Investigation of the microstructures, properties, and toughening

mechanism of polypropylene/calcium carbonate toughening

masterbatch composites
Qi-Cheng Lu, Qiang Dou
College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
Correspondence to: Q. Dou (E - mail: douqiang.njut@163.com)

ABSTRACT: The morphologies, crystallization and melting behaviors, and mechanical, thermal and processing properties of polypro-
pylene (PP)/CaCO3 toughening masterbatch (CTM) composites were investigated. The good dispersion of CaCO3 particles via appro-
priate surface encapsulation in the composites is proven by density measurements and scanning electron microscopy images. The
crystallinity and tensile strength of PP decrease with the addition of CTM. The flexural modulus and storage modulus (E0 ) at 23 8C
increase with CTM content, implying improved stiffness. A sharp increase in the Izod notched impact strength can be observed for
the composites, and the critical ligament thickness (sc) is calculated to be 1.31 and 2.46 lm for PP (S1003) and PP (001 G) compo-
sites, respectively. The morphologies of the impact-fractured surfaces of the specimens were observed, and the shear deformation is
enhanced by the addition of CTM. The presence of CTM also increases the melt flowability and decreases the shrinkage of the com-
posites. VC 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45515.

KEYWORDS: crystallization; microscopy; morphology; polyolefins; structure-property relationships

Received 19 April 2017; accepted 7 July 2017

DOI: 10.1002/app.45515

INTRODUCTION matrix. When the interparticle distance is below a critical value,

the brittle–ductile transition of the blend will be observed.3
Polypropylene (PP) is one of the most important thermoplastic
Nevertheless, the incorporation of rubbers and elastomers tends
polymers because of its excellent properties such as low
to decrease the rigidity of the matrix.
manufacturing cost, facile processing, and good mechanical and
thermal properties. However, its poor notch impact strength The introduction of inorganic rigid particles is another significant
and high brittleness at low temperature prevent its application method used to modify the toughness of PP. As a promising tough-
as an engineering plastic. To overcome this drawback, many ening method, rigid-particle toughening increases the modulus of
methods have been proposed. PP as well. The rigid particles must relieve volume strain in the
matrix polymer in order to promote shear yielding. When the
A popular way to improve the toughness of PP is by blending
stress is low, the interface between the rigid particles and the matrix
with rubbers and elastomers, e.g., ethylene-propylene-diene rub-
remains undamaged, permitting stress transfer between the rigid
ber (EPDM), ethylene-propylene rubber (EPR), styrene-
particles and the matrix.4 As a result, the modulus is increased.
butadiene-styrene elastomer (SBS), and ethylene-octene elasto-
Low interfacial strength is necessary for this method to allow the
mer (POE). The toughening mechanisms of rubber particles
rigid particles to debond from the matrix upon the application of
have been researched for a long time. It is generally accepted
excessive stress. The cavitations created by debonding at the
that rubber particles act as stress concentrators because of the
boundaries between the rigid particles and the matrix serve as
difference in stiffness of the modifier particles and the matrix
stress concentrators, which is similar to the behavior of rubber par-
polymer. The stress concentration results in microvoids inside
ticles. The widespread cavitations change the stress state, which
the rubber particles or cavitations at the interface between the
relieves the plastic constraints and makes yielding easier.5 During
particles and the matrix.1 The formation of voids releases the
this process, a great quantity of energy is absorbed.
volume strain and plastic constraints, which promotes plastic
deformation of the matrix. During deformation, energy is The high surface free energy of inorganic rigid particles will
absorbed by shear yielding or crazing of the matrix.2 The inter- lead to aggregation and inhomogeneous dispersion in the
particle distance is a major factor affecting the toughness of the matrix and reduces the effect of modification.6 The most

C 2017 Wiley Periodicals, Inc.

