermogravimetric and dynamic mechanical analysis. Less than ~ 0.25 wt% of the filler content substantially improved
the thermal stability by 34 ℃ and the average activation energy (­ Ea) of thermal degradation by 48 kJ/mol. The degradation
mechanism of the polymer nanocomposites was investigated by a generalized kinetic master plot technique. The neat EP,
EPH, and EPH-ZnAl followed the Avrami-Erofeev (A2) kinetic model; however, the ultrasonicated EPH-ZnAl followed the
random scission (L2) degradation kinetics.
Graphical Abstract

Extended author information available on the last page of the article

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2014 Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022
Keywords LLDPE · Ethylene-propylene-hexene terpolymer · Copolymer · LDH nanocomposite · Exfoliation ·
Ultrasonication · TGA​
1 Introduction
Metallocene catalysts have been successfully utilized in
olefin polymerization, in particular ethylene polymerization
with and without α-olefins, to not only demonstrate excellent
catalytic performance but also deliver a polymer product
with precisely controlled stereo-regular properties [1]. The
homogenous metallocene catalysts, in contrast to conven-
tional Ziegler–Natta catalysts, have produced polymers with
a low polydispersity index (PDI) and high yield. However,
metallocene-based polymers face challenges such as low
mechanical and thermal stabilities, which limit their use
in certain applications. Hence, the synthesis of polyolefin
with the required properties, including improved mechanical
properties and thermal stabilities [2], reduced gas perme-
ability [3], and flammability [4] is highly desired. Moreover,
incorporating nanomaterials into the polymer matrix to syn-
thesize their nanocomposites also leads to the improvement
of polymer properties [5].
Apart from ethylene-propylene (EP) copolymers, EP
polymerization with α-olefins to synthesize terpolymers
offers adaptable products with a wider range of proper-
ties [6]. Ziegler–Natta-based polymerizations demonstrate
that the incorporation of a short α-olefin to ethylene-long
α-olefin system generally assists the addition of long
α-olefin into the chain. This synergistic impact is absent
for metallocene-based terpolymerizations [7, 8]. Kamin-
sky and Drogemuller [9] utilized metallocene catalysts
­(Cp2ZrCl2 and/or rac-Et[Ind]2ZrCl2/MAO) for diene-based
ethylene polymerization with diene and found that metal-
locenes were able to incorporate 6 to 7 mol% of diene. In
another study, the evaluation of co and terpolymers with
1-butene and 1-decene using Cp2ZrCl2 / MAO showed a
significant improvement in catalytic activity and produced
polymers with complete solubility in n-heptane [7, 10].
The better diffusion of the monomer was the main factor
that facilitates the improvement in catalytic activity. Com-
pared to homopolymers, ethylene copolymers with 1-butene
and 1-decene demonstrated reduced molecular weight and
enhanced catalytic performance. Metallocene catalysts, with
or without bridging, showed no synergistic effect during eth-
ylene polymerization with 1-butene and 1-octadecene.
The synthesis technique of polymer nanocomposites has
a significant influence on the properties of the nanocom-
posite [11]. These synthesis techniques include (i) solution
casting, (ii) melt blending, and (iii) in-situ polymerization
[12]. Exfoliation, during in-situ polymerization, promotes
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nanofiller dispersion within the polymer matrix [13]. As
described earlier, graphene, CNM, LDH, and other hybrid
nanofiller materials are utilized during in-situ olefin
polymerization that imparts superior electrical, mechani-
cal, and thermal properties. Among these nanofillers, LDH
exhibits advantages such as ease of synthesis, lower cost,
mechanical and chemical stability, easily tuned proper-
ties, and versatility. Furthermore, LDH-based nanofiller
improves the fire resistance of nanocomposites [14], serves
not only as a heat sink [15] but also as fire retardant [16].
LDHs are reported to have been utilized during ethylene
polymerization as a support material for metallocene as
well as Ziegler–Natta catalysts. Furthermore, the role of
LDH as a filler in synthesizing several polymers has also
been explored [17–20]. The investigation of the extent of
various LDH fillers within polyethylene and polypropyl-
ene matrices demonstrates that LDH plays a vital role in
influencing polymerization activity and polymer properties
such as morphology, molecular weight distribution, and
crystallinity. In recent years, our group has reported the
synthesis of PE using a graphite-LDH-supported metal-
locene catalyst [21], thermally stable EP-LDH nanocom-
posites [12, 22]. The polymer-nanofiller interfacial area
plays a vital role in improving the mechanical and physical
properties of polymer nanocomposites compared to the
neat polymer. Furthermore, the polymer-nanofiller interac-
tion and the extent of filler dispersion regulate the nano-
composite characteristics. Therefore, synthesizing nano-
composites with uniform nanomaterial/filler dispersion is
