Journal of Polymers and the Environment (2019) 27:37–49

https://doi.org/10.1007/s10924-018-1320-6

ORIGINAL PAPER

Recycled Poly(Ethylene Terephthalate)/Clay Nanocomposites:

Rheology, Thermal and Mechanical Properties
Ravindra Reddy Chowreddy1   · Katrin Nord‑Varhaug1 · Florian Rapp2

Published online: 19 October 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Polymer nanocomposites containing recycled poly(ethylene terephthalate) (r-PET) as a polymer matrix and ­Cloisite® 10A
as a reinforcement were prepared through melt compounding. First, a masterbatch containing 20 wt% of C ­ loisite® 10A clay
was prepared and later diluted with neat r-PET to obtain nanocomposites containing 1, 2, 4 and 6 wt% of clay. The rheologi-
cal, thermal, mechanical and morphological properties of the PET–clay nanocomposites were characterized. The complex
viscosity of the nanocomposites gradually increases with increase in clay content. The storage modulus and loss modulus of
nanocomposite containing 1 wt% of clay was similar to neat r-PET but increases with increase in clay content. Incorporation
of clay into a r-PET slightly increases the crystallisation temperature and degree of crystallinity due to the heterogenous
nucleating effect of clay. Thermal stability and glass transition temperature of nanocomposite containing ­Cloisite® 10A
clay at lower loadings was similar to r-PET and gradually decreases with increase in clay content. The tensile properties of
PET–clay nanocomposites increased gradually with clay content. The impact strength of nanocomposites was not altered
until 4 wt% and decreased at 6 wt%. Morphological investigations indicated homogeneous dispersion of clay in r-PET.

Keywords  Polyethylene terephthalate · Recycled · Cloisite® 10A · Clay · Polymer nanocomposites · Rheology · Tensile
properties

Introduction The increased consumption of PET, especially in the

Poly(ethylene terephthalate), (PET), is an important poly-
ester which may exist both as an amorphous and semi-crys-
talline polymer. PET possess excellent properties such as
tensile and impact strength, chemical resistance, process-
ability, transparency, and appropriate thermal stability [1]
and it is widely utilized in industrial sectors such as food
and beverages packaging, textiles, photographic films, X-ray
films, audio video tapes, etc.
* Ravindra Reddy Chowreddy
ravindra.chowreddy@norner.no
Katrin Nord‑Varhaug
katrin.nord‑varhaug@norner.no
Florian Rapp
florian.rapp@ict.fraunhofer.de
1
Norner Research AS, Asdalstrand 291, 3962 Stathelle,
Norway
2
Fraunhofer Institute for Chemical Technology ICT,
Joseph‑von‑Fraunhofer‑Straße 7, 76327 Pfinztal, Germany
packaging sector is creating serious environmental problems
as the vast amount of plastic waste is generated every year
due to the short life of packaging. PET is a non-biodegrada-
ble plastic material which has high resistance to weathering
and biological agents under normal conditions. Disposal of
the waste to the landfill is becoming undesirable due to leg-
islation pressures, rising costs and the poor biodegradability
of polymers [2]. Therefore, other ways of PET waste treat-
ment, such as recycling is highly desired.
Recycling processes are the best way to economically
reduce PET waste [3, 4] and PET is one of the most exten-
sively recycled polymeric materials [5]. There are three
distinct approaches to the recycling of post-consumer plas-
tic packaging materials. Primary recycling means that the
recyclable material/product is recovered and reused without
being changed in any way and usually for the very same pur-
pose. Secondary recycling, also defined as physical, mechan-
ical or material recycling, means that the material/product
is reused in some other way without reprocessing, while
tertiary recycling refers to a process that involves chemical
altering of the material/product in order to make it reusable.

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Vol.:(0123456789)