V

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Figure 1. The schematic structure of CTM.
common way to improve the dispersion of rigid particles in the
matrix is to treat the inorganic rigid particles with organic com-
pounds, i.e., coupling agents and organic acids.5,7–9 Moreover,
the particle size must be fine and its distribution should be nar-
row to avoid crack initiation by the large rigid particles. The
interparticle distance also plays a very important role in tough-
ening. Below a certain distance, a spectacular toughness jump is
likely to occur.10 Among various inorganic fillers, CaCO3 is one
of the most widely used to improve the toughness of the poly-
mer matrix, and has achieved success in HDPE and PP.11–13
However, toughening with rigid particles has very strict condi-
tions and remains a subject for further development in indus-
trial application.
The molecular weight (MW) of the matrix also has an influence
on the toughness of PP and PP/CaCO3 composites. The defor-
mation and failure of PP are related to the crazes formed in the
weak points, which assemble in the neighborhood of intercrys-
talline regions.14 The tie molecules interconnect crystalline
regions and thus cause the deformation and failure of PP. The
concentration of the tie molecules is increased with increasing
MW, which accounts for the high fracture strength of high-MW
Table I. Composition of PP/CTM Composites
PP/CTM (wt %/wt %) CaCO3 (wt %)
100/0 0 0
90/10 7.43
80/20 14.86
70/30 22.29
60/40 29.72
50/50 37.15
40/60 44.58
30/70 52.01
a
The composition of CTM is based on TG/DSC data.
The PP used is 001 G or S1003.
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PP.14–16 In addition, Lin and co-workers17 found that the
improvement in impact strength of PP/nano-CaCO3 compo-
sites, and the enhancement of higher-MW PP are more signifi-
cant because of the higher concentrations of tie molecules.
The incorporation of both elastomers and inorganic rigid par-
ticles into the polymer matrix is an effective way to modify both
the toughness and stiffness of the matrix. The performance of the
composite is greatly dependent on the phase morphology and the
dispersion of the filler in the matrix.18 The encapsulation of the
filler by the elastomer, producing core-shell particles, have been
designed to satisfy the demands for high performance. The struc-
ture, size and distribution of core-shell particles can be controlled
to influence the spatial arrangement of the ternary composite.6
Jancar and Dibenedetto19 proposed some models to predict the
elastic moduli of PP/EPR/CaCO3 and PP/EPR/Mg(OH)2 compo-
sites in two limiting cases, i.e., complete separation of the filler
and the elastomer and good coverage of the filler by the elasto-
mer. Good agreement was achieved between the experimental and
theoretical results, which provided new ideas for material design.
Elloumi and co-workers20 investigated the effects of particle size
and filler treatment of CaCO3 on the properties of PP/EPR/
CaCO3 composites. They found that improvements in the
notched impact strength could be obtained by nano-CaCO3 and
that the treated particles had a tendency to form complicated
structures with EPR, which could attain better impact strength.
A proprietary CaCO3 toughening masterbatch (CTM) for poly-
olefin was developed by Prof. Dr. Yuancan Zhang and cow-
orkers21,22 at Nanjing University of Chemical Technology. It
greatly improves the toughness of PE and polyolefin blends and
has been successfully used in plastic articles such as barrels, con-
tainers, pipes and automobile bumpers, panels and dashboards,
among others.23 The structure of CTM is shown in Figure 1. In
this article, we blended CTM with iPP [two grades with differ-
ent MWs and MW distributions (MWDs)] to investigate the
structures and properties of the composites.
EXPERIMENTAL
Materials
PP powders (001, MFR 5 0.1 g 10 min21 under 2.16 kg load
and 230 8C) were obtained from Nanjing Jinling Plastic &
Components in the CTMa
PE (wt %) Additives (wt %)
0
1.95 0.62
3.90 1.24
5.85 1.86
7.80 2.48
9.75 3.10
11.70 3.72
13.65 4.34
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Table II. The MWs and MWDs of PPs
