J Polym Eng 2017; 37(7): 715–727
Yingchun Li, Shuai He, Hui He*, Peng Yu and Dongqing Wang
Study on low temperature toughness and
crystallization behavior of polypropylene
random copolymer
DOI 10.1515/polyeng-2016-0169
Received May 16, 2016; accepted November 4, 2016; previously
­published online December 15, 2016
Abstract: This research designed a series of novel
approaches aiming to tackle a long-standing problem that
is the brittleness of polypropylene (PP) random copoly-
mer (PPR) at low temperature. By introducing polyolefin
elastomer (POE), the toughness of PPR was improved; talc
improved the stiffness of PPR, low density polyethylene
(LDPE) or high density PE (HDPE) improved the low tem-
perature toughness of PPR, and annealing treatment also
improved the low temperature toughness of PPR signifi-
cantly. The addition of dicumyl peroxide (DCP) and trial-
lyl isocyanurate (TAIC) increased its stiffness through the
formation of cross-linking networks. Also, the crystalliza-
tion behavior and morphology were investigated in detail.
Differential scanning calorimetry (DSC) results indicated
that the adoption of annealing treatment can improve
the crystallinity of PPR, while a polarizing microscope
revealed that the incorporation of foreign matter can facil-
itate the crystallization process of the matrix. X-ray dif-
fraction (XRD) tests showed an unchanged polymorphic
composition of PPR after introducing different additives,
and scanning electron microscopy (SEM) indicated that
annealing treatment can enhance interfacial interactions
between the matrix and fillers.
Keywords: annealing; cross-linking; crystallization behav-
ior; low temperature toughening; polypropylene random
copolymer.
*Corresponding author: Hui He, College of Materials Science
and Engineering, South China University of Technology, No. 381,
Wushan Street, Tianhe, Guangzhou 510640, China,
e-mail: pshuihe@scut.edu.cn
Yingchun Li, Shuai He, Peng Yu and Dongqing Wang: College
of Materials Science and Engineering, South China University of
Technology, No. 381, Wushan Street, Tianhe, Guangzhou 510640,
China
1 Introduction
Polypropylene (PP) is one of the most widespread general
polymers, which is utilized in various parts of our daily
life, such as automobiles, architecture, water pipe and
packaging industry, etc. due to its high mechanical per-
formances, superior processing properties and low man-
ufacturing costs [1]. However, a long-standing problem,
that is the brittleness of PP, especially at low temperature,
has largely restricted its further applications in frigid
environment. In recent years, researchers have devel-
oped several approaches to enhancing the toughness of
PP through different ways of integrating ethylene chain
segments, and thus they have successfully synthesized
polymers like PP homopolymer (PPH), PP block copoly-
mer (PPB) and PP random copolymer (PPR) [2–7]. Among
these materials, PPR exhibits superior properties, such as
good impact resistance and cold resistance, high elasticity
and outstanding creep resistance, etc. [8]. PPR is a crys-
talline-amorphous structure, and the amount of crystal-
line phase determines the stiffness and impact resistance.
Stiffness increases proportionally to the crystalline ratio.
In addition, PPR has advantageous mechanical properties
at a low price compared with polyethyleneterephthalate
(PET), polyamide (PA), polyoxymethylene (POM), polycar-
bonate (PC), etc., so its price performance ratio is good.
Therefore, PPR is a commodity polymer and the engineer-
ing polymers have excellent mechanical performance; the
applications of PPR are becoming increasingly extensive,
especially in household and industrial fields [9–11].
However, people have found an evident low tem-
perature brittleness of PPR, which is a severe problem in
outdoor water supply application, where the environment
is constantly frigid, particularly in the regions of north-
ern China. The toughening of PP has been investigated
thoroughly throughout the world, but the mechanism of
toughening PPR has yet to be fully developed, especially at
low temperature. Currently, the mainstream methodology
of PPR toughening is directly replicated from that of PP,
instead of exploiting an exclusive approach to enhancing
PPR. Basically, because PPR is a semi-crystalline polymer,
the toughening process of PPR must involve changes of its
