polymers

Article
Effects of Organic Based Heat Stabilizer on Properties of
Polyvinyl Chloride for Pipe Applications: A Comparative Study
with Pb and CaZn Systems
Chanchira Jubsilp 1 , Aran Asawakosinchai 2 , Phattarin Mora 1 , Duangporn Saramas 3 and Sarawut Rimdusit 2, *

1 Department of Chemical Engineering, Faculty of Engineering, Srinakharinwirot University,

Nakhon Nayok 26120, Thailand; chanchira@g.swu.ac.th (C.J.); phattarin@g.swu.ac.th (P.M.)
2 Research Unit in Polymeric Materials for Medical Practice Devices, Department of Chemical Engineering,
Faculty of Engineering, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand;
llxartxll@hotmail.com
3 Vinythai PLC, 2 Map Ta Phut Industrial Estate, I-3 Rd., Map Ta Phut, Muang, Rayong 21150, Thailand;
Duangporn.sara@agc.com
* Correspondence: sarawut.r@chula.ac.th; Tel.: +66-2218-6862

Abstract: In this paper, the effects of organic based stabilizers (OBS) are investigated and compared
with traditional lead (Pb) and calcium zinc (CaZn) heat stabilizers regarding their processability,
mechanical property, and thermal degradation behaviors in rigid PVC pipe applications. In addition,
the effects of repeated processing cycles on the degree of gelation and the impact strength of the
PVC/OBS, PVC/CaZn, and PVC/Pb are also examined. A repeated processing cycle of those three





 types of the heat stabilizers up to four cycles was found to increase the degree of gelation and proved
Citation: Jubsilp, C.; no significant effect on the impact strength and heat resistance of the resulting PVC samples. The
Asawakosinchai, A.; Mora, P.; OBS showed a positive effect on preventing the autocatalytic-typed thermal degradation of the PVC
Saramas, D.; Rimdusit, S. Effects of samples. This leads to a longer retention time for the initial color change of the PVC/OBS compared to
Organic Based Heat Stabilizer on PVC/Pb or PVC/CaZn systems. This characteristic was related to a more uniform fusion behavior of
Properties of Polyvinyl Chloride for
the PVC/OBS, i.e., the lowest gelation speed and the longest fusion time. The non-isothermal kinetic
Pipe Applications: A Comparative
parameter determined by the Kissinger and Flynn–Wall–Ozawa methods of the dehydrochlorination
Study with Pb and CaZn Systems.
stage of the PVC/OBS was in satisfactory agreement and continued to compare with the PVC/Pb
Polymers 2022, 14, 133. https://
and PVC/CaZn systems. The results indicated that the OBS might decrease the dehydrochlorination
doi.org/10.3390/polym14010133
rate of PVC, implying that PVC/OBS was more stable than PVC/Pb and PVC/CaZn systems.
Academic Editors: Andrea
Antonino Scamporrino and Chiara Keywords: fusion time; gelation; color change; activation energy; mechanical property
Maria Antonietta Gangemi

Received: 4 December 2021

Accepted: 23 December 2021
Published: 30 December 2021 1. Introduction
Publisher’s Note: MDPI stays neutral
Polyvinyl chloride (PVC) is a well-known commodity plastic with a broad spectrum of
with regard to jurisdictional claims in properties that are rigid, semi-flexible, and flexible. It is widely used in various construction
published maps and institutional affil- applications, including water, sewage, or drainage pipes and in many extruded profiles.
iations. The rigid PVC form has broad acceptance and exhibits a good market growth in major
PVC product applications, i.e., pipes, due to its outstanding functional properties and cost
competitiveness [1,2]. However, PVC is thermally unstable at processing temperatures.
When PVC is heated to 170–180 ◦ C, chlorine and hydrogen in the molecules are eliminated,
Copyright: © 2021 by the authors. and it releases hydrochloric acid (HCl), which in turn accelerates the thermal degradation
Licensee MDPI, Basel, Switzerland. process of the number of conjugated double bonds formed during the processing. It also
This article is an open access article causes the level of color in the sample to range from yellow to black [1–3]. Hydrochloric acid
distributed under the terms and can also deteriorate the mechanical, thermal, and physical properties of PVC. Therefore,
conditions of the Creative Commons
heat stabilizers were widely used to safeguard the vinyl products at all stages by improving
Attribution (CC BY) license (https://
the heat resistance of PVC products at high temperatures, preventing the chain reaction
creativecommons.org/licenses/by/
of degradation. They can also impart PVC to enhance daylight resistance, weathering,
4.0/).

Polymers 2022, 14, 133. https://doi.org/10.3390/polym14010133 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 133 2 of 16

and heat ageing. Recently, heat stabilizers contributed more than 30% of the global PVC
additive demand. Heavy metal-based heat stabilizers such as lead (Pb)-based products are
responsible for a large proportion of products in the heat stabilizer group. These products
are widely used for the stabilization of pipe in Europe and Asia (except Japan). However,
in 2003, the European Union passed regulations that stated the use of Pb will be limited
in the production of PVC pipes, as well as in a number of other manufacturing processes.
As a consequence, considerable efforts have been expended towards the development of
new stabilization systems for PVC processing, which is driven by a desire to move away
from stabilizers based on heavy metals [4,5]. An alternative stabilizer to replace Pb-based
stabilizers such as calcium zinc (CaZn) is investigated. CaZn stabilizers are preferred for
use in critical applications because of low toxicity; however, they are the least effective
option in terms of thermal performance. In addition, CaZn was used by pipe producers but
not advanced further due to relatively high costs [5]. Therefore, to ensure that PVC meets
the regulations and remains an acceptable material for use in pipe applications, organic-
based stabilizers (OBSs) have been developed to replace traditional Pb-based stabilizers
and to overcome the disadvantage in long-term stability of CaZn-based stabilizers.
Organic based stabilizers for PVC have been recognized as a new technology for pro-
viding environmentally friendly heat stabilizers in PVC pipe production. Their usage has
been increased in recent years due to economic growth in emerging markets and increased
knowledge about the benefits of organic based stabilizers for PVC [6,7]. In addition, organic
based stabilizers deliver several other advantages, such as outstanding paint fastness even
after many processing rounds. In fact, it typically consists of components that are stated
positively, making it ideal for interaction with food. Organic based stabilizers for PVC
exhibit high thermal stability and excellent properties for recycling. These reasons have
motivated producers all over the world, and many are switching to organic alternatives
because of legislation, market pressure, or on a voluntary basis. However, there is very little,
or no information in comparison to rheology, thermal stability in terms of color change, heat
resistance, and thermal degradation kinetic as well as the recycling ability of PVC stabilized
with traditional Pb and CaZn heat stabilizers. There is also a lack of comparison to OBS
which is a more eco-friendly heat stabilizer, essentially free of heavy metals—such as lead,
barium, zinc, tin, or cadmium—which contains calcium in these solid metals. Therefore,
in this present work, we are motivated to investigate the performance of organic based
stabilizers (OBS). The rheological behaviors, color change, thermal stability, and mechanical
property of PVC/OBS systems compared with those of PVC/Pb and PVC/CaZn systems
were also studied. The recycling ability of the PVC/OBS, PVC/CaZn, and PVC/Pb was
evaluated. PVC/OBS was expected to have a better performance than PVC/CaZn and
PVC/Pb. This work also focused on thermal degradation kinetics through TGA mea-
surement under non-isothermal conditions in a nitrogen atmosphere for the PVC/OBS,
which, to the best of our knowledge, has not been reported on in the literature. The kinetic
parameters based on the Kissinger method, using the peak temperature as the maximum of
the reaction rate, and the isoconversional method, Flynn–Wall–Ozawa (FWO), based on
the extent of reaction (conversion), were studied.

2. Materials and Methods

2.1. Materials
Suspension-grade PVC resin with a K-value of 66, calcium carbonate filler, and a lead
(Pb) stabilizer was supplied by Vinythai PCL (Bangkok, Thailand). Calcium zinc (CaZn)
stabilizer was supplied by Dalian Chemson Technical Co., Ltd. (Dalian, China). Organic
based stabilizer (OBS) was provided by Brenntag Ingredients (Thailand) PCL (Bangkok,
Thailand). All PVC heat stabilizers, i.e., Pb, CaZn, and OBS are one-pack systems.