PP Mw (g mol21) Mn (g mol-1) Mw/Mn
001G 1158786 223858 5.18
S1003 426995 109086 3.91
Petrochemical Co. Ltd. (Nanjing, China); PP granules (S1003,
MFR 5 3.5 g 10 min21 under 2.16 kg load at 230 8C) were pro-
duced by PetroChina Dushanzi Petrochemical Co. (Dushanzi,
China). CaCO3 toughening masterbatch granules (CTM, 500 A)
were obtained from Nanjing Tough Plastic Co., Ltd. (Nanjing,
China). Industrial antioxidant (B215, antioxidants 1010/
168 5 1/2 wt %/wt % mixture) and calcium stearate (acid scav-
enger and lubricant) were provided by Nanjing Hua Lim Chem-
ical Co., Ltd. (Nanjing, China).
Preparation of Samples
Considering that the form of the raw material may influence
the blending effect, 001 granules were prepared first. The 001
powder was premixed with 0.1 wt % B215 and 0.1 wt % cal-
cium stearate (a common formula for commodity PP granules).
The mixture was compounded in a single-screw extruder (SJ30–
28, D 5 30 mm, L/D 5 28/1, Zhongsu Haichuang Plastic
Technology Co., Ltd., Wuhan, China) at a temperature of 215 8C
and rotational speed of 32 rpm. The melt was cooled and pellet-
ized, and 001 granules (001 G) were obtained. Then, 001 G and
S1003 granules were mixed with variable amounts of CTM gran-
ules, respectively, and their compositions are listed in Table I. The
mixtures were compounded in the same single-screw extruder
under the same extrusion conditions. The melt was cooled and
pelletized. Standard test specimens were injection-molded with a
reciprocating-screw injection molding machine (CJ80M3V, Chen
De Plastics Machinery Co., Ltd., Foshan, China). The injection
temperature and mold temperature were 215 8C and 20 8C, and
the injection pressure was 70 MPa.
Gel Permeation Chromatography Characterizations
Two PP granules were used in this experiment, namely, 001 G
(pipe grade, high MW) and S1003 (filament grade, medium
MW). The MW and MWD (MWD 5 Mw/Mn) of the granules
were determined by using an Agilent PL-GPC220 (USA)
equipped with two chromatographic columns (Plgel 10 lm
MIXED-B) at a temperature of 160 8C. 1,2,4-Trichlorobenzene
was used as the eluent at a flow rate of 1 mL min21, and poly-
styrene (PS) with a narrow MWD was used to obtain the pri-
mary calibration curve. The results are listed in Table II.
Thermogravimeter/Differential Scanning Calorimeter Test
Thermogravimeter/differential scanning calorimeter (TG/DSC)
testing of CTM was carried out in a Netzsch STA 449 C instru-
ment (Germany). The sample was scanned from 40 8C to
1000 8C at a heating rate of 10 8C min21 under a dry nitrogen
atmosphere.
Density Measurements
The densities of PP composites and CTM were measured by a
digital density tester (JL3002, Suzhou Yinganyang Instruments
Co., Ltd., Suzhou, China). The density of CaCO3 powder (2.546
g cm23) used in the CTM was provided by Prof. Dr. Yuancan
Zhang. According to the density and the weight fraction of the
component, the volume fraction of the component can be cal-
culated by using eq. (1):
Volume fraction% 5 100%3w3q=q0 (1)
where w is the weight fraction of CTM or CaCO3 in the com-
posites, q0 is the original density of CTM or CaCO3, and q is
the density of the corresponding composite. The volume frac-
tions of CTM and CaCO3 are listed in Table III.
DSC Measurements
The melting and crystallization behaviors of the samples were
measured by using a DSC apparatus (ZF-DSC-D2, Shanghai
Zufa Industry Co., Ltd., Shanghai, China) under a dry nitrogen
atmosphere. The instrument was calibrated with an indium
standard before measurement. Each sample of 5 6 0.5 mg was
placed in an aluminum pan and heated from room temperature
to 210 8C at a heating rate of 10 8C min21, then held at 210 8C
for 5 min to remove the thermal history. Then the melted sam-
ple was cooled to 100 8C at a cooling rate of 10 8C min21 and
held at 100 8C for 5 min. Finally, the sample was reheated to
210 8C at a heating rate of 10 8C min21. The peak melting tem-
perature (Tm) and peak crystallization temperature (Tc) were
obtained from the melting and cooling curves. The crystallin-
ities (Xc) of each component in the composites were calculated
by using eq. (2):