a challenging task, and functionalizing the nanomaterial/
filler facilitates its dispersion. [23, 24]
One of the ways to enhance the filler dispersion and uni-
formity is using UT treatment (UT) [25]. During in-situ
polymerization, filler particle aggregation can be reduced by
using low-energy sonication in low-viscosity solvents such
as toluene [26]. Here, we introduce a novel technique for ole-
fine polymerization. The authors believe that no studies have
been reported on the in situ synthesis of ethylene-propylene-
1-hexene-LDH nanocomposites assisted by ultrasonication
in the literature. The UT exfoliated and dispersed the LDH in
the reaction mixture and polymer matrix, which significantly
influenced the catalytic activity and thermomechanical prop-
erties, respectively. The highly dispersed ZnAl promotes the
activity while their presence in the polymer matrix limits its
degradation. The thermal degradation kinetics of the result-
ant polymer composites were studied by differential master
plot technique and combined kinetic analysis.
Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022
2 Results and Discussion
2.1 LDH Characterization
ZnAl-NO3 and ZnAl-DDS LDHs were characterized by
X-ray diffraction in 2θ angle ranging from 2 to 80 degrees
(Figure S1). The XRD peak for ZnAl-CO3 appeared at
11.7 degrees, assigned to the 003 peak. The corresponding
basal spacing ­(d003 = 0.76 nm) is related to the basal spac-
ing of the layered material. [27]. The surfactant treatment
of ZnAl-CO3 with sodium dodecyl sulfate intercalated the
dodecyl sulfate anion in the galleries of ZnAl LDH. The
large size anion exfoliates the layered structure; an intense
003 peak appeared at 3.36 degrees, which corresponds to
enlarged basal spacing equal to 2.62 nm. This value of
­d003 was very close to that reported in the literature [28].
The organic treatment of the ZnAl with SDS makes the
nanosheet of organophilic nature. Further, to demonstrate
the effect of sonication over the layered structure of LDH
present in the reaction slurry, ZnAl-DDS in toluene (T)
was sonicated for 30 min and dried to afford ZnAl-DDS/T.
The XRD of ZnAl-DDS/T shows that 006 peak has shifted
from 10.53 (for ZnAl-DDS) to 10.12, indicating increased
interlayer spacing due to sonication. To understand the
interaction of the 1-Hexene monomer with ZnAl LDH,
the reaction slurry along with 1-hexene and dried to afford
ZnAl-DDS/1-H/T; the XRD showed the disappearance of
the 003 and 006 peaks of the LDH. This result confirms
complete exfoliation of LDH in the presence of 1-hex-
ene monomer. A similar observation of fully exfoliated
ZnAl LDH by poly(lactic) acid has been reported by Eili
et al. [29]. The enlarged basal spacing attributed to the
surfactant and ultrasonication treatment of the LDH facili-
tates the monomer molecules in accessing galleries of the
layered material.
Fig. 1  Polymer product yield (red bars) and weight average molecular weight (Mw) (blue bars) for a EPH and b EP systems. The polydispersity
index (PDI) is shown in parentheses above the bars (Color figure online)
2015
The SEM image (Figure S2) reveals the morphology
of the ZnAL-DDS LDH. The nanofiller exists in the form
of sheets. The diameter and thickness of the sheets are in
hundreds and tens of nanometers, respectively. The EDS
confirms the elemental composition of ZnAl LDH.
2.2 Polymerization
EP and EPH co- and ter-polymers and their nanocomposites
were synthesized using the Zr and t-Zr catalysts with and
without UT. The 1-hexene dosing in the reaction system
increased the polymer yield. Remarkably, the yield of EPH
(5.54 g) is approximately double in comparison with that
of EP yield i.e., 2.81 (Fig. 1a and Table 1). A similar trend
is also observed for the t-Zr catalyst system (Figure S3).
The enhanced product yield is ascribed to the “comonomer
effect,” i.e., the presence of the comonomer activates dor-
mant sites or the formation of new active sites. The increase
in comonomer solubility in the reaction system promotes
the diffusion of gases to the active sites [30–32]. Further, the
addition of LDH to the EPH polymerization demonstrated a
slight decrease in activity. This could be related to the loss of
active sites associated with the nanosheets due to prevailing
LDH agglomeration. Nonetheless, the ultrasonication of the
reaction mixture showed advancement in catalytic activity
compared to the control EP and EPH polymers. The ultra-
sonication treatment exfoliated the LDH into single or few
layers sheets [33] and could act as a ligand and, therefore,
contribute towards enhancing the activity of the Zr-catalyst.
The polymer microstructure is one of the crucial aspects
for a polymeric material to be analyzed for its processing
and applications. The GPC data (Table 1) demonstrate that
the presence of ZnAl LDH in the EP copolymer influences
the weight averaged molecular weight (Mw) and the poly-
dispersity index (PDI) of the EPLS polymer nanocomposites
(Fig. 1 a, b). The Mw and PDI values for neat EP are 10,388
and 6.3, respectively, which increases two to three times
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2016 Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022