716      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR
crystalline properties, including crystallinity, grain size
and crystallization rate, etc. [12]. Hence, investigations
into the crystallization behavior of PPR can be critical to
understand the mechanism of toughening.
A great amount of work has been done in order
to enhance the toughness of PPR. At present, the main
stream of toughening is still the incorporation of a finely
dispersed elastomer phase. In addition, the introduction
of inorganic particles, interfacial modifications, nuclea-
tion agents, annealing treatment, and targeted design
of molecular structure also can improve the toughness.
Rapa et  al. [13] added styrene-butadiene-styrene block
copolymer into PPR matrix for toughening, and the
results showed an evident increase of its toughness,
while the tensile strength experienced an opposite trend.
Also, Abreu et  al. [14] found that the introduction of
styrene-butadiene-styrene and styrene-ethylene-butyl-
ene-styrene block copolymer can function as hetero-
geneous nucleation agents in PPR, thus changing its
crystallization behavior and the corresponding mechani-
cal performances. Introducing polyethylene (PE) or PPB,
which exhibit great toughness, into PPR can be quite
effective due to their good compatibility [13, 15]. Meny-
hárd and coworkers [16] investigated the beta nucleation
ability of PPH/PPR blends. They found that the increase of
PPR amount decreases the structural stability of the beta
phase. Since the PPR and PPH are miscible, the increase
of PPR is accompanied by the proportional increase of
chain defects, which leads to the decrease of structural
stability of the beta phase. Luo et al. [17] observed a syn-
ergistic effect when introducing a β nucleation agent and
annealing treatment. In addition, the incorporation of
high density PE (HDPE) can improve the toughness of PP,
and it is particularly noticeable that annealing treatment
to this blend can surprisingly enhance the Izod impact
strength, up to 1107% [18]. To understand the correlation
chain from the polymer structure to the final application
properties of propylene-ethylene random copolymers,
Gahleitner et al. [5] studied four commercial grades with
different ethylene content (0–8  mol %) but identical
molecular weight distributions.
A B
Figure 1: Chemical structure: (A) dicumyl peroxide (DCP), (B) triallyl isocyanurate (TAIC).
Dicumyl peroxide (DCP) is a frequently used cross-
linker in rubber vulcanization, and the functioning
mechanism of DCP and its assistant cross-linker triallyl
isocyanurate (TAIC) has been thoroughly investigated
[19–21]. Their chemical structures can be seen in Figure 1.
Hopefully, by forming cross-linked networks, the mechan-
ical performances of PPR will be improved just as the way
it is in rubber vulcanization. The combination of DCP and
TAIC is named the DCP system.
This paper used polyolefin elastomer (POE) and talc
as a basic reinforcing formula to modify PPR, and then
the influence of introducing the DCP system, low density
PE (LDPE) or HDPE and annealing treatment were investi-
gated. Mechanical tests showed that the DCP cross-linking
system improves the stiffness of PPR dramatically, with
the strength and toughness decreasing to a certain extent.
While the introduction of LDPE or HDPE can enhance
the low temperature Izod impact strength of the material
significantly, it weakens the strength and stiffness of the
system. Differential scanning calorimetry (DSC) results
indicated that the adoption of annealing treatment can
improve the crystallinity of PPR, and a polarizing micro-
scope gave information on the crystallization behavior
and its corresponding parameters, like grain size and
crystallization rate. X-ray diffraction (XRD) showed that
the addition of additives does not influence PPR’s poly-
morphic composition, and scanning electron microscopy
(SEM) presented PPR’s fracture morphology, indicating
the interfacial changes after the introduction of LDPE and
DCP system.
2 Materials and methods
2.1 Materials
–– PPR was purchased from Korea Petrochemical Ind.
Co., Ltd. (Seoul, Korea), trade name: RP2400, melt
index (MI) = 0.25 g/10  min (test standard: ASTM
D-1238, 2.16 kg loading, density: 0.9 g/cm3).
 Y. Li et al.: Low temperature toughness and crystallization behavior of PPR      717
–– POE was provided by DuPont Dow Chemical Company
(MI, USA), trade name: Engage 8150, octene content:
25%, MI = 0.5 g/10  min (test standard: ASTM D-1238,
2.16 kg loading), density: 0.868 g/cm3.
–– Talc powder (3000  mesh) was kindly supplied by
Kingfa Scientific and Technological Co., Ltd. (Guang-
dong, Guangzhou, China).
–– DCP (chemical pure) was purchased from Shanghai
Ebi Chemical Reagent Co., Ltd. (Shanghai, China).
–– TAIC (chemical pure) was supplied by Quanzhou
Huashi Rubber Technology Co., Ltd. (Quanzhou,
Fujian, China).
–– LDPE was purchased from Daqing Petrochemical
Company (Daqing, Heilongjiang, China), trade name:
RP2426H, MI = 2.0 g/10  min (test standard: ASTM
D-1238, 2.16 kg loading, density: 0.923 g/cm3.
–– HDPE (trade name: 5000S) was provided by Petro-
China (Guangzhou, Guangdong, China). MI = 0.9
g/10 min (test standard: ASTM D-1238, 2.16 kg loading,
density: 0.954 g/cm3.
2.2 T
 he preparation of modified PPR
Ingredients, such as PPR, talc powder, POE, TAIC, LDPE,
and HDPE, were firstly melt-blended on a two-roll mill
(XKR-160A, Zhanjiang Machinery Factory, Zhanjiang,
Guangdong, China) after being precisely weighed. The
temperature of the mill was set to 150°C, and the above
materials were processed for at least 8  min. Then, DCP
was added and all the ingredients were mechanically
mixed for another 2 min. The mixture was then pressed
with the model for 3 min in the hot press machine (XLB-D
vulcanizing press, Zhejiang Hongtu Machinery Factory,
Huzhou, Zhejiang, China) at 190°C, and the product
was slowly cooled to obtain a sheet. The sheet was
then placed for at least 24  h. Finally, the sheet was cut
by a Dumbbell System Prototype (TF-2062, Tianfa Test
Machinery Co., Ltd., Yangzhou, Jiangsu, China) accord-
ing to the ISO standard to gain testing bars. Bars for the
Izod impact test were processed to obtain a notch as per
the ISO standard.
2.3 Annealing treatment
Samples ready for annealing were put into a vacuum oven
at 120°C for 12 h, and then they were cooled down along
with the vacuum oven to room temperature [22, 23]. The
annealed samples were tested as a comparison to the
annealing-free samples.
2.4 Mechanical performance test
Testing bars for the tensile, flexural, and Izod impact
tests were prepared according to ISO 527 : 1993, ISO
178 : 1993, and ISO 180 : 1993 on Shimadzu AG-1, Instron
4465 (Chengdu, Sichuan, China), and Zwick Pendulum
5113.300 (Germany), respectively. The Izod impact test
was carried out at 0°C, and this condition was fulfilled
through the following procedures. The samples were pre-
viously sealed in a plastic bag, and then they were put
into pure water under a frigid environment. This envi-
ronment was achieved through a refrigerator, and the
samples were ready for testing when an ice-water mixture
appeared. The time interval between taking out and
testing the samples was as short as possible. At least five
specimens were tested for each sample, and the averages
were calculated.
2.5 Melt flow rate test
Samples were fed into a melt flow indexer 7201 (CEAST
Company, Italy), and the testing condition was under
210°C with 2.16 kg loading. At least 10 drops were col-
lected and then precisely weighed to get an average value
for each sample.
2.6 DSC test
The DSC test was performed on an American DSCAQ20
automatic differential scanning calorimeter (TA Instru-
ment, USA). First of all, we erased the thermal and
mechanical prehistory; the operating temperature range
was 30 ~ 200°C, the heating rate was 20°C/min, and the
stable time was 5 min. The heating and cooling rate of the
melt and crystallization program to obtain melt and crys-
tallization curves were both 10°C/min, and the operating
temperature range was 30 ~ 200°C. In addition, the DSC
of annealing and frozen did not erase the thermal and
mechanical prehistory; the operating temperature range
was 30°C ~ 180°C and the heating rate was 10°C/min. This
whole procedure was under protection of nitrogen, and
the gas flow was 50 ml/min. DSC tests of frozen samples
were conducted by quickly taking samples out from the
0°C ice-water mixture and then feeding them into the
calorimeter.
DSC curves were tracked and the values of the melting
and crystallization curves’ peak temperatures were then
recorded, respectively, referred to as TMp and TCp. Samples’
starting and ending temperatures of the crystallization
were noted as Tonset and Tendset, respectively, while the
718      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR

relative crystallinity of PPR, Xc, can be calculated accord- using copper as a target. The scanning rate was 5°/min
ing to the following equation: and the range of diffraction angle was 1 ~ 30°.

∆H exp
Xc = × 100% (1) 2.9 SEM observation
∆H 0 

where melting enthalpy of PPR is calculated according to
the melting curves, and is the melting enthalpy of totally
crystallized α-PPR, which is 177 J/g [24].
2.7 P
 olarizing microscope observation
Crystallization behavior and crystalline features of
samples were tracked through a polarizing microscope,
BX51 (Olympus, Japan). A small quantity of samples
was put between two thin glass sheets, and then they
were heated on a heating platform. The temperature was
increased to 200°C at a heating rate of 40°C/min, and the
sample was gently pressed into a thin sheet (~ 50 μm).
Keeping this temperature for 5 ~ 10 min can eliminate the
materials’ heat history. After that, the sample was cooled
down to 115°C at a cooling rate of 40°C/min, and then
the crystallization behavior at the constant temperature,
115°C, was recorded through photographing. The magni-
fication was × 500.
2.8 XRD test
XRD test was performed on PAnalytical X’pert PRO X (Pan-
alytical Analytical Instruments, Almelo, The Netherlands),
The Bio-Rad SEM spray system was employed to spray
fracture surface of the samples with platinum. The Neth-
erlands FEI, Quanta 200 environmental SEM was then
utilized to observe the morphological characteristics of
the samples. Samples’ fracture surfaces were obtained
through several procedures. Firstly, they were frozen by
liquid nitrogen to become brittle, and then sudden impact
was used to break the samples. The smooth fracture sur-
faces were then obtained and utilized to conduct the SEM
characterization.
3 Results and discussion
Formulas shown in Table  1 will be adopted to prepare
modified PPR for characterizations within the entire
paper.
3.1 T
 he influence of different additives
on the melt flow rate value of PPR
Different additives, listed in Table 1, can exert an influence
upon the melt flow rate (MFR) of PPR, and such influence
was investigated as the data presented in Table 2.

Table 1: Basic formula (wt.%) for polypropylene random copolymer (PPR) systems.

Name PPR (%) POE (%) Talc (%) DCP (%) TAIC (%) LDPE (%) HDPE (%)

PPR 100 0 0 0 0 0 0
PPR-1 91 6 3 0 0 0 0
PPR-1x 90.7 6 3 0.06 0.3 0 0
PPR-2 86 6 3 0 0 5 0
PPR-2x 85.7 6 3 0.06 0.3 5 0
PPR-3 86 6 3 0 0 0 5
PPR-3x 85.7 6 3 0.06 0.3 0 5

DCP, Dicumyl peroxide; HDPE, high density polyethylene; LDPE, low density polyethylene; POE, polyolefin elastomer; PPR, polypropylene
random copolymer; TAIC, triallyl isocyanurate.

Table 2: The melt flow rate (MFR) of polypropylene random copolymer (PPR) and its modified counterparts.

Name   PPR   PPR-1   PPR-1x   PPR-2   PPR-2x   PPR-3   PPR-3x

MFR (g/10 min)  0.42   0.48   2.30   0.59   1.91   1.34   2.00

MFR, Melt flow rate; PPR, polypropylene random copolymer.

 Y. Li et al.: Low temperature toughness and crystallization behavior of PPR      719
The MFR value of virgin PPR, which is 0.42 g/10 min, is
relatively low before the introduction of a small amount of
additives increasing this figure slightly. When an amount
of POE and talc is added into virgin PPR, the increase of the
MFR of PPR is not obvious. It is particularly noticeable that
the introduction of the DCP system drastically increased
the MFR of PPR, reaching 2.30 g/10 min, and this trend was
also seen in PPR-2x and PPR-3x, but was not as evident as
that of PPR-1x. This might be attributed to the existence of
LDPE or HDPE, which induce more cross-linking reactions
within the materials. It shows that the addition of the DCP
system can improve the processability of PPR.
It can be well-explained by Figure  2 that the DCP
system could exert two completely different influences
on PPR molecular structure. On the one hand, DCP can
break PPR molecular chains into free radical pieces, and
TAIC itself owns three functional group points that will
capture PPR fragments to form a cross-linked network.
This reaction will enable the average molecular weight
of PPR to increase, thus decreasing the MFR value, but
this is an ideal and theoretical condition. In reality, on
the other hand, PPR fragments could either be captured
by a DCP free radical or end up integrating with other
small PPR fragments, hindering the cross-linking process.
Figure 2: The functioning mechanism of the dicumyl peroxide (DCP) system.
This reaction is referred to as degradation, and it can
greatly increase the MFR value of the material, lowering
its molecular weight. Actually, those two reactions form
a competitive relationship, and the result can be clearly
seen in Table 2 – the degradation process is more signifi-
cant. Therefore, the overall outcome is the increase of the
MFR value for PPR after the DCP system is introduced.
3.2 Mechanical performances test
3.2.1 The influence of different additives
on the mechanical properties of PPR
Virgin PPR and its modified samples listed in Table 1 were
tested, and the results can be seen in Figure 3.
The tensile strength of virgin PPR is around 21.8 MPa,
the largest figure among the materials. As for PPR-1,
because of the incorporation of POE and talc, the integ-
rity of PPR matrix in PPR-1 is blocked, and the tensile
force cannot transfer smoothly, as it does in virgin PPR.
The existence of POE and talc acts as millions of stress
concentrative points, which accelerates the propagation
of cracks and voids. The consequence of this is making
720      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR

Figure 3: The influence of different additives on mechanical properties of polypropylene random copolymer (PPR): (A) tensile strength, (B)
flexural strength, (C) flexural modulus, and (D) Izod impact strength at 0°C.

it easier to break the material. In addition, POE is a sort
of thermoplastic elastomer, exhibiting a superior tough-
ness, but regarding tensile strength, it will exert a negative
influence on PPR matrix. Therefore, the tensile strength of
PPR-1 is much lower than that of pure PPR. After incorpo-
rating a small amount of the DCP system, it can be seen
there is a slight increase in the tensile strength of PPR-1x.
This phenomenon can be explained by the networking
function of the DCP system, but degradation will diminish
that effect in an opposite way. Hence, the reinforcement is
not obvious. The incorporation of LDPE or HDPE plays a
similar role as POE and talc, and both of these can further
decrease the tensile strength of PPR.
In terms of the flexural strength, the introduction
of POE, talc and the DCP system does not jeopardize
the original strength of PPR much. In contrast, LDPE or
HDPE can greatly decrease the flexural strength of the
matrix, while adding the DCP system will slightly make
up for it. This might be a result of the relative inferior
flexural strength of LDPE or HDPE in comparison to PPR
matrix. Regarding the flexural modulus, it is particularly
noticeable that the addition of the DCP system can sig-
nificantly improve the flexural modulus of PPR, thus the
stiffness of PPR is improved. Although degradation will
harm its strength, the reinforcing function of the DCP
system enables PPR to possess a better capability fight-
ing against deformation. The highest figure among the
materials belongs to PPR-3x.
The main objective of adding different additives is to
enhance the toughness of PPR at a low temperature, and
this important reinforcing function can be best illustrated
by the Izod impact strength of different modified samples
at 0°C. As it can be seen from Figure 3D, the addition of
POE and talc doubles the impact strength of virgin PPR
due to the superior flexibility and good compatibility of
POE with PPR, but introducing the DCP system seems
 Y. Li et al.: Low temperature toughness and crystallization behavior of PPR      721

to weaken this reinforcement as a result of its degrada-
tion effect. Also, networks formed by the DCP system
can further restrict PPR molecular chains to migrate and
adjust themselves when sudden impact happens, thus
decreasing their toughness. Surprisingly, the incorpo-
ration of LDPE or HDPE can dramatically enhance the
impact strength of the matrix at 0°C to approximately
42  kJ/m2 and 28  kJ/m2, respectively, when comparing to
that of virgin PPR (3.7  kJ/m2). This phenomenon can be
explained by the excellent toughness and great compat-
ibility of LDPE or HDPE with PPR, thus directly improving
the Izod impact strength of the material at 0°C. Similarly,
the incorporation of the DCP system greatly jeopardizes
the reinforcing function of LDPE or HDPE. Hence, the
introduction of LDPE or HDPE can effectively enhance the
toughness of PPR at a low temperature.
3.2.2 The influence of annealing treatment
on mechanical properties of PPR systems
Annealing treatment was adopted, as mentioned above, to
investigate its actual effects on the mechanical properties
of PPR systems, especially toughness. The data obtained
from the mechanical tests is displayed in Figure 4.
According to Figure 4, it is evident that the annealing
treatment slightly affects the strength and stiffness of PPR
blends, with the tensile strength, flexural strength and
flexural modulus generally experiencing a mild down-
ward trend. This phenomenon might be attributed to the
integrity process of PPR crystallization with the annealing
treatment. During the annealing process, residual stress
accumulated from the processing procedures is gradu-
ally released within the materials. PPR molecular chains