Table III. The Volume Fractions of CTM and CaCO3 in the Composites

S1003 001G
PP/CTM (wt %/wt %) CTM (vol %) CaCO3 (vol %) CTM (vol %) CaCO3 (vol %)
100/0 0 0 0 0
90/10 5.30 3.74 5.33 3.77
80/20 10.86 7.67 11.20 7.91
70/30 17.53 12.38 17.69 12.50
60/40 24.90 17.60 25.06 17.71
50/50 33.27 23.51 33.44 23.63
40/60 42.66 30.14 42.82 30.26
30/70 53.50 37.80 53.46 37.78

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Xc 5 100%3DHm =ðw3DH0 Þ (2)

where DH0 is the enthalpy of fusion of a sample with 100%
crystallinity. For PP and PE, the values of DH0 were accepted to
be 207 J g21 and 277 J g21,24 respectively. The value w is the
weight fraction of PP or PE in the composite.
Dynamic Mechanical Analysis Tests
The samples were tested with a dynamic mechanical analysis
(DMA) instrument (DMA 1 450, 01db-Metravib, France) in the
tensile mode at a frequency of 1 Hz. The samples were prepared
in a rectangular form with dimensions of 15 3 10 3 1 mm3.
The tests were performed from 2100 8C to 150 8C at a heating
rate of 2 8C min21.
Mechanical Measurements
The tensile and flexural tests were carried out by using an elec-
tromechanical universal testing machine (SANS5254, Shenzhen Figure 2. TG/DSC curves of CTM. [Color figure can be viewed at
SANS Testing Machine Co., Ltd., Shenzhen, China) according to wileyonlinelibrary.com]
ISO 527 and ISO 178, respectively. The testing speeds for the
tensile and flexural tests were 20 and 2 mm min21, respectively. Shrinkage% 5 100%3 ðL2L0 Þ=L0 (3)
The Izod notched impact strength was measured by using a
where L0 is the length measured in the mold cavity and L is the
pendulum impact testing machine (YF8012, Yangzhou Yuanfeng
Testing Machine Factory, Yangzhou, China) according to ISO length of the specimen.
180. The specimens were notched on a specimen notcher RESULTS AND DISCUSSION
(MZ2061, Jiangdu Mingzhu Testing Machine Factory, Jiangdu,
TG/DSC Analysis
China). The impact tests were carried out at 23 8C and 0 8C.
Figure 2 shows the TGA/DSC curves of CTM. Additives (e.g.,
Optical Microscopy Observations coupling agents, lubricants) decomposed in the temperature
The fractured surfaces of impact specimens tested at 23 8C and range from 200 8C to 400 8C, and the weight drop was 6.2 wt
0 8C were observed by using a 3 D video microscope system %. As shown in the DSC curve, an endothermic peak located at
(TD300, Mingqu Enterprise Co., Ltd., Taiwan). 126.7 8C is considered the Tm of PE.26 The decomposition of PE
Scanning Electron Microscopy Observations occurred in the temperature range from approximately 400 8C
The injection-molded samples were cryogenically fractured in to 500 8C.27 A wide endothermic peak (400 8C–500 8C) is shown
liquid nitrogen. The micro-morphologies of the cryogenically in the DSC curve, and belongs to the decomposition of PE. The
fractured surfaces were observed by using a Scanning Electron weight drop of PE was 19.5 wt %. CaCO3 began to decompose
Microscopy (SEM) (JSM 6510, JEOL, Japan). The impact- at 600 8C. At 790 8C, CaCO3 decomposed completely and the
fractured surfaces tested at 23 8C and 0 8C were observed by weight drop was 32.8 wt %. This weight drop of CaCO3 was
using an FESEM (Quanta 250, FEI, USA). All the fractured sur- caused by the loss of CO2, and the slag remaining was CaO
faces were sputter-coated with gold for better conductivity (41.5 wt %). The total wt % of CaCO3 in the CTM is the sum
before observation. of CO2 and CaO, i.e., 74.3 wt %. In all, the proportions of