2.2. Sample Preparation

PVC compounds were prepared from PVC resin, calcium carbonate, and heat stabiliz-
ers such as Pb, CaZn, and OBS at a mass content of 3 phr. The PVC compounds were mixed
Polymers 2022, 14, 133 3 of 16

in a high-speed mixer (Plas Mec Turbomixer, Varese-Italy). The mixing process consists of
two mixing tanks, operating with two steps of hot and cold blending using temperature
levels of 70 and 30 ◦ C, respectively. The PVC compounds were then processed by two-roll
mills with a 0.125-mm gap at a temperature of 180 ◦ C for 3 min to yield a homogeneous
sample in sheet form.

2.3. Research Methods

2.3.1. Physical Property
The fusion behaviors of the PVC compounds were measured by torque rheometer
(Brabender kneader, Plasti–Corder Pl, Duisburg-Germany). The chamber temperature was
kept at 180 ◦ C, and the screw rotational speed was approximately 60 rpm.
Discoloration of strips was obtained by two-roll mills with a sample size of
1.5 cm × 30 cm × 1.0 mm and was observed in static thermal stability tests. The strips
were put in the Mathis thermotester (Zurich, Switzerland) at a temperature of 180 ◦ C and
held for 5 min and then automatically moved out of the box at 1 mm/min.
The degree of gelation was measured using differential scanning calorimetry (DSC),
model DSC1, STARe system, Mettler-Toledo (Zurich, Switzerland). Each sample of 10 mg
was put in an aluminum pan with a lid and scanned at a heating rate of 10 ◦ C/min from
50 to 250 ◦ C under nitrogen purging with a constant flow of 50 mL/min.

2.3.2. Mechanical Property

Flexural properties of samples were tested using a universal testing machine (UTM),
model 5567, Instron (Massachusetts, USA), according to ASTM D790. Three-point bending
was carried out using a crosshead speed of 1.2 mm/min with a support span of 48 mm.
The sample dimension was 4 mm × 12.7 mm × 64 mm. A five-averaged value was taken
and reported.
The notched Izod impact strength of the samples was measured using an impact
tester (Yasuda, Chiba-Japan) according to ASTM D256. The sample dimension was
12.7 mm × 60 mm × 3.2 mm, and the depth under the notch of the sample was 10.7 mm.

2.3.3. Thermal Degradation Analysis

TGA thermograms of samples were acquired using thermogravimetric analysis (TGA)
(model TGA1 STARe system, Mettler-Toledo, Zurich-Switzerland). A sample of approxi-
mately 10 mg was used for each test. The temperature program was heated with a heating
rate of 20 ◦ C/min from 25 to 800 ◦ C, under nitrogen purging with a constant flow of
50 mL/min.
The thermal degradation kinetics of the samples were studied by a thermogravimetric
analyzer. Each sample was scanned from room temperature to 800 ◦ C under the nitrogen
atmosphere at heating rates of 5, 10, and 20 ◦ C/min. Kinetic parameters, such as acti-
vation energy (Ea , kJ/mol), were calculated using the Kissinger and Flynn–Wall–Ozawa
(FWO) methods.

2.3.4. Kinetic Analysis and Methods

According to the non-isothermal kinetic theory of solid-state reactions [8,9], the rate of
conversion of the sample (dα/dt) is proportional to the concentration of the reacted sample.
It is a linear function of a temperature-dependent rate constant, k, and a temperature-
independent function of conversion (α), that is:

dα
= k f (α) (1)
dt
m0 − m t
α= (2)
m0 − m f
Polymers 2022, 14, 133 4 of 16

where mt is the measured experimental mass at time t, m0 is the initial mass, and mf is the
mass at the end of the non-isothermal experiments. 
− Ea
Substituting the Arrhenius equation k = Aexp RT into Equation (1), obtains:

− Ea
 
dα
= Aexp f (α) (3)
dt RT

where A is the Arrhenius pre-exponential factor (1/min), Ea is the activation energy

(kJ/mol), T is the absolute temperature (K), R is the gas constant (8.314 J/mol K), and f (α)
accounts for the reaction rate dependence on α. The kinetic model, f (α), is an algebraic
expression that is usually associated with a physical model that describes the kinetics of
the solid-state reaction.
For non-isothermal kinetic theory, the temperature of the sample is changed by a
controlled and constant heating rate, β(K/min) = dT/dt. Therefore, the reaction rate is
given by:
− Ea
 
dα A
= exp f (α) (4)
dT β RT
Integration of this equation from an initial temperature (T0 ) corresponding to a null
degree of conversion, to the peak temperature of the derivative thermogravimetric curve
(DTG), Tp , where α = αp gives:

− Ea
 
dα A
Z αp Z αp
g(α) = = exp dT (5)
0 f (α) β 0 RT

where g(α) is the integral function of conversion.

1. Kissinger method (Differential method) [10–12];
The Kissinger method is used to determine the activation energy of solid-state re-
actions. From the slope of the plots between the logarithms of the heating rate and the
inverse of temperature at the maximum of the reaction rate in constant heating rate experi-
ments, the activation energy can be obtained without precise knowledge of any thermal
degradation reaction mechanism, using the following equation:
 
β AR h
n −1 i Ea
ln 2 = ln + ln n 1 − α p − (6)
Tp Ea RTp

where Ea is the activation energy, β is the heating rate; Tp is the temperature corresponding
to the inflection point of the thermal degradation curves, which corresponds to the maxi-
mum reaction rate; A is the pre-exponential factor; αp is the maximum conversion; and n is
the reaction order.
2 Flynn–Wall–Ozawa (FWO) method (Isoconversional integral method) [13,14]
FWO is one of the integral methods used to calculate the kinetic parameters using
Doyle’s approximation of a temperature integral. This method can be employed to quantify
the activation energy at given values of conversion (Ea,∝ ) without any knowledge of the
reaction mechanisms, using the following equation:
 
Aα Ea,α 0.456Ea,α
logβ = log − 2.315 − (7)
g(α) R RTα
dα
Rα
where g(α) = 0 f (α) is the integral conversion function.
Polymers 2022, 14, 133 5 of 16

3. Results
Polymers 2021, 13, x FOR PEER REVIEW
3.1. Fusion Characteristics of PVC Compounds Stabilized with Various Heat Stabilizers5 of 17

Fusion characteristics, consisting of fusion torque, fusion time, and fusion temperature,
are an important rheological behavior that helps to understand the processability of PVC
PVC compounds
compounds and machine
and machine safety. safety. The processability
The processability of PVCofcompounds
PVC compoundsis usuallyis usually
measured
inmeasured in terms
terms of fusion of fusion characteristics.
characteristics. It is a well‐known
It is a well-known fact that
fact that a grain a grain
of PVC of PVC is
compounds
compounds
the largest unitisof the largest particles
primary unit of primary
having an particles having anapproximately
agglomeration, agglomeration,1 µm. approxi‐
During
the processing of PVC grains, primary particles are broken down to produce a down
mately 1 μm. During the processing of PVC grains, primary particles are broken to
continuous
produce a continuous phase. Therefore, the rheological data, such as torque and temper‐
phase. Therefore, the rheological data, such as torque and temperature at constant rotational
ature at constant rotational speed versus time of PVC compounds under processing con‐
speed versus time of PVC compounds under processing conditions, was measured. The
ditions, was measured. The plastograms of the fusion characteristics measured from the
plastograms of the fusion characteristics measured from the torque rheometer of PVC
torque rheometer of PVC compounds, i.e., PVC/Pb, PVC/CaZn, and PVC/OBS, are pre‐
compounds, i.e., PVC/Pb, PVC/CaZn, and PVC/OBS, are presented in Figure 1. From the
sented in Figure 1. From the plots, the red line was a real PVC compound temperature,
plots, the red line was a real PVC compound temperature, whereas the blue line was the
whereas the blue line was the mixing torque as a function of mixing time. After the loading
mixing torque as a function of mixing time. After the loading stage, a significant increase
stage, a significant increase of the torque was observed (point A), while the temperature
ofalso
the rose
torqueduewas observed
to frictional (point
heat. The A), while
torque the to
started temperature
decrease near also roseAdue
point untiltopoint
frictional
B
heat. The torque started to decrease near point A until point B mainly
mainly due to the onset of homogenization and rose in temperature as a result of shear. due to the onset of
homogenization and rose
At point B, the torque in temperature
tended as a result
to increase because of shear.
of the At point
compaction, B, the torque
melting, and entan‐ tended
toglement
increaseofbecause of the compaction, melting, and entanglement of
the PVC molecules at the primary particle surface. Then, the inflection wasthe PVC molecules
atobserved
the primary particle
at point G, atsurface.
which the Then,
PVCthe inflectionwas
compound was observed
melted at point
and the torque G,rose
at which
again the
PVC compound was melted and the torque rose again up to X. Thereafter,
up to X. Thereafter, cross‐linking was facilitated. For the temperature curve, the tempera‐ cross-linking
was
turefacilitated. For the temperature
increased gradually, leading to the curve, theattemperature
fusion increased
point G. Finally, gradually,reached
the temperature leading to
the fusion at point
a steady‐state afterG. Finally,
point the point
X. After temperature
X, a slight reached
decreasea steady-state
and stabilizationafterofpoint X. After
the torque
point
can beX, aobserved
slight decrease
at pointand stabilization
E, whereas of the torquebetween
the temperature can be observed
points X andat point E, whereas
E remained
the temperature
relatively between
constant [15]. points X and E remained relatively constant [15].