Table 1  Polymerization results for co- and terpolymer and their ndanocomposites
Samples Yield (g) LDH (mg) 1-Hex- UT time (min) Activitya Mnb Mwb PDIb T0.9c Td Crystallinityd
ene (ml)

EP 2.81 0 0 0 795 1633 10,338 6.3 437 111.3 82.1

EPH 5.54 0 1 0 1565 1264 11,139 10.1 373 103.0 36.7
EPHL 4.79 15 1 0 1352 1017 4000 3.9 383 103.2 37.0
EPHLS 5.65 15 1 30 1597 1131 12,436 11.1 405 103.8 28.0
EPHLS60 6.86 60 1 30 1938 1207 11,159 9.2 405.8 104.3 29.0
EPLS 2.72 15 0 30 769 1876 25,986 13.9 443 113.9 81.5
EPLS30 3.48 30 0 30 984 2018 18,029 9.0 443 114.9 73.0
EPLS60 3.81 60 0 30 1075 2102 23,652 11.3 445 113.3 71.1
EPLS90 3.80 90 0 30 1074 3978 111,054 28.0 443 113.3 67.3
a
measured in k­ gproduct/mol/hr/bar, bcalculated by GPC, cAnalyzed by TGA, dAnalyzed by DSC

when ZnAl LDH is incorporated in UT, i.e., EPLS, EPLS30,
and EPLS60 show Mw values between 18,000 and 28,000
while PDI values range from 9 to 13.8. Despite the equal
product yield, the Mw (111,054) of EPLS90 was 10 times
and 5 times higher than that of EP and EPLS60, respectively.
This increase in Mw (for EPLS90) could be due to slow
chain transfer and termination.
Despite the higher activity of EPHLS system, the Mw
remains approximately the same as that of EP, i.e., Mw is
found to be in the range of 10,338 and 12,436 when EP
is compared with EPHLS system except for EPHL, which
shows lower Mw (4000). The lower Mw of EPHL could be
assigned to the high rate of chain termination. These results
suggest that UT contributes to the Mw.
The UT-assisted reaction slurry system produced polymer
nanocomposites with a wider molecular weight distribution
(MWD). The polymer thus produced was bimodal in nature
(Fig. 2a). The MWD of EPLS nanocomposites were of two
fractions. With the increase in the amount of LDH, the curve
shifts leftward, favoring the production of polymers having
a high fraction of large molecular chain. The presence of
1-hexene in the EPLS system (i.e., EPHLS) narrowed the
MWD of the polymer. Moreover, the MWD peaks tend to
merge from bimodal to unimodal distribution. There would
be a high rate of chain transfer, limiting the formation of
long chain molecules.
These bimodal behavior of MWD due to the LDH envis-
ages the formation of distinct active sites with different
reactivity. The LDH surface contains covalently bonded
hydroxyl groups and metal oxides [34]. These two different
sites would have distinct interaction with the incoming spe-
cies [34]. The UT of the toluene and ZnAl slurry could lead
to partial delamination of the stacked nanomaterial, there-
fore, furnishing more surface area of the LDH to interact
with the catalyst. It has been reported that the supported
catalyst yielded high Mw polyethylene [35–37].
In the present case, relatively high Mw of EP could
be an attribute of in-situ supported catalyst complex

Fig. 2  Retention time (RT) versus molecular weight distribution (dw/dlogMw) for a EPH and b EP systems