Heat Deflection Temperature Tests

Heat deflection temperature (HDT) tests were implemented by
using an HDT-VICAT tester (XRW300A, Chengde Jinhe Instru-
ment Manufacturing Co., Ltd., Chengde, China) according to
ISO 75. The heating rate was 120 8C h21 and the flexural stress
was 0.45 MPa.
Melt Flow Rate Measurements
The Melt flow rate (MFRs) of the samples were measured by
means of an MFR determinator (XNR-4, No. 2 Testing Machine
Factory of Changchun, Changchun, China) under a standard
load of 2.16 kg or 5 kg at a temperature of 230 8C according to
ISO 1133.
Shrinkage Measurements
The impact specimens were used to measure the linear shrink-
age along the flow direction. They were stored at 23 8C for a
week before the measurements. The formula of the shrinkage in Figure 3. Density of PP/CTM composites. [Color figure can be viewed at
percentage is given as follows25: wileyonlinelibrary.com]

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Figure 4. DSC curves of PP/CTM composites. (a) the second melting curves of S1003/CTM composites, (b) the second melting curves of 001 G/CTM
composites, (c) the cooling curves of S1003/CTM composites, (d) the cooling curves of 001 G/CTM composites. [Color figure can be viewed at wileyon-
linelibrary.com]

CaCO3, PE, and additives in the CTM are 74.3 , 19.5 , and 6.2
wt %, respectively.
Density Measurements
Figure 3 shows the density of the composites as a function of
the volume fraction of CTM. The densities of 001 G, S1003,
and CTM are 0.908, 0.909, and 1.799 g cm23, respectively. As
shown in Figure 3, a good linear relationship is obtained
between the density of the composites and the volume fraction
of CTM, which implies that a compact and dense combination
of the filler and the matrix is obtained during specimen prepa-
ration. Otherwise, the density will be reduced by the voids and
flaws in the specimens. The homogeneous and compact distri-
bution of the filler in the matrix is shown in the SEM images of
the cryogenically fractured surfaces of the impact specimens
(Fig. 9).

Table IV. DSC Parameters of S1003/CTM Composites

Crystallinity (%) Tm (8C) Tc (8C)

CTM (wt %) PP PE PP PE PP PE
0 28.71 — 167.9 — 109.1 —
10 28.12 9.26 151.5,167.7 128.6 112.5 —
20 21.86 16.59 167.7 129.1 111.9 —
30 20.70 20.80 166.2 129.3 111.6 —
40 19.61 22.73 165.6 129.4 111.3 —
50 18.02 27.88 164.9 129.2 110.7 —
60 19.21 30.58 163.6 129.1 110.7 107.8
70 15.98 44.77 162.7 129.1 110.5 107.0

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Table V. DSC Parameters of 001 G/CTM Composites

Crystallinity (%) Tm (8C) Tc (8C)

CTM (wt %) PP PE PP PE PP PE
0 26.17 — 167.7 — 105.8 —
10 28.07 9.81 151.2,166.4 128.4 109.3 —
20 19.49 13.99 166.2 129.1 109.9 —
30 18.70 18.70 166.3 130.0 109.1 —
40 18.62 23.46 165.8 129.6 109.1 —
50 18.44 24.87 165.0 129.7 109.7 —
60 16.39 31.10 164.0 130.1 110.6 106.7
70 15.87 42.26 163.9 130.8 110.4 106.4