Figure
Figure 1. PlastogramsofofPVC
1. Plastograms PVCcompounds:
compounds: (a)
(a) PVC/Pb,
PVC/Pb, (b)
(b)PVC/CaZn,
PVC/CaZn,(c) (c)
PVC/OBS.
PVC/OBS.

The
Therheological
rheological data,
data, such
such asas torque
torqueand
andtemperature
temperature atat a constant
a constant rotational
rotational speed
speed
versus
versus time of the PVC/Pb, PVC/CaZn, and PVC/OBS compounds, can be seen in Figure 1
time of the PVC/Pb, PVC/CaZn, and PVC/OBS compounds, can be seen in Figure
and tabulated
1 and in in
tabulated Table 1. 1.ItItcould
Table couldbe beobserved that the
observed that thefusion
fusiontime
timeofofthe
the PVC/Pb
PVC/Pb andand
PVC/CaZn
PVC/CaZn is is shorter thanthat
shorter than thatofofthe
thePVC/OBS.
PVC/OBS. TheThe order
order of fusion
of fusion timetime is PVC/OBS
is PVC/OBS >
Polymers 2022, 14, 133 6 of 16

> PVC/CaZn > PVC/Pb. This may be due to the fact that the PVC/Pb and PVC/CaZn
interacted and formed powerful elements with less absorbed energy compared to PVC/OBS.
Therefore, the PVC/Pb and PVC/CaZn tends to be easier to process than the PVC/OBS.
However, the degradation behavior of the compounds is also considered in PVC processing.
From the fusion time values, it is indicated that the PVC/OBS would degrade slower
than the PVC/Pb and the PVC/CaZn. This result was in agreement with the longer
degradation time (the difference in time between A and E) of PVC/OBS measured as 895 s
compared to that of the PVC/Pb and the PVC/CaZn along 590 s and 892 s, respectively. In
addition, the degradation behavior of the PVC compounds can also be evaluated from the
gelation speed related to the crosslinking of the compounds under processing conditions.
From Table 1, the lowest gelation speed related to the highest crosslinking belonged to
the PVC/OBS. It confirms that the PVC/OBS compound was degraded slower than the
other two aforementioned compounds. Therefore, it summarizes that the addition of OBS
may significantly inhibit the degradation behavior of the PVC compound compared to the
addition of Pb and Ca/Zn stabilizers.

Table 1. Maximum torque and fusion time of PVC compounds.

Gelation
PVC Brabender Plasticorder Torque Stock Temp. Fusion Time
Time (s) Speed
Compound Value (Nm) (◦ C) (A–X) (s)
(Nm/min)
Loading peak, A 40 10 150
Minimum, B 8.5 135 178
PVC/Pb Inflection point, G 19 290 187 5.64 320
Maximum, X 31.0 330 193
End, E 27.5 600 202
Loading peak, A 39 8 148.5
Minimum, B 6.5 82 172.5
PVC/CaZn Inflection point, G 18.5 420 185 4.11 452
Maximum, X 31.5 460 192
End, E 26.5 900 201
Loading peak, A 33.5 5 143.5
Minimum, B 6.5 135 174
PVC/OBS Inflection point, G 16.5 527 187 2.73 581
Maximum, X 26.7 586 193
End, E 23.0 900 198.5

3.2. Static Thermal Stability of PVC Stabilized with Various Heat Stabilizers
Static thermal stability of rigid PVC/Pb, PVC/CaZn, and PVC/OBS samples processed
by two roll mills at 180 ◦ C for 3 min was revealed by the observation of a visual change in
color due to heating at 180 ◦ C as a function of time, as shown in Figure 2. However, this
practice is particularly applicable for determining gross differences in the heat stabilities of
the PVC compositions that are detectable as a color change that is not intended to measure
absolute thermal stability. From the figure, the color of PVC/Pb was changed rapidly from
white to light yellow within 30 min, and then a gradual change in color from light yellow
to yellow, turning brown within 160 min. The color of the PVC/CaZn could maintain its
original white color for approximately 40 min and then experienced a gradual change in
color from light yellow to yellow, turning to dark brown within 130 min. The PVC/OBS
revealed that no color change was obtained up to 50 min, then the sample changed to yellow
and turned dark brown within 140 min. It was found that the addition of the OBS stabilizer
in the PVC showed better results in maintaining the initial color than the PVC/Pb and the
PVC/CaZn. This behavior may confirm that the OBS can restrain the PVC degradation
effectively during its processing. A similar behavior was also observed in the PVC/organic
stabilizer, i.e., PVC/N-monomethyl-6-amino-thiouracil (MATU), showing better results in
maintaining the initial color compared to the PVC/ZnSt2 [16]. In addition, the degradation
 Polymers 2021, 13, x FOR PEER REVIEW 7 of 17

PVC degradation effectively during its processing. A similar behavior was also observed
Polymers 2022, 14, 133 7 of 16
in the PVC/organic stabilizer, i.e., PVC/N‐monomethyl‐6‐amino‐thiouracil (MATU),
showing better results in maintaining the initial color compared to the PVC/ZnSt2 [16]. In
addition, the degradation behavior by observation of color change in the PVC/OBS was
behavior by observation
significantly related to of
thecolor change
highest in the
fusion, PVC/OBStimes,
degradation was significantly related
and the lowest to the
gelation
speed,fusion,
highest which resulted in slower
degradation times,degradation. These
and the lowest characteristics
gelation would
speed, which cause ainhigher
resulted slower
quality of theThese
degradation. PVC/OBS at the end of
characteristics the processing.
would cause a higher quality of the PVC/OBS at the
end of the processing.

Figure2.2.Color
Figure Colorchange
changeofofrigid
rigidPVC
PVCstabilized
stabilized with
with various
various heat stabilizers.
stabilizers. (All
(Allsample
samplestrips
strips were
were processed
processed by two‐roll
by two-roll mills at 180at◦ 180
mills °C3for
C for min3 min
andand then
then automatically
automatically movedout
moved outofofthe
thebox at
box at 1 mm/min by a Mathis thermotester ◦at 180 °C under
1 mm/min by a Mathis thermotester at 180 C under air atmosphere). air atmosphere).