Figure 4: The influence of annealing treatment on polypropylene random copolymer (PPR) systems’ mechanical properties: (A) tensile
strength, (B) flexural strength, (C) flexural modulus, and (D) Izod impact strength at 0°C.
722      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR
are empowered to stretch and re-arrange due to the energy
provided by annealing treatment, and the grain size
becomes bigger, which enables PPR crystalline grains to
migrate easily against external forces. Additionally, the
high temperature and long hour treatment could facilitate
the degradation of PPR. Therefore, the strength and stiff-
ness of the material are slightly weakened. By contrast,
concerning the toughness of PPR at low temperatures, they
all witness an amazing rise, with the Izod impact strength
at 0°C nearly doubled, or even more. The most remark-
able figure belongs to PPR-2, rising from around 42  kJ/
m2 to 64  kJ/m2, nearly 20 times larger than that of virgin
PPR (3.7  kJ/m2). As the crystallization process within the
materials tends to be more complete during the annealing
treatment, the grain size and grain integrity are gradually
increased. After annealing, the amorphous region’s molec-
ular chains’ mobility is significantly improved, which
enables them to move and adjust themselves easily, absorb-
ing a great amount of energy caused by sudden impact.
With respect to PPR-2 and PPR-3, the possible mechanism
of their remarkable reinforcing effects on toughness was
proposed in previous research work [18]. It is speculated
that the interfacial interactions between PPR and LDPE or
HDPE are enhanced as a result of the greater entanglement
of their molecular chains during the annealing process.
3.3 C
 haracterizations on the crystallization
behavior of PPR blends
3.3.1 D
 SC analysis on the melting and crystallization
behavior of PPR blends
DSC tests were carried out to investigate the influence of
different additives as well as pre-treatments, like freeze
and annealing, on the crystallization behavior of PPR. The
data acquired from the tests is exhibited in Figures 5 and 6.
Information, such as crystallinity, peak melting tempera-
ture and half-peak width, etc., is calculated according to
the instructions mentioned above. The figures are shown
in Tables 3 and 4.
As can been seen from Table 3, by incorporating dif-
ferent additives into the PPR matrix, the crystallization
parameters of the materials, such as Tonset, Tendset and TCp, are
increased, which indicates better crystallizing capability of
PPR. The existence of POE, talc, LDPE and HDPE could be
regarded as foreign matters, as well as heterogeneous nucle-
ation agents, facilitating the crystallization process of PPR.
In contrast, as expected, the addition of the DCP system
decreases the crystallization parameters of the blends. The
mechanism is similar to the previous explanation.
Figure 5: Differential scanning calorimetry (DSC) crystallization
curves of polypropylene random copolymer (PPR) blends.
From Table 4, it is obvious that the introduction of
annealing treatment can improve the crystallinity of virgin
PPR, with the figure rising from 33.5% to 40.2%. The same
phenomenon can be observed from PPR-1 and PPR-1x. The
reason for this is that during processing procedures, PPR
matrix has not got enough time to arrange its molecular
chains, and residual stresses accumulated at that time
can further jeopardize the crystallization of PPR. Thus,
a certain amount of molecular chains are still in a “half-
way” condition. The introduction of annealing treatment
offers them a second chance. The difficulties of crystalliz-
ing caused by residual stress will be greatly eliminated,
and meanwhile, PPR molecular chains are provided with
sufficient energy. These two advantages help PPR to crys-
tallize again, improving the crystallization integrity as
well as the crystallinity. At the same time, the mobility of
the molecular chains in the amorphous area is improved
and this has a bigger influence on the properties of mate-
rials. The structural changes enable PPR to possess a
better performance, exhibiting superior resistance against
sudden impact. Also, the peak melting temperature of
PPR, TMp, is increased, indicating the perfection of crys-
tallization that improves the thermal performances of the
materials. By contrast, freezing the materials cannot influ-
ence their structural characters, which means that the
crystallization features, like TMp and crystallinity, will not
be affected, but the low temperature condition certainly
influences the mechanical behavior of PPR molecular
chains under external forces. The molecular chains are
frozen under a frigid environment and their mobility is
decreased, therefore, the capability of moving and adjust-
ing for those macromolecules is weakened. The actual
effect resulting from that condition is the decrease of the
 Y. Li et al.: Low temperature toughness and crystallization behavior of PPR      723

Figure 6: (A) Melting curves of polypropylene random copolymer (PPR), (B) melting curves of PPR-1', (C) melting curves of PPR-1x.

Table 3: Data obtained from the differential scanning calorimetry
(DSC) crystallization scans of polypropylene random copolymer
(PPR) blends.
Name PPR PPR-1 PPR-1x PPR-2 PPR-2x PPR-3 PPR-3x
that can both block the crystallization of PPR, breaking
the normal pattern of PPR molecular chains’ self-arrange-
ment. Hence, the crystallinity of PPR is decreased.