DSC Analysis
The melting and crystallization behaviors of the PP/CTM com-
posites are shown in Figure 4. The relevant parameters are pre-
sented in Tables IV and V. Neat 001 G and S1003 have Tm
values of 167.7 8C and 167.9 8C, corresponding to a-phase PP,
and crystallinities of 26.17% and 28.71%, respectively. With the
addition of CTM, endotherm peaks located at approximately
129 8C appear in the melting curves, which are related to the
melting of PE in the CTM. With increasing CTM content, the
melting peaks of PP weaken and the peaks of PE are enhanced.
When the CTM content is 10 wt %, the crystallinity of PP is
slightly affected because of the heterogeneous nucleation of
CaCO3. The weak b-phase melting peaks located at approxi-
mately 151 8C appear at 10 wt % CTM in both PP composites
and disappear with increasing CTM content. This behavior
implies that the surface-treated CaCO3 may induce the forma-
tion of b-PP at an appropriate low content. An obvious
decrease in the crystallinity of PP is obtained for higher CTM
content. The crystallinity of PP in the S1003/CMT composite
decreases from 28.12% to 15.98%, while the crystallinity of PE
increases from 9.26% to 44.77% when the CTM content
increases from 10 wt % to 70 wt %, i.e., the PE content
increases from 1.95 wt % to 13.65 wt % (as shown in Table I).
Likewise, the 001 G/CTM composite has the same tendency. In
addition, the crystallinities of PP and PE are positively corre-
lated with their respective contents. This phenomenon was also
found in Wang’s study.28 Moreover, the Tm values of 001 G and
S1003 both exhibit an obvious decline with the addition of
CTM. The changes in the crystallinity and the Tm values may

Figure 5. DMA spectra of PP/CTM composites. (a) storage modulus of S1003/CTM composites, (b) storage modulus of 001 G/CTM composites, (c)
loss modulus of S1003/CTM composites, (d) loss modulus of 001 G/CTM composites, (e) tan d of S1003/CTM composites, (f) tan d of 001 G/CTM
composites. [Color figure can be viewed at wileyonlinelibrary.com]