InInprinciple,
principle,the the thermal
thermal degradation
degradation process
process of of
PVCPVC involves
involves three
three major
major steps:
steps: (1)(1)
the
the initiation
initiation of dehydrochlorination,
of dehydrochlorination, (2) the (2)elimination
the elimination of hydrochloride
of hydrochloride (HCl)(HCl) and sim‐
and simultane-
ultaneous
ous formation formation of conjugated
of conjugated double double
bonds, bonds,
and (3)and (3) termination
termination of the dehydrochlo‐
of the dehydrochlorination
rination process. The exact mechanism of the thermal
process. The exact mechanism of the thermal degradation of PVC is still degradation of PVC is still contro‐
controversial, but
versial, but it is generally accepted that the thermal degradation
it is generally accepted that the thermal degradation process with the evolution process with the evolu‐
of HCl
tion
via of HCl
chain via chain
reaction reaction
called zipper called zipper elimination
elimination or unzipping or unzipping
process takes process
placetakes place
[1,17–20].
[1,17–20].
Color change Color change
of the PVCoffrom the PVC from the
the thermal thermal degradation
degradation process has process
been has been at‐to
attributed
tributed
the to theofformation
formation a conjugatedof a conjugated
polyene sequencepolyene sequence
of 5 to 25ofdouble
5 to 25 bonds.
double bonds.
Therefore, There‐
the
fore, the incorporation
incorporation of heat stabilizers
of heat stabilizers such as Pb, suchCaZn,
as Pb,and CaZn,OBS andcanOBS can stabilize
stabilize or pro‐
or prolong its
long itsintegrity
thermal thermal integrity
by preventingby preventing
the chainthe chain reaction
reaction of degradation
of degradation of theas
of the PVCs PVCs as
a result
ofaprocessing
result of processing
temperature temperature
and time.and Fromtime. From2,Figure
Figure it was2, it was observed
observed that the that the sta‐
stabilization
bilization of OBS and CaZn in the PVC is better than Pb by
of OBS and CaZn in the PVC is better than Pb by maintaining the initial color, while maintaining the initial color,
Pb
while Pb can help in the long term thermal stabilization
can help in the long term thermal stabilization of the PVC within 200 min. PVC/CaZn of the PVC within 200 min.
PVC/CaZn
can can holds
holds a better a better
initial colorinitial color compared
compared to the PVC/Pb
to the PVC/Pb and may andbe may anbeeffective
an effectiveHCl
HCl scavenger of strongly basic carboxylates derived
scavenger of strongly basic carboxylates derived from calcium, having little or from calcium, having little
no or no
Lewis
Lewis Zinc
acidity. acidity. Zinc exhibits
exhibits strongerstronger
Lewis acid Lewis acid features
features that formthat form covalent
covalent carboxylates.
carboxylates. It cannot
It cannot
only scavengeonlyHCl scavenge
but can HCl
alsobut can also carboxylate
substitute substitute carboxylate
for the allylicfor chlorine
the allylicatoms
chlorine
and
atoms and thus terminates the growth of the polyene sequences
thus terminates the growth of the polyene sequences [21]. However, the CaZn are generally [21]. However, the CaZn
areleast
the generally the least
effective option effective option
in terms in terms of
of thermal thermal performance
performance and relatively
and relatively high cost. highIn
cost. In the case of PVC/OBS, more effective maintenance
the case of PVC/OBS, more effective maintenance of the initial color than the PVC/Pb of the initial color than the
PVC/Pb was also observed. This behavior can be attributed
was also observed. This behavior can be attributed to the major component of patented to the major component of
patented OBS chemistry based on uracil [22]. The uracil‐based
OBS chemistry based on uracil [22]. The uracil-based stabilizer can retard the degradation stabilizer can retard the
degradation
process process by
by scavenging thescavenging
HCl/Cl radical the HCl/Cl
generatedradical generated
during processingduringandprocessing
suppresses and
the
suppresses the crosslinking, which is more effective
crosslinking, which is more effective than Pb and CaZn stabilizers. than Pb and CaZn stabilizers.

3.3. Thermal Degradation Behaviors of PVC Stabilized with Various Heat Stabilizers
3.3.1. Thermogravimetric Analysis (TGA)
The thermal stability of rigid PVC/Pb, PVC/CaZn, and PVC/OBS samples can be
determined by monitoring the weight change that occurs as a function of temperature
at a constant heating rate. In this study, it was investigated by TGA. Derivative thermo-
gravimetry (DTG) and TGA thermograms of the PVC/Pb, PVC/CaZn, and PVC/OBS
samples compared with PVC samples are depicted in Figure 3. It was found that the
addition of heat stabilizers could enhance the degradation temperature of PVC in the first
stage, evaluated at a 5% weight loss of the PVC/Pb, PVC/CaZn, and PVC/OBS at 295 ◦ C,
293 ◦ C, and 297 ◦ C, respectively, while that of PVC was 276 ◦ C. It showed that the OBS
 297 °C, respectively, while that of PVC was 276 °C. It showed that the OBS as an organic
component could better prevent the chain reaction of degradation of the PVC sample than
the PVC stabilized with Pb and CaZn. This behavior was similar to PVC/eugenol (organic
compound) that showed a longer thermal stability value (Ts) than PVC, PVC/DBLC,
PVC/Ca‐Zn soap, and PVC/OTM [23].
Polymers 2022, 14, 133 8 of 16
Furthermore, the char yield (CR) of the samples at 800 °C was also obtained. The Pb,
CaZn, and OBS stabilizers can increase the CR of the PVC obtained at 16.9%, 19.1%, and
14.3%, respectively, compared with PVC at around 7.9%. The CR of the PVC stabilized
aswith
an OBS
organic
was component could
lower than those of better
Pb andprevent the chain that
CaZn, confirming reaction of degradation
the addition of OBS into of the
PVCsample
PVC reducedthan
char the
formation. However,with
PVC stabilized the PVC/OBS sampleThis
Pb and CaZn. can be classified
behavior as asimilar
was self‐ to
extinguishing (organic
PVC/eugenol category compound)
(LOI > 21) according to thea van
that showed Krevelen
longer thermaland Hoftyzer
stability equation
value (Ts) than
[24], which
PVC, is the same
PVC/DBLC, as the PVC/Pb
PVC/Ca-Zn soap,and
andPVC/CaZn
PVC/OTM samples.
[23].

100
0
Residual weight (%)

80 PVC
PVC/Pb PVC

DTG (%/ C)
PVC/CaZn ‐0.002 PVC/Pb

o
PVC/OBS PVC/CaZn
60 PVC/OBS

40 ‐0.004

20
‐0.006

0
0 200 400 600 800 0 200 400 600 800
o o
Temperature ( C) Temperature ( C)
(a) (b)
Figure 3. (a) TGA thermograms
Figure 3. (a) and
TGA(b) DTG thermograms
thermograms of rigid
and (b) DTG PVC stabilized
thermograms with
of rigid various
PVC stabilizers.
stabilized with various stabilizers.

The CR can bethe

Furthermore, applied as a decisive
char yield (CR) of factor for estimating
the samples at 800 ◦the limiting
C was oxygen index
also obtained. The Pb,
(LOI) of the polymers based on the van Krevelen and Hoftyzer equation,
CaZn, and OBS stabilizers can increase the CR of the PVC obtained at 16.9%, as presented in and
19.1%,
Equation (8).
14.3%, respectively, compared with PVC at around 7.9%. The CR of the PVC stabilized
with OBS was lower than those of Pb 𝐿𝑂𝐼and17.5
CaZn,0.4𝐶𝑅
confirming that the addition of OBS (8) into
PVC reduced char formation. However, the PVC/OBS sample can be classified as a self-
The calculated LOI values derived from their CR of the PVC/Pb, PVC/CaZn, and
extinguishing category (LOI > 21) according to the van Krevelen and Hoftyzer equation [24],
PVC/OBS were 24.3, 25.1, and 23.2, respectively, while the LOI value of the PVC was ap‐
which is the same as the PVC/Pb and PVC/CaZn samples.
proximately 20.7. The results revealed that the addition of Pb, CaZn, and OBS stabilizers
The CR can be applied as a decisive factor for estimating the limiting oxygen index
could help enhance the fire resistance of the PVC, and adding OBS can maintain the fire
(LOI) of the polymers based on the van Krevelen and Hoftyzer equation, as presented in
resistance of the PVC. This suggests that the formation of a solid char barrier would block
Equation (8). oxygen caused by the generation of combustion barriers and delay the flame
the available
LOI = 17.5
propagation by adiabatic effect. In addition, in +
the0.4CR
case of OBS, the organic compounds (8)
would
Thedecompose
calculatedinLOI and water,
CO2values reducing
derived from the LOI
their value.
CR However,
of the PVC/Pb,despite this, the and
PVC/CaZn,
PVC/OBS still maintains an adequate LOI level.
PVC/OBS were 24.3, 25.1, and 23.2, respectively, while the LOI value of the PVC was
approximately 20.7. The results revealed that the addition of Pb, CaZn, and OBS stabilizers
could help enhance the fire resistance of the PVC, and adding OBS can maintain the fire
resistance of the PVC. This suggests that the formation of a solid char barrier would block
the available oxygen caused by the generation of combustion barriers and delay the flame
propagation by adiabatic effect. In addition, in the case of OBS, the organic compounds
would decompose in CO2 and water, reducing the LOI value. However, despite this, the
PVC/OBS still maintains an adequate LOI level.
Moreover, the thermal degradation process of the PVC and all stabilized-PVCs, as can
be seen in Figure 3b, showed two stages, i.e., 250–400 ◦ C and 400–550 ◦ C, respectively. The
first stage is mainly attributed to dehydrochlorination by the removal of hydrogen chloride
from the PVC main chain, thus forming a conjugated polyene structure. The second stage is
mainly attributed to the fracture of conjugated polyene structures to form small molecular
weight linear or cyclic hydrocarbons, and finally tar formation [25,26]. In addition, it was
observed that there is a substage in the first stage of the PVC, indicating the existence
of different events in this stage, suggesting a complex dehydrochlorination mechanism.
While all stabilized-PVC samples still showed the substage with more overlapping, it
is possible that the addition of Pb, CaZn, and OBS in the PVC showed a less complex
dehydrochlorination mechanism of the PVC.
 Moreover, the thermal degradation process of the PVC and all stabilized‐PVCs, as
can be seen in Figure 3b, showed two stages, i.e., 250–400 °C and 400–550 °C, respectively.
The first stage is mainly attributed to dehydrochlorination by the removal of hydrogen
chloride from the PVC main chain, thus forming a conjugated polyene structure. The sec‐
ond stage is mainly attributed to the fracture of conjugated polyene structures to form
small molecular weight linear or cyclic hydrocarbons, and finally tar formation [25,26]. In
Polymers 2022, 14, 133 addition, it was observed that there is a substage in the first stage of the PVC, indicating 9 of 16
the existence of different events in this stage, suggesting a complex dehydrochlorination
mechanism. While all stabilized‐PVC samples still showed the substage with more over‐
lapping, it is possible that the addition of Pb, CaZn, and OBS in the PVC showed a less
3.3.2.complex
Thermal Degradation Kinetics
dehydrochlorination mechanismAnalysis
of the PVC.
The thermal stability effects of Pb, Ca/Zn, and OBS on PVC were compared by TGA at
3.3.2.heating
diverse Degradation
Thermalrates, i.e., 5, Kinetics
10, and Analysis
20 ◦ C/min from 30 to 800 ◦ C in a nitrogen atmosphere.
The thermal stability
Figure 4 show TGA and DTG thermograms effects of Pb, Ca/Zn, and OBSPVC/Pb,
of the on PVC were compared byand
PVC/CaZn, TGAPVC/OBS.
at diverse heating rates, i.e., 5, 10, and 20 °C/min from 30 to 800 °C in a nitrogen atmos‐
The DTG thermograms of all PVC samples showed two thermal degradation stages, and
phere. Figure 4 show TGA and DTG thermograms of the PVC/Pb, PVC/CaZn, and
indicated
PVC/OBS that. The
chemical bonds of the
DTG thermograms second
of all degradation
PVC samples showedstage were more
two thermal difficult to break
degradation
thanstages,
the first degradation stage. As mentioned in item 3.3.1, the behaviors
and indicated that chemical bonds of the second degradation stage were more proved
dif‐ that the
stability
ficult of
to the
breakchemical bonds
than the first of C-Clstage.
degradation wereAslower than in
mentioned the C-C
item bonds.
3.3.1, Therefore, when
the behaviors
PVCproved that the stability
is pyrolyzed, of the chemical
the chemical bonds of bonds
C-Clofwould
C‐Cl were lower
break than
first, the C‐C
while bonds.
weight loss of PVC
Therefore, when PVC is pyrolyzed, the chemical bonds of
in the second stage was assumed as the breaking of the C-C bonds [27]. In C‐Cl would break first, while
two thermal
weight loss of PVC in the second stage was assumed as the breaking of the C‐C bonds
degradation stages, the first stage is considered as the most important stage because the
[27]. In two thermal degradation stages, the first stage is considered as the most important
C-Clstage
bond in thethe
because PVC,
C‐Clhaving lessPVC,
bond in the energy than
having lessthe C-Cthan
energy bond, dissociates
the C‐C first, resulting in
bond, dissociates
the volatilization of the hydrogen chloride molecule.
first, resulting in the volatilization of the hydrogen chloride molecule.