Tonset/°C 102.3 110.1 108.5 108.3 105.7 108.4 106.2

3.3.2 XRD analysis on the crystalline features of PPR
Tendset/°C 92.2 102.5 99.5 100.9 97.6 98.5 96.7
blends
TCp/°C 98.0 106.9 104.7 105.0 102.3 105.1 102.6

PPR, Polypropylene random copolymer.
Izod impact strength. In addition, the introduction of the
DCP system can significantly impair the crystallization
ability of PPR-1, with the crystallinity dropping from 33.9%
to 27.3%. This can be attributed to the two opposite func-
tions of the DCP system, degradation and cross-linking,
XRD tests were conducted to investigate the impacts of
additives and annealing treatment on the crystalline fea-
tures of PPR, like crystalline interplanar spacing etc. The
results acquired from this experiment are displayed in
Figure 7.
In these profiles, the diffraction peaks at 2θ = 14.1°,
16.9°, 18.6°and 21.0° represent the principal reflections

Table 4: Data obtained the differential scanning calorimetry (DSC) melting scans of polypropylene random copolymer (PPR) blends.

Name   PPR  Annealed PPR  Frozen PPR  PPR-1  Annealed PPR-1  Frozen PPR-1  PPR-1x  Annealed PPR-1x  Frozen PPR-1x

TMp/°C   141.0  142.3  141.7  142.7  142.2  142.2  142.4  143.7  143.4
Xc/%   33.5  40.2  41.2  33.9  39.8  39.6  27.3  39.6  40.9

PPR, Polypropylene random copolymer.

724      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR

A B

C D

Figure 7: The X-ray diffraction (XRD) spectra of virgin polypropylene

random copolymer (PPR) and its modified counterparts.

Figure 8: Polarized optical images of isothermal crystallization of

(110, 040, 130 and 111, respectively) of the alpha form [17],
while the diffraction peak at 2θ = 28.6° represents the prin-
cipal reflection (006) of talc [25]. According to Figure  7,
it is noticeable that although annealing treatment can
increase the crystallinity of PPR, changing its polymor-
phic composition seems impossible. Also, the addition of
POE and talc will not induce the formation of β-crystals
in PPR matrix, but their existence does hinder the normal
crystallization patterns of virgin PPR, weakening the peak
intensity at around 14.1° and 21°. Additionally, introduc-
ing the DCP system does not change the locations of the
XRD pattern, which means PPR molecular chains can still
arrange themselves as they did previously, although their
capability of arranging is weakened.
polypropylene random copolymer (PPR): (A) t = 0 s, (B) t = 90 s, (C)
t = 120 s, and (D) t = 180 s.
spherulites continue to develop, but the number of new
emerging spherulites decreases. Then, the crystallization
process draws to a close at 180 s. The spherulites still keep
growing and merge with each other, and their bounda-
ries become less clear. This entire process takes PPR more
than 3 min to complete, and the distribution of numerous
spherulites is quite uniform, which may explain the decent
mechanical performances of PPR.
After the introduction of POE and talc, the crystalline
features of PPR can be dramatically changed, as shown in

B
3.4 C haracterizations on the structural A
­morphology of PPR blends

3.4.1 T
 he influence of additives on the crystalline
morphology of PPR

A polarizing microscope was employed in this experi-

ment to investigate the influence of several additives on
C D
the crystalline morphology of the matrix. Before that, the
isothermal crystallization process of virgin PPR was char-
acterized, as presented in Figure 8.
Virgin PPR is a member of the semi-crystalline polymer
family, thus the isothermal crystallization behavior is
similar to its counterparts. Figure 8 clearly displays the
crystalline characteristics of PPR. When t = 0 s, PPR has not
started to crystallize yet, and there is almost nothing that Figure 9: Polarized optical images of isothermal crystallization of
can be observed. After 90 s, millions of spherulites begin polypropylene random copolymer (PPR)-1: (A) t = 0 s, (B) t = 10 s, (C)
to appear and then constantly grow. At the next stage, PPR t = 20 s, and (D) t = 60 s.
 Y. Li et al.: Low temperature toughness and crystallization behavior of PPR      725