38
Physical recycling involves several treatments or opera-
tions such as waste collection, grinding, melting, and reform-
ing plastic material. Prior to melting and reprocessing, the
ground, flaked, or pelletized polymer is generally washed to
remove contaminants. Recycled PET is more sensitive to ther-
mal and hydrolysis degradation. Recycling of PET gives rise
to a decrease in the melt viscosity, average molecular weight,
thermal and mechanical properties of the material due to the
hydrolytic chain scission and thermomechanical degradation
during material processing [6]. To produce a plastic with the
desired performance characteristics, small amounts of virgin
PET resin and/or additives such as chain extenders, antioxi-
dants, processing aids or fillers are added to the recycled resin.
Currently physical recycled PET is being used to make food
and non-food containers, straps, sheeting, and textile fibres.
Incorporation of small quantities of nano-fillers into pol-
ymeric matrices is known to improve the mechanical, elec-
trical, barrier and thermal properties [7–10]. The improved
properties in polymeric matrices with nano-fillers is due to
the efficient reinforcing of nano-filler in polymer matrix. Vari-
ous nano-fillers, like clays [11–14], carbon nanotubes, CNTs
[15–19], graphene [20–22], silica [23–25] have been explored
in reinforcement of PET. Incorporation of nano-fillers in recy-
cled PET could increase the viscosity, thermal stability and
mechanical properties. Incorporation of inexpensive clay into
recycled PET is an efficient route to improve the processability
and performance. The literature available in this area is how-
ever limited. In a study, C­ loisite® Na+ and organo-modified
® mixed well using a kitchen blender and dried under vac-
clay, ­Cloisite 25A have been investigated as fillers in recycled
PET [26]. The authors concluded that C ­ loisite® 25A is a bet-
­ loisite® Na+. In another study, the
ter reinforcing filler than C
authors have shown that the silane modification of C ­ loisite®
clays makes them efficient reinforcing fillers for recycled PET
[27].
In the present study, we are reporting the preparation and
characterization of recycled PET nanocomposites containing
­Cloisite® 10A as a reinforcement. The ­Cloisite® 10A clay is an
organically modified bentonite, treated with dimethyl benzyl
hydrogenated tallow, a quaternary ammonium species by ion-
exchange. The C ­ loisite® 10A clay was chosen in the present
study due to the better compatibility with aromatic polyester.
The nanocomposites containing 1.0–6.0 wt% C ­ loisite® 10A
clay were produced by conventional melt compounding by
using twin-screw extruder via masterbatch dilution. The rheo-
logical, thermal and mechanical properties, and the morphol-
ogy of nanocomposites have been investigated.
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Journal of Polymers and the Environment (2019) 27:37–49
Materials and Methods
Materials
Recycled poly(ethylene terephthalate) (rPET), TEXPET R
760 was purchased from Texplast GmbH, Germany. The
TEXPET R 760 was received in the form of pellets and
was a regranulate from the post-consumer PET bottles
used in the beverage industry. The intrinsic viscosity (IV)
of the material was 0.80 ± 0.02 dL/g.
The clay utilized in the study was C­ loisite® 10A, an
organically modified bentonite and was received from
BYK Additives, Germany. The organic modifier present
in ­Cloisite® 10A is dimethyl benzyl hydrogenated tallow, a
quaternary ammonium species. The quaternary ammonium
modifier is incorporated into bentonite by cation exchange
process. These quaternary ammoniums modified benton-
ites are known to be suitable as fillers in thermoplastic
applications.
Methods
Production of PET–Cloisite Nanocomposites
First, a PET–clay masterbatch containing 20 wt% of
­Cloisite® 10A was made by melt compounding. Required
amounts of milled recycled PET and ­Cloisite® 10A were
uum at 80 °C for 2 days. The mixture was melt extruded
using twin screw Prism 24 extruder with L/D is equal to
30. The extrusion was performed at 270 °C and a screw
speed of 300 rpm. After compounding, the polymer string
was cooled under water bath and pelletized.
The PET nanocomposites containing 1.0, 2.0, 4.0 and
6.0 wt% of ­Cloisite® 10A were produced by an extrusion
dilution technique. Like the masterbatch production, first
required amounts of masterbatch and milled recycled PET
(neat) were mixed well using a kitchen blender and dried
overnight at 120 °C. Later, the dried mixture was melt
extruded using a twin-screw Prism 16 extruder with L/D
is equal to 25. The extrusion was performed at 260 °C
and a screw speed of 500 rpm. After compounding, the
polymer string was cooled under water bath and pelletized.
Composition of the different PET–clay nanocomposites
are presented in Table 1.
Journal of Polymers and the Environment (2019) 27:37–49 39

Table 1  Composition of PET– Sl. no. Sample designation Cloisite content in the Content of recy- Content of PET–
cloisite nanocomposites nanocomposite (wt%) cled PET (wt%) cloisite masterbatch
(wt%)

1 Ref. PET 0.0 100 0

2 PET–clay (1.0) 1.0 95 5
3 PET–clay (2.0) 2.0 90 10
4 PET–clay (4.0) 4.0 80 20
5 PET–clay (6.0) 6.0 70 30

Characterization of Nanocomposites temperature and 750 °C with heating rate of 10°C/min in