100 0
Residual weight (%)

80 o ‐0.001
 = 5 C/min o
 = 5 C/min
o
DTG (%/ C)
 = 10 C/min o
 = 10 C/min
o

60 o
 = 20 C/min o
 = 20 C/min
‐0.002

40
‐0.003
20
‐0.004
0
Polymers 2021,013, x FOR 200 400
PEER REVIEW o
600 800 0 200 400
o
600 800
10 of 17
Temperature ( C) Temperature ( C)
(a) (b)

105
0
84
Residual weight (%)

o
 = 5 C/min ‐0.001 o
 = 5 C/min
DTG (%/ C)

o
 = 10 C/min
63 o
= 10 C/min
o

o
= 20 C/min o
‐0.002 = 20 C/min

42
‐0.003
21
‐0.004
0
0 200 400 600 800 0 200 400 600 800
o o
Temperature ( C) Temperature ( C)
(c) (d)

100
0
Residual weight (%)

80
o
 = 5 C/min ‐0.001 o
 = 5 C/min
DTG (%/ C)

o
 = 10 C/min o
 = 10 C/min
o

60 = 20 C/min
o o
 = 20 C/min
‐0.002

40
‐0.003

20
‐0.004

0 200 400 600 800 0 200 400 600 800

o o
Temperature ( C) Temperature ( C)
(e) (f)
Figure 4. TGA and DTG thermograms of PVC/Pb (a,b), PVC/CaZn (c,d), PVC/OBS (e,f).
Figure 4. TGA and DTG thermograms of PVC/Pb (a,b), PVC/CaZn (c,d), PVC/OBS (e,f).
Therefore, to study the thermal degradation kinetics of the PVC stabilized with Pb,
CaZn, and OBS, the first stage of dehydrochlorination in the PVC/Pb, PVC/CaZn, and
PVC/OBS was the focus of this work. The conversion (extend of reaction) at different tem‐
peratures of the first stage for each heating rate is plotted in Figure 5.

1 1 1
 ‐0.003

Re
20
‐0.004

0 200 400 600 800 0 200 400 600 800

o o
Temperature ( C) Temperature ( C)
Polymers 2022, 14, 133 10 of 16
(e) (f)
Figure 4. TGA and DTG thermograms of PVC/Pb (a,b), PVC/CaZn (c,d), PVC/OBS (e,f).

Therefore, to study the thermal degradation kinetics of the PVC stabilized with Pb,
Therefore, to study the thermal degradation kinetics of the PVC stabilized with Pb,
CaZn, and OBS, the first stage of dehydrochlorination in the PVC/Pb, PVC/CaZn, and
CaZn, and OBS, the first stage of dehydrochlorination in the PVC/Pb, PVC/CaZn, and
PVC/OBS
PVC/OBSwaswas the focusofof
the focus this
this work.
work. The conversion
The conversion (extend(extend of reaction)
of reaction) at differentat different
tem‐
temperatures of the first stage for each heating rate is plotted in
peratures of the first stage for each heating rate is plotted in Figure 5.Figure 5.

1 1 1

o
0.8 o
 = 5 C/min 0.8  = 5 C/min 0.8 o
 = 5 C/min
o
o
 = 10 C/min  = 10 C/min o
 = 10 C/min
o
 = 20 C/min

Conversion

Conversion
o
Conversion

o
= 20 C/min  = 20 C/min
0.6 0.6 0.6

0.4 0.4 0.4

0.2 0.2 0.2

0 0 0
200 250 300 350 400 200 250 300 350 400 200 250 300 350 400
o o o
Temperature ( C) Temperature ( C) Temperature ( C)
(a) (b) (c)
Figure 5. Conversion as a function of the temperature to dehydrochlorination stage: (a)
Figure 5. Conversion
PVC/Pb, as a(c)function
(b) PVC/CaZn, PVC/OBS.of the temperature to dehydrochlorination stage: (a) PVC/Pb,
(b) PVC/CaZn, (c) PVC/OBS.
Polymers 2021, 13, x FOR PEER REVIEW 11 of 17