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Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022
formation due to the weak interaction of C­ p2ZrCl2 with the
ZnAl-DDS filler surface. The peak shift of Al solid-state
magnetic angle spinning (MAS) NMR spectra (Fig. 3a) for
ZnAl and ZnAl/Cp2ZrCl2 indicates the interaction of the
molecular catalyst with the filler surface. Figure 3 shows
that there could be three possible ways the catalyst can
interact with ZnAl-DDS, i.e., (b) Bronsted acid site, (c)
the Zr atom forms a bond with surface oxygen by releas-
ing HCl [38], and (d) the interaction of the metal oxides
present in the LDH with the catalyst [39].
The DSC plots of the EP and EPH polymers are shown
in Figure S3. The melting temperature (Tm) and crystalli-
zation temperature (Tc) of EP copolymer was 123.5 ℃ and
111.3 ℃, respectively. The in-situ addition of 1-Hexene
during the polymerization influenced the microstructure of
the polymer as had been discussed above and therefore has
lower Tm and Tc values of 114.5 ℃ and 103 ℃, respec-
tively. The peak integral of the DSC cooling cycle is asso-
ciated with the crystallinity of the polymer. EP copolymer
was 82 percent crystalline, while the crystallinity of EP
dropped by 55 percent and was equal to 36.7 percent. The
decrease in Tm, Tc and crystallinity of the polymer could
be attributed to short-chain branching (SCB) induced by
the in-situ addition of 1-hexene. Polymers with a high
SBC content has a poor chain arrangement, consequently,
a lower crystallinity and melting temperature [30, 40].
Additionally, the crystallinity of EP and EPH polymers
dropped slightly with an increase in ZnAl filler content
(Table 1).
Fig. 3  a 27Al solid state magic angle spinning nuclear magnetic res-
onance spectra (MAS NMR) of ZnAl LDH and Possible interaction
of the surface of catalyst complex with the ZnAl-DDS through the
2017
TG analysis was performed at a heating rate of 10 ℃/min
for all samples, as shown in Fig. 4. The temperature at 10%
weight loss of the polymer sample was denoted as ­T0.9, and
the values of which for EP and EPH samples were 428 and
372 ℃, respectively. The drop in thermal stability could be
related to the high branching and lower number averaged
molecular weight (Mn) of EPH induced due to 1-hexene
addition (Table 1). The LDH dose to the EPH terpolymer
(EPHL) increased the T ­ 0.9 value by 12 ℃. Remarkably, the
the in-situ ultrasonication treatment of these samples greatly
enhanced their thermal stability. The T ­ 0.9 values of EPHLS
and EPHLS60 were found to be 405 and 405.8 ℃, respec-
tively, which was approximately 34 ℃ higher than that of the
EPH sample. The advancement in the thermal stability of
EPH/LDH polymer nanocomposite could be an attribute of
well dispersed ZnAl LDH in the polymer matrix. A similar
observation was reported by He et al. [41] for PE produced
by a ZnAl-supported Nickel diamine catalyst. Uniformly dis-
persed nanomaterials (LDH) in a polymer matrix act as a
thermal barrier and offer impedance to the diffusion of com-
bustible gases in the nanocomposite, resulting in improved
thermal stability. Similar studies based on the formation of
nanocomposites constituting nanomaterials (LDH and gra-
phene) and polymers have been reported in literature. [21,
42, 43]. Moreover, the T ­ 0.9 of EPLS samples were slightly
enhanced by 8 ℃ as compared to the EP (Fig. 4b) which
could be related to their increased Mw. Uniform dispersion
of LDH and the structure of EPHLS polymer nanocomposite
confirmed by the TEM imaging as shown in Fig. 5a.
scheme; (a) Bronsted acid site, b the Zr atom forms a bond with sur-
face oxygen by releasing HCl, [38] and c the interaction of the metal
oxides present in the LDH with the catalyst. [39]
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2018