Rheological Measurements
Dynamic rheology measurements on the nanocompos-
ites were performed on Dynamic Analyser RDA II from
Rheometrics. The measurements were carried out with
parallel plate flow geometry using 25 mm diameter plates
at 270 °C. Steady shear viscosity measurements were made
in a shear rate range varying from 0.1 to 300 rad/s. For
rheology measurement, circular specimens with 30 mm
diameter and 1.5 mm thickness were made by compression
moulding. Prior to making the specimens by compression
moulding, the nanocomposite pellets were dried well to
avoid any degradation during compression moulding. The
storage modulus, loss modulus and complex viscosity was
measured.
Differential Scanning Calorimetry (DSC)
Differential scanning calorimetry (DSC) analysis on nano-
composites was performed using Netzsch 204-F1 instru-
ment. About 10–15 mg of pellet sample was encapsulated
into sealed aluminium pans and analysis. The analysis
involved three cycles of heating and cooling (1) heating the
sample from room temperature to 280 °C at a heating rate
of 10°C/min and held for 5 min, (2) cooling from 280 to
30 °C at a cooling rate of 10°C/min and held for 5 min and
(3) heating the sample from 30 to 280 °C at a heating rate of
10°C/min. The glass transition temperature, melt tempera-
ture, crystallization temperature, crystallinity and enthalp-
ies of melting and crystallization of nanocomposites was
determined from DSC analysis.
Thermogravimetric Analysis (TGA)
Thermogravimetric analysis (TGA) on nanocomposites sam-
ples was carried out using Q500 from TA instruments. Ther-
mograms obtained from TGA analysis provides the infor-
mation related to the thermal stability of material. About
10–15 mg of the sample was subjected for TGA analysis.
TGA analysis was performed on the samples between room
both air and nitrogen atmospheres.
Dynamic Mechanical Analysis (DMA)
Dynamic mechanical analysis (DMA) on nanocomposites
was performed on DMA Q800 from TA Instruments using
single cantilever in bending mode. Analysis was performed
on bar-like cut specimens from compression moulded plate.
The specimen had length, width and thickness respectively
40 mm, 5.0 mm and 2.0 mm. Experiments were performed
between room temperature and 190 °C at the heating rate
of 3°C/min. The frequency of bending was fixed at 1 Hz.
DMA analysis was performed to evaluate the dynamic
mechanical properties of nanocomposites and glass transi-
tion temperature.
Tensile Testing
Tensile testing on the nanocomposites was performed on
Zwick Z010 according to ISO 527. A multipurpose type
1B injection moulded dog-bone specimens were utilized for
testing. The measurement was carried out at a crosshead
rate of 5 mm/min. Five parallel measurements were made
at room temperature and average values are reported. Ten-
sile properties such as tensile strength, modulus, elonga-
tion at yield and elongation break were measured from the
stress–strain curves.
Charpy Impact
Charpy impact strength on the nanocomposite samples was
measured on Resilvis 125 Cryo according to ISO 179-1.
A notched specimen was made from the injection moulded
bars and utilized in testing. Five parallel measurements were
made at room temperature. The amount of energy absorbed
by the sample before it breaks was measured.
Gel Permeation Chromatography (GPC) Analysis
Gel permeation chromatography (GPC) analysis on the ref-
erence PET and nanocomposites provides the information