It can be seen that an average conversion of 68.3% for the PVC/Pb, 69.5% for the
PVC/CaZn, and 67.0% for the PVC/OBS was resulted by the end of the first stage. There-
It it
fore, can bebe
can seen that an average
summarized thatconversion of 68.3% for the PVC/Pb,
the dehydrochlorination stage was 69.5% for the
approximately 68%,
PVC/CaZn, and 67.0% for the PVC/OBS was resulted by the end of the first stage. There‐
70%, and 67% of the conversion of the total degradation process of the PVC stabilized with
fore, it can be summarized that the dehydrochlorination stage was approximately 68%,
Pb, CaZn, and OBS, respectively.
70%, and 67% of the conversion of the total degradation process of the PVC stabilized with
To calculate
Pb, CaZn, the kinetic parameter, according to the Kissinger method, the average
and OBS, respectively.
activation energy of the parameter,
To calculate the kinetic first thermal degradation
according stage (Emethod,
to the Kissinger a1 ) wasthe evaluated
average from the
slopes ofenergy
activation the plots in Figure
of the 6 and ordered
first thermal degradationas follows:
stage (Ea1PVC/OBS (140 kJ/mol)
) was evaluated from the> PVC/Pb
(132 kJ/mol)
slopes > PVC/CaZn
of the plots in Figure 6 and (110ordered
kJ/mol). While, according
as follows: PVC/OBS (140 to the PVC/Pb the Ea1 at
FWO>method,
kJ/mol)
each
(132 conversion
kJ/mol) of the (110
> PVC/CaZn PVC/Pb, PVC/CaZn,
kJ/mol). and PVC/OBS
While, according to the FWOdetermined
method, the from Ea1 at the slopes
each conversion
of the plots inofFigure
the PVC/Pb, PVC/CaZn,inand
7 is depicted PVC/OBS
Figure determined
8. The averagefrom Ea1theof slopes
the PVC of samples
the plots
from in Figure
Figure 7 is depicted
8 showed in Figure
the same 8. The
trend, which average
was Ecalculated
a1 of the PVC by samples from method
the Kissinger
Figure
such as 8 showed
PVC/OBS the same
(155trend, which
kJ/mol) was calculated
> PVC/Pb (147 by the Kissinger
kJ/mol) method such
> PVC/CaZn (129askJ/mol). It
PVC/OBS (155 kJ/mol) > PVC/Pb (147 kJ/mol) > PVC/CaZn (129 kJ/mol). It should be noted
should be noted that the Ea1 averaged from the Kissinger and FWO methods for the
that the Ea1 averaged from the Kissinger and FWO methods for the PVC/OBS was 148
PVC/OBS was 148 kJ/mol, indicating that much more energy was required for thermal
kJ/mol, indicating that much more energy was required for thermal degradation than the
degradation
other thani.e.,
two samples, theapproximately
other two samples, i.e.,for
140 kJ/mol approximately
the PVC/Pb and140 120kJ/mol
kJ/mol forforthe
the PVC/Pb
PVC/CaZn. The addition of the OBS in PVC might decrease the rate of the dehydrochlo‐ the rate
and 120 kJ/mol for the PVC/CaZn. The addition of the OBS in PVC might decrease
of the dehydrochlorination
rination process; thus the PVC/OBS process; thus stable
was more the PVC/OBS was more
than the PVC/Pb and stable than the PVC/Pb
the PVC/CaZn
and the temperature
PVC/CaZnwas when thethan
temperature ◦
when lower 400 °C. was lower than 400 C.

‐9.5

‐10
2)
ln(/Tp

‐10.5

‐11

‐11.5
1.6 1.65 1.7 1.75 1.8
1000/Tp (K‐1)

Figure
Figure6. 6.
Kissinger method
Kissinger plotsplots
method for average activation
for average energy energy
activation determination of the dehydrochlo‐
determination of the dehydrochlori-
rination stage: () PVC/Pb, () PVC/CaZn, () PVC/OBS.
nation stage: (l) PVC/Pb, () PVC/CaZn, (u) PVC/OBS.
2 2 2

1.5 1.5 1.5

 ‐11.5
1.6 1.65 1.7 1.75 1.8
1000/Tp (K‐1)
Polymers 2022, 14, 133 11 of 16
Figure 6. Kissinger method plots for average activation energy determination of the dehydrochlo‐
rination stage: () PVC/Pb, () PVC/CaZn, () PVC/OBS.

2 2 2

1.5 1.5 1.5

ln()
ln()
ln()

1 1 1
0.1
0.1
0.2 0.2 0.1
0.3 0.2
0.3
0.5 0.5 0.4 0.5 0.3
0.4
0.5 0.4
0.5
0.6 0.5
0.6
0.6

0 0 0
1.5 1.6 1.7 1.8 1.9 1.5 1.6 1.7 1.8 1.9 1.5 1.6 1.7 1.8 1.9
‐1 ‐1
1000/Tp (K ) 1000/Tp (K ) 1000/Tp (K‐1)
(a) (b) (c)

PolymersFigure 7.xFlynn–Wall–Ozawa
2021, 13, FOR PEER REVIEW (FWO) plots for average activation energy determination of the dehydrochlorination stage: 17
Figure 7. Flynn–Wall–Ozawa (FWO) plots for average activation energy determination12ofofthe dehy-
(a) () PVC/Pb, (b) () PVC/CaZn, (c) () PVC/OBS.
drochlorination stage: (a) PVC/Pb, (b) PVC/CaZn, (c) PVC/OBS.

200

PVC/Pb
180 PVC/CaZn
PVC/OBS
Ea (kJ/mol)

160

140

120

100
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Conversion

Activationenergy
Figure 8.8.Activation
Figure energyasas a function
a function of conversion
of conversion of dehydrochlorination
of the the dehydrochlorination
stage stage according
according
to the Flynn–Wall–Ozawa (FWO) method.
the Flynn–Wall–Ozawa (FWO) method.

Moreover,
Moreover,ininFigure
Figure8,8,the activation
the activation energy for for
energy the the
firstfirst
substage of theofdehydrochlo‐
substage the dehydrochlo-
rination
rinationofofPVC/Pb
PVC/Pb andandPVC/CaZn
PVC/CaZn tended to decrease
tended from 10%
to decrease fromconversion until approx‐
10% conversion until ap-
imately 40% conversion
proximately and increasing
40% conversion thereafter
and increasing as similarly
thereafter reported in
as similarly Ref. 25. in
reported These
Ref. [25].
characteristics confirmed
These characteristics that the that
confirmed energytherequired to break the
energy required C‐Cl bond
to break in the
the C-Cl firstin
bond sub‐
the first
stage
substage of dehydrochlorination is high. As a result, the formed HCl acted as athe
of dehydrochlorination is high. As a result, the formed HCl acted as a catalyst in catalyst
degradation reaction,reaction,
in the degradation where the interaction
where of HCl with
the interaction ofpolyenes
HCl withforms a chemical
polyenes formsspecies
a chemical
whose reaction with the normal monomer unit gives new sites for
species whose reaction with the normal monomer unit gives new sites for initiation,initiation, allowing aallow-
decrease in the activation
ing a decrease energy. energy.
in the activation After 40% conversion,
After or in the second
40% conversion, substage
or in the second ofsubstage
de‐
hydrochlorination, the participation of chlorine atoms added to a large
of dehydrochlorination, the participation of chlorine atoms added to a large number ofnumber of polyene
chain sequences is reflected by an increase in the activation energy [28,29]. In the case of
polyene chain sequences is reflected by an increase in the activation energy [28,29]. In the
PVC/OBS, the activation energy was increased with an increase of conversion in the first
case of PVC/OBS, the activation energy was increased with an increase of conversion in the
substage of the dehydrochlorination. It is possible that the uracil in the OBS stabilizer can
first substage of the dehydrochlorination. It is possible that the uracil in the OBS stabilizer
retard the degradation process by scavenging the HCl/Cl radical generated during pro‐
can retard the degradation process by scavenging the HCl/Cl radical generated during
cessing, resulting in requiring the higher energy to break the C‐Cl bond [2,16].
processing, resulting in requiring the higher energy to break the C-Cl bond [2,16].
3.4. Effect of Repeated Processing Cycles on Gelation Behavior of PVC Stabilized with Various
3.4. Effect of Repeated Processing Cycles on Gelation Behavior of PVC Stabilized with Various
Heat Stabilizers
Heat Stabilizers
Achieving the optimum level of gelation or fusion can cause a variety of faults and
Achieving the optimum level of gelation or fusion can cause a variety of faults and
failures in order to obtain the maximum mechanical properties. The gelation embraces
failures in order to obtain the maximum mechanical properties. The gelation embraces
changes involved in the conversion of separated particles of the polymer to a more or less
changes involved in the conversion of separated particles of the polymer to a more or less
continuous polymeric matrix. The morphology of PVC resin particles is complex, and it
continuous polymeric matrix. The morphology of PVC resin particles is complex, and it
has been known for a long time. This can have a major effect on the processing and the
has been known for a long time. This can have a major effect on the processing and the
mechanical properties of the finished product [20].
mechanical
To findproperties
the degreeofof
thegelation,
finishedDSC
product [20].
thermograms of PVC/Pb, PVC/CaZn, and
PVC/OBS compounds are plotted in Figure 9. The PVC compounds exhibited two endo‐
thermic peaks. The glass transition temperature of three PVC compounds measured at the
first transition was approximately 90 °C. Then, a small additive peak was observed at 110
°C, 105 °C, and 115 °C for the PVC/Pb, PVC/CaZn, and PVC/OBS, respectively. Moreover,
Polymers 2022, 14, 133 12 of 16

To find the degree of gelation, DSC thermograms of PVC/Pb, PVC/CaZn, and

PVC/OBS compounds are plotted in Figure 9. The PVC compounds exhibited two en-
dothermic peaks. The glass transition temperature of three PVC compounds measured at
the first transition was approximately 90 ◦ C. Then, a small additive peak was observed
at 110 ◦ C, 105 ◦ C, and 115 ◦ C for the PVC/Pb, PVC/CaZn, and PVC/OBS, respectively.
Moreover, the degree of gelation (G) of PVC compounds stabilized with each heat stabilizer
was estimated from the area of lower melting endotherm, which was divided by the sum of
the areas of lower and higher melting endotherms and can be calculated using the following
equation [30]:
HA
G (%) = × 100 (9)
H A + HB
Polymers 2021, 13, x FOR PEER REVIEW 13 of 17
where G is degree of gelation (%), HA is melting enthalpy of primary crystallites (J/g), and
HB is the melting enthalpy of secondary crystallites (J/g).