A B
C D
Figure 10: Polarized optical images of isothermal crystallization of
polypropylene random copolymer (PPR)-1x: (A) t = 0 s, (B) t = 20 s, (C)
t = 30 s, and (D) t = 70 s.
Figure 9. At first, PPR has not begun to crystallize, thus the
bright point is ascribed to the existence of talc. After this,
the appearance of PPR spherulites can be seen, but much
smaller and vaguer than that of virgin PPR. Some 10 s later,
the blurred outline of PPR spherulites becomes clearer
and bigger, indicating the growth of PPR spherulites. This
process tends to complete within 1 min. Overall, the incor-
poration of foreign matter facilitates the crystallization
of PPR, which greatly reduces the time consumption for
PPR to crystallize. Also, the improved crystallization rate
of PPR benefits from the heterogeneous nucleation func-
tions of POE and talc. PPR molecular chains will wind
around the talc particles, and then arrange themselves
to form numerous small spherulites. Therefore, the grain
size of PPR is decreased along with the increased spher-
ulite quantity. These structural changes enable PPR to
own better mechanical performances, like stiffness and
toughness.
By introducing the DCP system into PPR-1, the crys-
tallization of PPR will be further affected, which can be
observed from Figure  10. According to this figure, it can
be noticed that the time consumption for PPR to crystal-
lize is increased compared to PPR-1, but it is still much
less than virgin PPR. Also worth mentioning is the further
blurred profile of PPR spherulites, indicating the weak-
ened crystallizing capability. From these phenomena, it
can be concluded that the DCP system will jeopardize PPR

A B C

mode HV mag det WD vac mode 200 µm mode HV mag det WD vac mode 200 µm mode HV mag det WD vac mode 200 µm
SE 12.50 kV 500 x ETD 11.5 mm High vacuum SE 12.50 kV 500 x ETD 11.5 mm High vacuum SE 12.50 kV 500 x ETD 11.8 mm High vacuum

mode HV mag det WD vac mode 200 µm mode HV mag det WD vac mode 200 µm mode HV mag det WD vac mode 200 µm
SE 12.50 kV 500 x ETD 11.9 mm High vacuum SE 12.50 kV 500 x ETD 11.7 mm High vacuum SE 12.50 kV 500 x ETD 11.4 mm High vacuum

Figure 11: The impact fracture surface morphologies (500) of polypropylene random copolymer (PPR) systems: (A) PPR, (B) PPR-2, (C)
PPR-2x, while (A′), (B′) and (C′) represent annealed (A), (B) and (C), respectively.
726      Y. Li et al.: Low temperature toughness and crystallization behavior of PPR
crystallization because of its distinct functions. Therefore,
the introduction of the DCP system decreases the crystal-
lization rate of PPR and weakens its ability to crystallize.
3.4.2 I nvestigations on the interior morphology of PPR
blends
Virgin PPR and its modified samples were chosen to
characterize their interior morphology by SEM, aiming to
investigate the actual interfacial interactions between PPR
matrix and additives. Considering the best Izod impact
strength at 0°C of PPR-2, we choose this to investigate
the interior morphology. The information is presented in
Figure 11.
According to Figure 11, the fracture surface of virgin
PPR exhibits relatively smooth patterns, indicating its
inferior toughness at low temperature. After the annealing
treatment, its fracture surface transforms dramatically,
with obvious layered wrinkles uniformly dispersed. The
introduction of LDPE significantly and positively affects
the toughness of PPR, making the fracture surface rougher
and less smooth compared to that of virgin PPR. By incor-
porating the annealing process, this surface presents
typical plastic fracture features with wave-like layers. The
further roughened surface reveals the enhanced interfa-
cial interactions between PPR and LDPE, which explains
the superior low temperature impact strength of PPR-2.
Regarding PPR-2x, the DCP system jeopardizes the molec-
ular interactions in PPR-2, and its fracture surface seems
to be smoother. This intervention is alleviated by anneal-
ing, and then a rugged fracture surface appears.
4 Conclusion
The addition of POE and talc doubles the low temperature
Izod impact strength of virgin PPR (3.7 kJ/m2), and intro-
ducing LDPE or HDPE substantially enhances the tough-
ness of PPR, with the figure reaching 42 kJ/m2 and 28 kJ/
m2, respectively. The adoption of these foreign matters
can greatly facilitate the crystallization process of the
matrix, and refine its grain size without transforming the
polymorphic composition. In addition, annealing treat-
ment largely affects the interior structure of PPR blends,
refining the crystallization process with increased rela-
tive crystallinity. Also, the annealing process strengthens
the interfacial interactions between PPR and other addi-
tives, which dramatically enhances the low temperature
toughness of PPR, with the highest figure standing at
64  kJ/m2. Furthermore, the DCP system exerts two com-
petitive influences on PPR, which are degradation and
cross-linking, and the proportion of degraded PPR is
much more than that of cross-linked PPR. By adopting
the DCP system, although there is a negative impact on
the toughness of the materials, the stiffness of PPR is
improved significantly. Also, the introduction of the DCP
system jeopardizes the crystallization process of PPR,
decreasing its relative crystallinity.
Acknowledgments: The authors gratefully acknowl-
edge The Science and Technology Project of Guangzhou
(201508020090) for financial support.
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