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40
about the average molecular weights, ­Mn and ­Mw, and the
molecular weight distribution M­ w/Mn. The GPC analysis was
performed on Viscotek TDA 301 from Malvern. GPC anal-
ysis was performed on the samples using 1,1,1,3,3,3-hex-
afluoro-2-propanol (HFIP) as solvent. Chromatograms were
obtained by using a refractive index detector, equipped with
a PL HFIPgel guard plus 2 × PL HFIPgel 300 × 7.5 mm,
9 µm columns at a flow rate of 0.8 mL/min and a nominal
temperature of 40 °C. Poly(methyl methacrylate) (PMMA)
was utilized to calibrate the GPC system and the results are
expressed in “PMMA equivalent” molecular weights, suit-
able for comparative purpose among the samples.
Light Microscopy (LM)
In order to see how well the clay is dispersed in the nano-
composites, light microscopy (LM) investigations was per-
formed. A specimen with 20 µm cross sections was prepared
from injection moulded dog-bone samples by microtome
cutting by using Leica M2500 microtome cutter. A transmis-
sion light/light field technique was utilized for microscopic
investigation. Microscopy analysis was carried-out using
Zeiss Axiophot microscope.
Scanning Electron Microscopy (SEM)
Scanning electron microscopic (SEM) investigation was
investigated using Philips XL-30 ESEM. For SEM analysis,
a specimen was prepared by etching. First, a small piece of
injection moulded specimen was embedded into an epoxy
resin, and polished after curing. The polished specimen was
exposed to 4M aqueous potassium hydroxide (KOH) solu-
tion at around 80 °C to remove the surface PET resin by
etching. The etched specimen was washed with water, dried
and a thin layer of gold was sputter coated for SEM analysis.
The SEM analysis was performed using secondary electron
(SE) detector at an accelerating voltage of 30 kV.
Results and Discussion
Rheological Characterization
Rheological characterization of polymer nanocomposites
is important to understand the effect of nano-fillers on the
structure and the processing characteristics. In addition,
rheological characterization is extensively used to probe dis-
persion states of organoclay in polymer matrices [28–30].
Rheological investigation of polymer nanocomposites pro-
vides the information related to percolation threshold of the
nano-filler in the resin [31].
Variations of complex viscosity of the reference PET and
PET–clay nanocomposites as a function of frequency are
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Journal of Polymers and the Environment (2019) 27:37–49
presented in the Fig. 1a. The complex viscosity of refer-
ence PET is independent of frequency, indicating a New-
tonian behaviour in the investigated frequency range. The
nanocomposite sample containing 1 wt% of clay presented
Newtonian behaviour similar to reference PET. However, the
nanocomposite samples containing 2 wt% of clay and above,
exhibited a pronounced shear thinning response. The shear
thinning behaviour for the nanocomposites increases with
increase in clay concentration, and the shear thinning effect
was most pronounced at the low frequencies. The complex
viscosity is increasing with higher loading of clay, and the
increase is most pronounced for a clay content of 2 wt% and
above. The complex viscosity of the nanocomposite sam-
ples decreased at higher frequency due to the shear thinning
effect. Similar observations were made in the literature [32,
33].
The variation of storage modulus (Gʹ) and the loss modu-
lus (G″) of reference PET and nanocomposites as a func-
tion of frequency respectively is presented in Fig. 1b, c. The
storage modulus for reference PET and nanocomposites
increases with frequency and clay content. The magnitude
of storage modulus increase with frequency is higher for ref-
erence PET and PET–clay (1.0) compared to other nanocom-
posite samples. The dependence of storage modulus with
frequency for both reference PET and PET–clay (1.0) was
similar indicating the samples possess similar viscoelastic
properties. However, for nanocomposite samples containing
2 wt% of clay and above, less pronounced dependency of
storage modulus with frequency is observed. Especially, the
nanocomposite samples containing 4 wt% and 6 wt% of clay
presents nearly frequency-independent storage modulus. In
addition, the storage modulus curves exhibit a plateau at
the lower frequencies (Fig. 1b) which is attributed to the
delaminated structures clay in polymer matrix [33]. Such
interactions indicate a percolation network structures in the
nanocomposite samples. Similar observations are reported
in the literature for other polymer composites [34–36].
The trend in the variation of loss modulus with frequency
for nanocomposites (Fig. 1c) is similar to the storage modu-
lus (Fig. 1b). However, the nanocomposite samples with
higher clay content (4 and 6 wt%) presented plateau at lower
frequencies in loss modulus curves compared to storage
modulus curves. In addition, the increase in loss modulus
with increase in clay content is less pronounced compared
to storage modulus.
The variation of storage modulus (Gʹ) and the loss
modulus (G″) with frequency for nanocomposite sam-
ples containing different amounts of clay are presented in
Fig. 2a–d. These plots can provide better insight into the
changes in the microstructure and hence the viscosity of
the systems. It is clear from the Fig. 2a, G″ is higher than
Gʹ in the frequency range investigated, indicating normal
viscoelastic response. However, for the nanocomposite
Journal of Polymers and the Environment (2019) 27:37–49 41
Fig. 1  Variation of a complex
viscosity, b storage modulus
and (C) loss modulus of PET–
clay nanocomposites
sample containing 2 wt% clay, Gʹ becomes higher than
G″ (cross over) at lower frequency. As the clay content
in PET matrix is increased, solid-like behaviour becomes
more pronounced as Gʹ dominates G″ in the entire fre-
quency range investigated. The nanocomposite sample
with 6 wt% of clay presented higher Gʹ compared to G″
and almost no cross over is observed indicating that the
sample has transformed from the liquid-like behaviour to
more elastic behaviour over whole frequency range. This
further suggests a stronger network structure between the
delaminated clay particles in the PET matrix.
TGA Analysis
In order to investigate the thermal stability of the
PET–cloisite composites, thermogravimetric analysis (TGA)
was performed. The TGA was performed under both nitro-