DSCthermograms
Figure9.9.DSC
Figure thermograms ofof PVC
PVC stabilized
stabilized with
with various
various types
types of heat
of heat stabilizers:
stabilizers: (l) PVC/Pb,
() PVC/Pb,
)) PVC/CaZn,
(( PVC/CaZn,() (u)PVC/OBS.
PVC/OBS.
(all(all samples
samples werewere processed
processed by two-roll
by two‐roll mills mills for◦ C
at 180at°C180 for 3 min
3 min
during
duringthe
thefirst
firstcycle).
cycle).

From
FromFigure
Figure9,9,thethepercent
percent of of
thethe
degree of gelation
degree of the
of gelation of PVC
the PVCstabilized with Pb,
stabilized with Pb,
CaZn,
CaZn, and OBS processed during the first by two-roll mills at 180 C for calcu‐
and OBS processed during the first by two‐roll mills at 180 °C for 3 ◦
min was 3 min was
lated to be to
calculated 64.0%, 70.2%,70.2%,
be 64.0%, and 59.0%, respectively.
and 59.0%, TypesTypes
respectively. of heatof stabilizers, therefore,
heat stabilizers, therefore,
showed significant effects on the degree of gelation of the starting PVC
showed significant effects on the degree of gelation of the starting PVC compounds. compounds. TheseThese
characteristics
characteristicsmay maydepend
dependon on the
the additive
additive formulations
formulationsin in each
each heat
heat stabilizer
stabilizer that
that re‐
resulted
sulted in different
in different ease
ease of of processing
processing or other
or other necessary
necessary properties
properties ofofthethePVC
PVCcompounds.
compounds.
In
Inaddition,
addition,the thedegree
degree ofof
gelation
gelationdetermined
determinedfrom the the
from DSCDSC thermogram
thermogram for each
for each
PVC compound as a function of repeated processing cycles is plotted in
PVC compound as a function of repeated processing cycles is plotted in Figure 10. It was Figure 10. It was
observed
observedthat thatthe
thedegree
degree ofof
gelation
gelationof each PVC
of each compound
PVC compound fromfrom
1 to 51 processing cyclescycles
to 5 processing
showed similar trends. An increase of the repeated processing cycle resulted in an increase
showed similar trends. An increase of the repeated processing cycle resulted in an increase
in the degree of gelation up to the third cycle for the PVC/Pb and PVC/CaZn, and up to
in the degree of gelation up to the third cycle for the PVC/Pb and PVC/CaZn, and up to
the fourth cycle for the PVC/OBS from the first processing cycle (or the original granules).
the fourth cycle for the PVC/OBS from the first processing cycle (or the original granules).
It then tended to decrease in the fifth cycle. This was due to an increase in the number of
It then tended to decrease in the fifth cycle. This was due to an increase in the number
repeated processing cycles which resulted in smaller grains (crystallites). There were re‐
of repeated processing cycles which resulted in smaller grains (crystallites). There were
maining crystallite after each repeated processing cycle, being molten until up to the third
remaining
or crystallite
fourth cycle. A decreaseafterineach repeated
the degree processing
of gelation cycle, being
was observed in themolten until up to the
fifth cycle.
third or fourth cycle. A decrease in the degree of gelation was observed in the fifth cycle.
 showed similar trends. An increase of the repeated processing cycle resulted in an increase
in the degree of gelation up to the third cycle for the PVC/Pb and PVC/CaZn, and up to
the fourth cycle for the PVC/OBS from the first processing cycle (or the original granules).
It then tended to decrease in the fifth cycle. This was due to an increase in the number of
repeated processing cycles which resulted in smaller grains (crystallites). There were re‐
Polymers 2022, 14, 133
maining crystallite after each repeated processing cycle, being molten until up to the third 13 of 16
or fourth cycle. A decrease in the degree of gelation was observed in the fifth cycle.

Polymers 2021, 13, x FOR PEER REVIEW 14 of 17

Figure
Figure10.
10.Effect of of
Effect repeated processing
repeated processing cyclecycle
on the
on degree of gelation
the degree of PVC
of gelation of compound with with
PVC compound
various heat stabilizers: ( ) PVC/Pb, (  ) PVC/CaZn, () PVC/OBS.
various heat stabilizers: (l) PVC/Pb, () PVC/CaZn, (u) PVC/OBS.

3.5. Mechanical
3.5. MechanicalProperty
Propertyasasa aFunction
Functionof of Repeated
Repeated Processing
Processing Cycle
Cycle of Rigid
of Rigid PVCPVC Stabilized with
Stabilized
Various HeatHeat
with Various Stabilizers
Stabilizers
AA notched
notchedIzod Izodimpact
impact test
test waswas used
used in studying
in studying an ability
an ability to absorb
to absorb energy energy during
during
plastic deformation,
plastic deformation,such suchas astoughness
toughnessand andthetheability
abilityofofimpact
impactresistance
resistance[31].
[31].TheThe impact
im‐
strength
pact of the
strength PVC
of the stabilized
PVC stabilizedwith
withvarious
varioustypes
typesofofheat
heat stabilizers asaafunction
stabilizers as functionofof the
number
the numberof of
processing
processingcycles
cyclesareareplotted in Figure
plotted in Figure11.11.It It
waswas found
found thatthat the PVC/OBS
the PVC/OBS
showed aahigher
showed higherimpact
impactstrength
strengththanthan the
the PVC/Pb
PVC/Pb andandthe the PVC/CaZn,
PVC/CaZn, whilewhile the degree
the degree
of
of gelation
gelationofofthethe
PVC/OBS
PVC/OBS was was
lowerlower
when when
compared to the above
compared to thematerials. It is possi‐ It is
above materials.
ble that the
possible thatmore effective
the more use ofuse
effective theofOBS stabilizer
the OBS one‐packs
stabilizer provided
one-packs the improved
provided the improved
mechanical
mechanicalproperty
propertyofofthe thePVC/OBS
PVC/OBS sample.
sample.

Figure 11.
Figure Relationshipbetween
11. Relationship between repeated
repeated processing
processing cycles
cycles and and notched
notched Izod Izod impact
impact strength
strength of of
rigid PVC
rigid PVCwith
withvarious
variousheat
heatstabilizers:
stabilizers:
()(l) PVC/Pb,
PVC/Pb, () PVC/CaZn,
() PVC/CaZn, (u) PVC/OBS.
() PVC/OBS.

Inaddition,
In addition,thethe impact
impact strength
strength of allofPVC
all samples
PVC samplestendedtended to increase
to increase from the
from the first
first
to thetothird
the processing
third processing
cycle andcycle
thenand thendecreased
slightly slightly decreased
at the fourthatprocessing
the fourthcycle.
processing
It
cycle.
is It is that
possible possible that an increased
an increased processingprocessing
cycle of up cycle of up
to a third to enhance
can a third can enhance
a more contin‐a more
uous polymeric
continuous matrix matrix
polymeric which can
whichbe related to an increased
can be related degree of
to an increased gelation,
degree which inwhich
of gelation,
turn
in turn increases the impact strength. An increment of the degree of gelation infourth
increases the impact strength. An increment of the degree of gelation in the the fourth
processing
processingcycle cycletended
tendedtotodecrease
decrease thethe
impact
impactstrength of all
strength ofPVC samples.
all PVC This indicated
samples. This indicated
that
that the
thesample
samplewas waschanged
changed toto
become
become more
morebrittle.
brittle.
The impact strength values of the
The impact strength values of the PVC/Pb,PVC/Pb, PVC/CaZn,
PVC/CaZn,and PVC/OBS reprocessed
and PVC/OBS up
reprocessed
to five cycles were in the range of 102.7–104.8 J/m (10.3–10.5 kJ/m 2), 103.8–106.3
up to five cycles were in the range of 102.7–104.8 J/m (10.3–10.5 kJ/m ), 103.8–106.3 J/m 2 J/m (10.4–
10.6 kJ/m2),kJ/m
(10.4–10.6 and 103.8–108.9 J/m (10.4–10.9
2 ), and 103.8–108.9 kJ/m2), respectively.
J/m (10.4–10.9 It was foundItthat
kJ/m2 ), respectively. wasthe im‐ that
found
pact strength of the rigid PVC stabilized with Pb, CaZn, and OBS reached the requirement
of commercial PVC pipes, i.e., 3.98 kJ/m2 and 5.0 kJ/m2, as reported by Georg Fischer
Harvel LLC and Thai Pipe Industry Co., Ltd., respectively [32,33]. However, the PVC/OBS
still showed higher impact strength than the PVC/Pb and the PVC/CaZn. Therefore, the
OBS can help to preserve the impact strength of the rigid PVC sample. In addition to the
Polymers 2022, 14, 133 14 of 16