Fig. 4  Thermogravimetric analysis plot of a EPH and b EP systems showing weight loss as a function of temperature in a nitrogen environment
Further, the polymer degradation kinetics were analyzed
by the generalized master plot technique and combined
kinetics analysis (CKA). The activation energy associated
with thermal degradation of the polymers was evaluated
by isoconversional using the differential Friedman method
(Eq. 4 in supplementary material) by plotting fractional
conversion (α) versus Ea curve. The average Ea for EP and
EPH was found to be equal to 244 and 207 kJ/mol, respec-
tively. The drop in the Ea value of EPH could be related to
low Mn and branching. Low Ea is required to break down
smaller molecules and branches [44]. On the contrary, the
ultrasonication treated samples were thermally more stable
and required more activation energy to thermally degrade.
The average Ea for EPHLS and EPHLS60 were 255 and
258 kJ/mol respectively.
The degradation kinetics of the polymer samples were
fitted to the theoretical model f (α) in a generalized master
plot using Eq. 6 in supplementary material. The master plot
infers that EP, EPH (Fig. 5d) and EPHL (Figure S5b) fol-
lowed the kinetic model of Avrami–Erfeev (A2), the poly-
mers underwent random nucleation and growth of nuclei
through different nucleation sites during thermal degrada-
tion and therefore the degradation was associated with the
nucleus growth model (Avrami–Erofeev equation, model
A2). However, the UT samples EPHLS and EPHLS60 suf-
fered random scission of C–C bond of polymer backbone
and followed L2 kinetic model of degradation (Fig. 5d, f).
The confirmation of the degradation kinetic model was dem-
onstrated by the goodness of regression of in the combined
kinetic analysis (CKA) using equation-7 in supplementary
material. The activation energy calculated by CKA for all
polymers were in close range to the on evaluated by the
isoconversional method. The Ea of thermal degradation for
EP evaluated using CKA was 228 kJ/mol, which is close to
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Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022
the value of Ea as reported in our previous work [22]. Fur-
thermore, the regression coefficients for CKA (Table 2) were
appreciably high and support the already predicted kinetic
model by the generalized master plot.
The dynamic machinal analysis of EPHLS and EPLS was
studied (Fig. 6). The specimens were subjected to dynamic
loads in a single cantilever mode of the DMA. An increase
in loss modulus was observed with the addition of the
filler. Moreover, an increase in the filler concentration also
increased the loss modulus of the polymer. The improve-
ment in the loss modulus is related to the chain mobility
of the polymer. In a well-dispersed filler-polymer system,
it is expected that there will be a greater number of chain
segments which are mobile. Increased mobility can cause
increased internal friction leading to increased loss modulus
[45].
3 Conclusion
In summary, the results of this study demonstrated a novel
approach of polymerization for the synthesis of EP/ZnAL
and EPH/ZnAl polymer nanocomposites. It highlights the
role of ultrasonication in the exfoliation and dispersion
of LDH nanosheets. The exfoliation of the stacked LDH
due to ultrasonication provided more surface area of the
LDH to interact with the catalyst, which was confirmed by
the peak shift of [27] Al MAS NMR spectra. The interac-
tion of the catalyst with ZnAl LDH strengthen the active
sites causing high activity and produced EP with high
molecular weight. Moreover, in synthesis of EPH, 1-hex-
ene addition enhanced the catalytic activity by the virtue
of “comonomer effect”. The presence of 1-hexene along
with the delaminated LDH showed a synergistic effect on
Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022 2019