gen and air atmospheres. The TGA of samples under nitro-
gen and air atmospheres respectively represent pyrolytic and
thermo-oxidative conditions. The TGA weight loss curves
and first derivative TGA curves for reference PET and the
nanocomposite samples under air atmosphere are presented
in Fig. 3. The first derivative TGA curves present variations
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42
Fig. 2  Variation of Gʹ and G″ with frequency for PET–clay nanocomposites. a PET–clay (1.0), b PET–clay (2.0), c PET–clay (4.0) and d PET–
clay (6.0)
in the thermal stability among the samples. It is clear from
Fig. 3 that the samples exhibit a two-step decomposition
during TGA analysis under air, an oxidative environment.
According to literature, the first step of decomposition
for reference PET is due to overlapping of two decomposi-
tion processes [37]. The first process is mainly due to the
degradation of polymer chain through end group initiated
mechanism and the second degradation process is due to
the thermal degradation of the products formed during first
decomposition process. The second degradation step for ref-
erence PET in the temperature range 520–640 °C is due to
the decomposition of thermally stable species formed dur-
ing the first degradation step. The thermally stable species
formed during first degradation step could be cross-linked
carbonaceous structures. In case of PET nanocomposite
samples, the first step of decomposition took place similar
to reference PET, where the decomposition is due to both
PET resin and organic modifier present in the clay. The
second decomposition step for PET nanocomposites was
broader and the broadness increased with increase in clay
content. The second decomposition step took place in the
temperature range 520–720 °C for PET–cloisite (6%). This
observation could be due to the formation of the reasonably
large amounts of cross-linked carbonaceous species which
undergo slow decomposition in a wide temperature range.
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Journal of Polymers and the Environment (2019) 27:37–49
The TGA weight loss curves and first derivative TGA
curves for reference PET and the nanocomposite samples
under nitrogen atmosphere (pyrolytic environment) are
presented in Fig. 4. Unlike TGA analysis under air atmos-
phere, in nitrogen atmosphere the reference PET and the
PET nanocomposites exhibited only one step decomposition.
The main degradation process during TGA analysis under
nitrogen atmosphere is due to the combined degradation
processes—polymer chain degradation through end group
initiated mechanism and the thermal degradation of the
products formed during polymer chain degradation. Under
nitrogen environment, the thermal decomposition of poly-
mer is leading to thermally stable cross-lined carbonaceous
species which are not undergoing any further decomposition
due to the presence of inert nitrogen atmosphere and hence
the large amounts of reside at the end of TGA analysis.
The results of TGA analysis such as temperature at 1%
weight loss, temperature at 5% weight loss, onset of decom-
position, and the amount of residue at end of TGA analysis
(at 750 °C) are summarized in the Table 2. It is clear from
the results that the temperatures at 1% and 5% weight loss
as well as the onset of decomposition is lower for the nano-
composites compared to reference PET. This observation
could be due to the degradation of alkyl ammonium modi-
fier which is present in Cloisite 10A. The alkyl ammonium
Journal of Polymers and the Environment (2019) 27:37–49 43
Fig. 3  a TGA weight loss curves and b first derivative TGA curves
for PET–clay nanocomposites during TGA analysis under air atmos-
phere
present in the Cloisite is known to undergo Hoffman degra-
dation around 200 °C [38, 39]. The amount of residue left
over on TGA analysis (at 750 °C) under nitrogen atmosphere
is higher than that of the TGA analysis under air atmosphere.
DSC Analysis
The influence of clay on thermal properties and crystalliza-
tion behaviour of recycled PET was investigated by using
differential scanning calorimetry (DSC). Thermal properties
of PET–clay nanocomposites, such as glass transition tem-
perature ­(Tg) crystallization temperatures ­(Tc), melting tem-
peratures ­(Tm), enthalpies of melting (ΔHm), and the degree
of crystallinity were obtained from the DSC analysis. The
results of the DSC analysis are presented in the Table 3. The
degree of crystallinity (Xc) was determined from the melting
enthalpy values using Eq. (1) [40].
𝛥Hm
Xc = × 100 (1)
(1 − φ)𝛥H om
where 𝛥Hm is second melting enthalpy of the samples (J/g),
𝛥H om is the enthalpy value of melting of a 100% crystalline
form of PET, 117.6 J/g [41], and ϕ is the weight fraction
of filler.
Fig. 4  a TGA weight loss curves and b first derivative TGA curves
for PET–clay nanocomposites during TGA analysis under nitrogen
atmosphere
It is clear from the results in the Table 3 that incorpora-
tion of clay into the PET matrix reduces the ­Tg of the PET
matrix. The reason for the reduction in ­Tg with incorporation
of clay could be due to the higher polymer chain mobility
in presence of clay. In addition, the modifier present in the
clay could act as a plasticizer and increase polymer chain
motion. Similar reduction in ­Tg is reported in the literature
for nanocomposites based on PET and organo-modified clay
[42–44]. Addition of clay into PET has very little influence
on melting temperature, T ­ m2 of nanocomposite samples.
However, incorporation of clay into PET slightly increases
the crystallization temperature, ­Tc of nanocomposites. With
increase in clay loading, the T ­ c of nanocomposites gradu-
ally increases. In addition, the degree of crystallinity of the
PET–clay nanocomposites slightly increase with increase in
clay content. This increase in crystallization temperature and
the degree of crystallinity in the nanocomposites could be
due to the nucleation effect of clay platelets in PET matrix.
Presence of nano-reinforcements, such as clays and CNTs
are known to exhibit nucleating effect in polymer matrices
[8, 45, 46].
The DSC second heating curves and cooling curves of
PET nanocomposites containing different amounts of clay
are presented in Fig. 5a. A double melting peak appeared for
both reference PET and the nanocomposites. This behaviour
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44 Journal of Polymers and the Environment (2019) 27:37–49