the impact strength of the rigid PVC stabilized with Pb, CaZn, and OBS reached the
requirement of commercial PVC pipes, i.e., 3.98 kJ/m2 and 5.0 kJ/m2, as reported by
Georg Fischer Harvel LLC and Thai Pipe Industry Co., Ltd., respectively [32,33]. However,
the PVC/OBS still showed higher impact strength than the PVC/Pb and the PVC/CaZn.
Therefore, the OBS can help to preserve the impact strength of the rigid PVC sample. In
addition to the rather high toxicity of the Pb stabilizer and the least effective option in
terms of thermal performance of CaZn stabilizer, it seems that the OBS can be stabilized to
substitute both Pb and CaZn stabilizers.

3.6. Heat Distortion Temperature as a Function of Repeated Processing Cycle of Rigid PVC
Stabilized with Various Heat Stabilizers
Heat distortion temperature (HDT) is the measure of a polymer’s resistance to dis-
tortion
Polymers 2021, 13, x FOR PEER REVIEW under a given load at elevated temperatures (short-term heat resistance) and is a
15 of 17
useful indicator of the temperature limit above that region where the material cannot be
used for structural applications. From Figure 12, the more eco-friendly heat stabilizers such
as CaZn and OBS, compared to Pb stabilizer, can still maintain the HDT of the PVC at the
such as CaZn and OBS, compared to Pb stabilizer, can still maintain the HDT of the PVC
first processing cycle at 76 ◦ C for the PVC/OBS, 74.5 ◦ C for the PVC/CaZn, and 75 ◦ C for
at the first processing cycle at 76 °C for the PVC/OBS, 74.5 °C for the PVC/CaZn, and 75
the PVC/Pb. Moreover, it was observed that the softening temperature of the rigid PVC
°C for the PVC/Pb. Moreover, it was observed that the softening temperature of the rigid
stabilized
PVC withwith
stabilized Pb, CaZn, and and
Pb, CaZn, OBSOBSreached the requirement
reached the requirementof commercial PVCPVC
of commercial pipes, i.e.,
70 ◦ C and 75–82 ◦ C, as reported by Georg Fischer Harvel LLC and Thai Pipe Industry Co.,
pipes, i.e., 70 °C and 75–82 °C, as reported by Georg Fischer Harvel LLC and Thai Pipe
Ltd., respectively
Industry [32,33]. In addition,
Co., Ltd., respectively the
[32,33]. In effect ofthe
addition, theeffect
repeated processing
of the cycle of the rigid
repeated processing
cycle of the rigid PVC samples on the HDT was also reported. It seems that the HDTsamples
PVC samples on the HDT was also reported. It seems that the HDT of all PVC of all was
relatively constant in each repeated processing cycle, and the PVC/OBS
PVC samples was relatively constant in each repeated processing cycle, and the PVC/OBS showed better heat
showed better heat resistance than the PVC/CaZn and the PVC/Pb within five repeated It is
resistance than the PVC/CaZn and the PVC/Pb within five repeated processing cycles.
expected that
processing theItPVC/OBS
cycles. is expectedcan
thatbe
theused in wider
PVC/OBS canapplications that require
be used in wider heat that
applications resistance
at higher
require heattemperatures.
resistance at higher temperatures.

Figure 12. Effects of repeated processing cycles on heat distortion temperature of PVC with various
Figure 12. Effects of repeated processing cycles on heat distortion temperature of PVC with various
heatstabilizers:
heat stabilizers:
((l) PVC/Pb,
) PVC/Pb, () PVC/CaZn,
() PVC/CaZn, (u) PVC/OBS.
() PVC/OBS.

4. Conclusions
4. Conclusions
Considering environmentally friendly heat stabilizers for rigid PVC pipes, PVC stabi-
Considering environmentally friendly heat stabilizers for rigid PVC pipes, PVC sta‐
bilized with
lized theorganic
with the organicbased
based stabilizer
stabilizer (OBS)
(OBS) waswas prepared
prepared andrheological
and the the rheological behavior,
behavior,
color change, and thermal stability were compared with PVC stabilized with Pb andPb and
color change, and thermal stability were compared with PVC stabilized with
CaZn.InIn
CaZn. addition,
addition, heat
heat andand impact
impact resistance
resistance at repeated
at repeated processing
processing cyclescycles
of the of
PVCthe PVC
stabilized with Pb, CaZn, and OBS were also compared. The
stabilized with Pb, CaZn, and OBS were also compared. The obtained PVC samples were obtained PVC samples
were characterized
characterized using rheometer,
using a torque a torque rheometer,
DSC, UTM,DSC, impactUTM,
tester,impact
and TGAtester, and TGA
analyzer. As ana-
a lyzer.
result,As
theaPbresult, the Pb
stabilizer stabilizer
provided provided
higher long‐termhigher
heatlong-term heat than
stability rather stability
CaZnrather
and than
CaZn
OBS and OBS
stabilizers in stabilizers
terms of thein terms
color of the
change of color
the PVC,change
whileofOBS
the and
PVC, while
CaZn canOBS and CaZn
prolong
canthermal
the prolong the thermal
stability time bystability timethe
maintaining by initial
maintaining the initial
color better than Pbcolor
in thebetter
PVC.than
The Pb in
the PVC.of
increment The increment
repeated of repeated
processing processing
up to four cycles wasup to fourtocycles
found wasthe
increase found to of
degree increase
gelation and impact strength and showed no effect on the heat distortion temperature of
all rigid PVC samples. The addition of Pb, CaZn, and OBS can significantly enhance the
thermal stability, i.e., degradation temperature and char yield of the rigid PVC samples.
The thermal degradation kinetics of the PVC/Pb, PVC/CaZn, and PVC/OBS samples were
studied by a non‐isothermal multiple scan rate method. It was found that there are two
Polymers 2022, 14, 133 15 of 16

the degree of gelation and impact strength and showed no effect on the heat distortion
temperature of all rigid PVC samples. The addition of Pb, CaZn, and OBS can signifi-
cantly enhance the thermal stability, i.e., degradation temperature and char yield of the
rigid PVC samples. The thermal degradation kinetics of the PVC/Pb, PVC/CaZn, and
PVC/OBS samples were studied by a non-isothermal multiple scan rate method. It was
found that there are two distinct stages in the thermal degradation process of the sam-
ples. The first stage for dehydrochlorination released 68.3%, 69.5%, 67.0% mass basis
for the PVC/Pb, PVC/CaZn, and PVC/OBS, respectively. Two mathematical methods
were used to determine the activation energy of the dehydrochlorination stage and found
the following results: Kissinger’s method, Ea for the PVC/Pb = 132 kJ/mol, Ea for the
PVC/CaZn = 110 kJ/mol, and Ea for the PVC/OBS = 140 kJ/mol; and the Flynn–Wall–
Ozawa method, Ea for the PVC/Pb = 147 kJ/mol, Ea for the PVC/CaZn = 129 kJ/mol, and
Ea for the PVC/OBS = 155 kJ/mol. Higher energy is required for the thermal degradation
of PVC/OBS which decrease the rate of dehydrochlorination process in the PVC. Therefore,
the organic based stabilizer showed high potential to be used as a heat stabilizer for rigid
PVC for pipe applications due to good heat resistance and high mechanical property.

Author Contributions: Conceptualization, S.R. and C.J.; methodology, C.J.; S.R., A.A. and D.S.;
validation, C.J. and S.R.; formal analysis, C.J.; data curation, A.A. and P.M.; writing—original draft
preparation, C.J. and P.M.; writing—review and editing, C.J. and S.R.; supervision, S.R. and C.J.;
funding acquisition, S.R. and C.J.; D.S. assisted on PVC processing. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by Vinythai Public Company Limited (Thailand), The Fac-
ulty of Engineering, Srinakharinwirot University, grant number 233/2561(2018) and grant number
462/2563(2020), Research Unit on Polymeric Materials for Medical Practice Devices, Chulalongkorn
University, and The National Research Council of Thailand.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data is contained within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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