Fig. 5  a EPHLS60 TEM image, b TEM image of EPHL, c activation energy plot for EPHLS system, d Master plot of EPH and EPHLS, e CKA
analysis plot of EPH, and f EPHLS

catalytic activity. The well-dispersed the LDH in the EPH
polymer matrix led to improved loss modulus and thermal
stability. About less than 0.25 weight percent LDH filler
content in the EPH increased the thermal stability and acti-
vation energy by 34 ℃ and 48 kJ/mol, respectively. The
degradation kinetics of the EPHLS were accessed by an
isoconversional method; interestingly, the ultrasonication
caused the polymer to degrade differently than the control
sample. The EPH followed Avrami–Erfeev (A2) kinetic
model while the EPHLS followed random scission kinet-
ics of degradation.

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2020 Journal of Inorganic and Organometallic Polymers and Materials (2023) 33:2013–2022

Table 2  Lists the degradation Sample Kinetic model α-range R2 Ea [kJ/mol] Ea (kj) Iso-
kinetic model corresponding to CKA conversional
different polymer samples method

EP Avrami-Erofeev A2 0.05 < α < 1 0.99 228 244

EPH 0.15 < α < 1 0.98 185 207
EPHL 0.18 < α < 1 0.986 187 207
EPHLS Random scission L2 0.13 < α < 1 0.985 266 255
EPHLS60 0.12 < α < 1 0.98 258 258

Fig. 6  Variation in the loss modulus values with respect to temperature as determined by dynamics mechanical analysis (DMA) for a EPHLS
and b EPLS systems

Supplementary Information The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10904-0​ 23-0​ 2646-4.
Acknowledgements The authors are thankful to the S-Oil Corporation,
Republic of Korea and KFUPM, for funding this work under Project
CHE02475. The authors declare no conflict of interest.
Author Contributions HM: methodology, conceptualization, data
curation, original manuscript preparation. WK: wrote the original
manuscript. FS: review and editing. SGH: supervision, funding, and
chemicals. MH: supervision, conceptualization, review, lab facility,
and funding acquisition.
Funding S-Oil Corporation South Korea, CHE02475.
Declarations
Conflict of interest The authors declare no competing interests.
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Authors and Affiliations
Hassam Mazhar1 · Wasim Ullah Khan2 · Farrukh Shehzad1 · Sung‑Gil Hong3 · Mamdouh A. Al‑Harthi1,2
* Mamdouh A. Al‑Harthi
mamdouh@kfupm.edu.sa
1
Department of Chemical Engineering, King Fahd University
of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
13
44. P. Das, P. Tiwari, Thermal degradation kinetics of plastics and
model selection. Thermochim. Acta. 654, 191–202 (2017). https://​
doi.​org/​10.​1016/j.​tca.​2017.​06.​001
45. M.A. Bashir, Use of dynamic mechanical analysis (DMA) for
characterizing interfacial interactions in filled polymers. Solids
2(1), 108–120 (2021). https://​doi.​org/​10.​3390/​solid​s2010​006
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such publishing agreement and applicable law.
2
Interdisciplinary Research Center for Refining and Advanced
Chemicals, The Research Institute, King Fahd University
of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
3
TS&D Center, S-OIL Corporation, Seoul 07793,
Republic of Korea