Table 2  The results of TGA Sample Temp. at 1% Temp. at 5% Onset of Wt. loss during Residual
analysis on reference PET and weight loss weight loss decomposition 2nd decomp. mass at
PET–clay nanocomposites (%) 750 °C (%)
Air N2 Air N2 Air N2 Air N2 Air N2

Ref. PET 369 391 407 412 429 429 14.3 NA 0.1 6.7
PET–clay (1.0) 372 378 408 405 430 425 15.2 NA 1.0 10.0
PET–clay (2.0) 370 368 401 400 426 424 15.8 NA 1.4 12.5
PET–clay (4.0) 364 363 399 398 424 424 17.1 NA 2.7 13.2
PET–clay (6.0) 352 352 400 399 425 425 17.3 NA 3.8 17.1

Table 3  Results of DSC Sample Tg (°C) Tm1 (°C) Tm2 (°C) Tc (°C) Enthalpy of Crystallinity (%)
analysis—Tg, ­Tm1, ­Tm2, ­Tc, melting (J/g)
enthalpy of melting and degree
of crystallinity Ref. PET 79.5 242 249 196 44.0 37.4
PET–clay (1.0) 79.5 242 249 197 43.5 37.0
PET–clay (2.0) 78.8 242 249 199 46.5 39.5
PET–clay (4.0) 78.5 242 250 200 47.0 40.0
PET–clay (6.0) 76.0 242 251 200 45.0 38.3

peaks, indicating that added clay has no influence on the

crystal morphology in the PET–clay nanocomposites. As
seen from the thermograms, the position of the first melt-
ing ­(Tm1) is unaltered and the second melting peak tem-
perature ­(Tm2) is slightly affected by presence of clay filler.
The low temperature first melting peak is observed at about
242 °C while the high temperature main peak position var-
ies between 249 and 251 °C depending on the clay content.
In addition, with increase in clay loading, the first melting
peak shoulder is less pronounced, being obvious for the
nanocomposite containing 6 wt% of clay. This is probably
because clay at higher loadings starts to influence crystal-
lization behaviour and morphology.
The DSC crystallization endotherms of PET and
PET–clay nanocomposites are presented in Fig. 5b. A slight
shift in the crystallization peak position towards the higher
temperature is observed for the nanocomposites containing
clay. This means that the nanocomposite samples crystallize
at higher temperature compared to the reference PET, as
also seen from the corresponding T ­ c values in Table 3. The
shift in crystallization peak towards higher temperature is
due to the heterogenous nucleating effect of dispersed clay
in PET matrix.

Fig. 5  DSC melting endotherms (a) and crystallization exotherms (b)
for reference PET and PET–clay nanocomposites
could be due to the presence of a dual lamella thickness dis-
tribution which is formed during crystallization of PET [47].
The nanocomposite samples also presented double melting
GPC Analysis
In order to understand the influence of clay on the molecular
weight of PET during the processing of nanocomposites,
GPC analysis was performed on PET–clay nanocomposites.
Thermal processing of PET in presence of clay could lead
to thermal, hydrolytic or oxidative degradation resulting in

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Journal of Polymers and the Environment (2019) 27:37–49 45

Table 4  The GPC analysis results of PET and PET–clay nanocom- decreases gradually with increase in clay content. This
posites observation indicates that melt processing of PET in pres-
Sample Mw Mn PDI ­(Mw/Mn) ence of clay leads to degradation of polymer, hence a reduc-
tion in molecular weight. The polydispersity index values
As received PET 34,350 7460 4.6
for the resin in nanocomposite samples is of similar order.
Ref. PET 31,950 8775 3.7
PET–clay (1.0) 31,150 8545 3.7
Dynamic Mechanical Analysis (DMA)
PET–clay (2.0) 31,150 8265 3.8
PET–clay (4.0) 29,000 8015 3.7
Dynamic mechanical analysis (DMA) was carried-out on
PET–clay (6.0) 27,750 7805 3.6
PET–clay nanocomposites to understand the influence of
clay on viscoelastic behaviour of the materials. The vari-
ation of the storage and loss moduli with temperature for
decrease of molecular weight. The properties of PET are PET–clay nanocomposites are presented in the Fig. 6a, b,
strongly linked to its molecular weight. For meaningful respectively. The storage modulus behaviour in Fig. 6a shows
comparison of properties among the nanocomposites, it is that the PET–clay nanocomposites possessed slightly higher
important to measure the molecular weight of PET matrix storage modulus compared to the reference PET below the
in different composite samples. The results of GPC analysis, Tg. A gradual increase in storage modulus is observed with
weight average molecular weight M ­ w, the number average increase in clay content in PET matrix. Among the nano-
molecular weight ­Mn and the molecular weight distribution composite samples, PET–clay (6.0) had the highest storage
­Mw/Mn for reference PET and PET–clay nanocomposites modulus (about 17%) compared to reference PET and other
are presented in Table 4. The reference PET and PET–clay nanocomposite samples. The improved storage modulus in
nanocomposites showed slightly lower molecular weights PET–clay nanocomposites is due to the reinforcement effect
compared to the as received PET material. The reference of clay in PET matrix. A sharp decrease in the moduli was
material and PET–clay nanocomposites have undergone observed corresponding to glass–rubber transition at around
similar thermal processing. Among the nanocomposite 80 °C. All nanocomposite samples had slightly higher stor-
samples, the molecular weight (both ­Mw and ­Mn) of PET age modulus at 30 °C and slightly lower storage modulus at
80 °C compared to reference PET.
Variation of loss modulus with temperature for PET–clay
nanocomposites is presented in Fig. 6b. Compared to PET,
the nanocomposites had the maxima of peak at lower tem-
peratures. The glass transition, Tg was estimated based on
the temperature maxima in the loss modulus curves. The
reference PET sample showed a Tg of 79.6 °C while the
nanocomposites had lower Tg values, the lowest Tg being for
the nanocomposite with highest amount of clay. A similar
trend in Tg is observed from DSC analysis.

Fig. 6  Variation of storage modulus (a) and loss modulus (b) with

temperature for PET–clay nanocomposites Fig. 7  Variation of impact strength among PET–clay nanocomposites

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46
Mechanical Properties of Nanocomposites
Impact Properties
The effect of clay incorporation on impact strength of
PET–clay nanocomposites was investigated. The variation
of impact strength among the nanocomposites containing
different amounts of clay is presented in Fig. 7. Incorpora-
tion of clay into the PET resin at low loadings, up to 4 wt%
did not alter the impact strength. However, increasing the
clay loading beyond 4 wt%, for example, the nanocomposite
containing 6 wt% of clay [PET–clay (6.0)] presented 28%
reduction in impact strength compared to the reference PET.
In addition, the standard deviation for the same is high. Such
reduction in impact strength in clay reinforced polymeric
materials is reported in the literature [7].
Tensile Properties
The influence of clay on tensile properties of PET–clay
nanocomposites was also investigated. The variations of the
tensile strength and tensile modulus of the PET–clay nano-
composites are presented in Fig. 8a. The tensile strength and
modulus increases gradually with increase in clay content
in nanocomposites. In case of PET–clay (1.0), the average
tensile strength was slightly lower compared to reference
Fig. 8  Tensile strength and tensile modulus (a) and elongation at
yield and elongation at break for of PET–CNT nanocomposites (b)
13
Journal of Polymers and the Environment (2019) 27:37–49
PET matrix. The decrease in tensile strength was within
the standard deviation. The higher standard deviation in
PET–clay (1.0) could be due to inhomogeneity of the sample
compared to others. The nanocomposite sample containing
6.0 wt% of clay [PET–clay (6.0)], presented increased tensile
modulus and tensile strength by about 28% and 10%, respec-
tively. The increased tensile properties are due to the rein-
forcement effect of homogeneously dispersed delaminated
clay platelets in the PET matrix. An even higher amount
of clay in the matrix could improve the tensile properties
even more. However, processing of PET matrix with high
loadings of clay may adversely affect the impact properties.
The variation of elongation at yield and break in nano-
composites is presented in Fig. 8b. The elongation at yield
for PET–clay nanocomposites decreases gradually with
increase in clay loading, from 3.7 to 3.3%. The reference
PET and nanocomposite material containing 1 and 2 wt% of
clay presented an elongation at break in the order of 220%.
With higher loadings (4 and 6 wt% of clay) the elongation
at break decreased significantly to 30 and 3% respectively.
Such reduction in elongation at break is common in clay
reinforced polymeric materials and similar observations are
reported in the literature [7, 27].
Morphology Investigation
Scanning Electron Microscopy
The morphology of the samples was investigated by using
SEM. The SEM analysis was performed on the etched sur-
faces of the injection moulded specimens. The SEM images
of the PET–clay (4.0) and PET–clay (6.0) nanocomposite
samples are respectively presented in Fig. 9a, b. Both the
nanocomposite samples presented no visible agglomerates
of clay platelets. However, the dispersed clay platelets in
PET matrix are not clearly visible in the microscopic images,
which could be caused by the coating of etched PET resin on
the clay platelets. An attempt was made to wash-off the PET
resin with alcohol during the etching process for the SEM
preparation, but this attempt was not successful. In addition,
an attempt to analyse the freeze fractured injection moulded
specimen surface by SEM did not provide useful information
regarding clay dispersion in the composite materials.
Light Microscopy
In order to see the micro-dispersion quality of clay in
PET–clay nanocomposites, light microscopy (LM) inves-
tigations was performed. Light microscopy images of
PET–clay (4.0) and PET–clay (6.0) nanocomposites are
respectively presented in the Fig. 10a, b. It is clear from the
microscopic images that the dispersion quality of clay par-
ticles in PET matrix is reasonably good and no microscopic
Journal of Polymers and the Environment (2019) 27:37–49 47
Fig. 9  SEM images of a PET–clay (4.0) and b PET–clay (6.0)
Fig. 10  Light microscopy images of a PET–clay (4.0) and b PET–clay (6.0)
agglomerates were observed. Since the specimens for LM
was made from injection moulded samples, material flow
lines were observed in the LM images.
Conclusion
Recycled poly(ethylene terephthalate) nanocomposites con-
taining ­Cloisite® 10A as a reinforcement were prepared by
conventional melt compounding method via masterbatch
dilution. The rheological, thermal, mechanical and morpho-
logical properties were investigated in the nanocomposites.
Incorporation of clay into recycled PET greatly influence
the rheological properties. The complex viscosity, storage
and loss modulus of the nanocomposites gradually increases
with increase in clay content. In addition, rheological inves-
tigation indicates that complete percolation occurs at 6
wt% of clay loading. The nanocomposites a slightly higher
crystallisation temperature and degree of crystallinity com-
pared to reference PET. The increased crystallization tem-
perature and degree of crystallinity of nanocomposites is
due to a heterogenous nucleating effect of clay. The thermal
stability and glass transition temperature of nanocomposite
at lower clay loadings are similar to r-PET but gradually
decrease with increase in clay content. The tensile proper-
ties of PET–clay nanocomposites increased gradually with
clay content. The impact strength of nanocomposites was
not altered until 4 wt% of clay and decreased at 6 wt% clay
loading. Morphological investigations did not provide the
nano-scale dispersion quality of clay in r-PET matrix. The
future study in this direction will focus on EDAX, TEM,
XRD, WAXS, etc. characterization of the nanocomposites
produced in this work.
The incorporation of clay into recycled PET increases
the viscosity and mechanical properties and makes the
material suitable for extrusion and injection moulding
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48
applications. The recycled PET–clay nanocomposites
could find applications in value-added technical products.
Acknowledgements  The research leading to these results has received
funding from the European Union’s Seventh Framework Programme
(FP7) under Grant agreement no. 309985. The authors would like to
thank the Smithers Rapra, UK for their support with GPC analysis on
the samples.
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