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Table VI. DMA Parameters of PP/CTM Composites
b-Transition (8C)
Samples S1003 001G
PP 1.5 2.3
PP/CTM (70/30) 23.3 21.3
PP/CTM (40/60) 24.5 23.8
indicate improved interaction between PP and CTM. The intro-
duction of PE may also reduce the grain size of PP and develop
the multi-phase structure.29
As shown in the cooling curves of PP/CMT composites [Figures
4(c,d)], it is difficult to confirm the exact Tc of PE because the
peak of PE is covered by that of PP. A relatively weak crystalli-
zation peak can be observed when the CTM content is above 60
wt % (PE content  11.70 wt %) in both PP/CTM composites.
The small peak behind the main peak is because of the subse-
quent crystallization of PE.30 The Tc values of neat 001 G and
S1003 are 105.8 8C and 109.1 8C, respectively. S1003 has a higher
Tc than that of 001 G, indicating that high-MW PP may hinder
crystallization. It may also result from the slightly higher crys-
tallinity of S1003. Compared with the neat PPs, Tc values shift
to higher temperatures with the addition of CTM in both com-
posites, indicating that CaCO3 particles have a heterogeneous
nucleating effect.31 When the content of CTM is 10 wt %
(CaCO3 content is 7.43 wt %), the Tc values are approximately
3.5 8C higher than those of the unfilled PPs. There is no distinct
effect on Tc with further increases in CaCO3 content.
DMA Measurements
To clarify the interaction in the multi-component composites,
the dynamic mechanical properties of neat PP, the PP-rich com-
posite (PP/CTM 5 70/30 wt %/wt %) and the CTM-rich com-
posite (PP/CTM 5 40/60 wt %/wt %) were characterized. The
results of DMA [storage modulus (E0 ), loss modulus (E”), and
damping factor (tan d 5 E00 /E0 )] of the PP/CTM composites are
illustrated in Figure 5, and the relevant parameters are listed in
Table VI. As shown in Figure 5(a), E0 decreases with tempera-
ture for both composites, which implies that the mobility of the
molecular chains is enhanced with increasing temperature. The
addition of CTM to the PP matrix increases E0 , indicating the
improvement of stiffness of the composites expected upon add-
ing rigid particles. The introduction of CaCO3 particles imposes
a mechanical restraint; thus, the mobility of the molecular
chains is weakened.32
Compared with 001 G, S1003 has medium MW and better
mobility of the molecular chain. E0 is sensitive to temperature
change for S1003 composites. E0 is greatly improved at low tem-
perature. The E0 of S1003/CTM (70/30) composite decreases to
the same level as that of S1003/CTM (60/40) from the tempera-
ture range of 225 8C to 140 8C. The increase in stiffness is lim-
ited at high temperature for 001 G/CTM composites. This limit
is attributed to the adverse effects of PE and additives in CTM
as they have more active molecular chains than PP.
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a-Transition (8C) E0 at 23 8C (MPa)
S1003 001G S1003 001G
95.4 99.5 1660 1940
83.9 82.8 2440 2170
76.1 76.7 2530 2580
The loss modulus (E”) is an important factor in energy con-
sumption. A larger value of E” indicates that more energy is
absorbed during the loading process and the toughness is bet-
ter.33 With the addition of CTM, the E” of 001 G/CTM compo-
sites increases obviously, while the E” of S1003/CTM
composites changes slightly. This behavior implies improved
toughness for the 001 G/CTM composites.
Figure 5(e,f) shows the temperature dependence of tan d for
S1003 and 001 G composites. In the measured temperature
range, two transitions located at approximately 0 8C and 100 8C
can be observed for neat PPs. The relaxation peak at approxi-
mately 0 8C, i.e., the b-transition, corresponds to the glass-
rubber transition for the amorphous region, and the peak
temperature is considered to be the glass transition temperature
(Tg). In the cases of neat S1003 and 001 G, the peak of the b-
transition is located at 1.5 8C and 2.3 8C, respectively. These Tg
values of PP are close to the value of 3 8C reported by Hassan
et al.34 The transition at approximately 100 8C is said to be the
a-transition. This transition is related to the relaxation of amor-
phous chains in the crystalline phases.35 The b-transition shifts
to lower temperatures with the addition of CTM in both PP/
CTM composites. Similarly, the increasing content of CTM also
represents increasing contents of PE and additives. The
decreased Tg of PP implies that the miscibility between PP and
CTM is improved regardless of the MW of PP. This dependence
is also indicated by the decreasing Tm of PP with increasing
CTM content in the composites. According to the literature,36
DMA of linear or branched polyethylene exhibits three peaks,
labeled the a, b, and g transitions, in order of decreasing tem-
perature. The g transition (Tg) for polyethylene occurs in the
range of 2150 8C to 2100 8C. No peak related to the transition
of PE could be found in Figure 5(e,f), suggesting that the Tg of
PE may be below 2100 8C. Otherwise, the additives in the CTM
may disturb the local molecular mobility and weaken the transi-
tions of PE. Chen and coworkers30 also found that the single Tg
of PP shifts to lower temperatures with increasing content of
PE in iPP/PE binary blends.
Mechanical Properties
Figure 6(a,b) show the stress-strain curves of PP/CTM compo-
sites. The distinct yield points are shown on the curves. Gener-
ally, before the yield points, the samples are uniformly
stretched. After the yield points, a flat region where the elonga-
tion of samples is enhanced several times their original length
appears with an almost constant load. The large deformation of
the samples is related to molecular orientation. The directional
movement of the molecular chain occurs under the function of
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 6. Mechanical properties of PP/CTM composites. (a) stress–strain curves of S1003/CTM composites, (b) stress-strain curves of 001 G/CTM com-
posites, (c) tensile strength of PP/CTM composites, (d) tensile yield strength of PP/CTM composites, (e) the dependence of ln rr on volume fraction of
CaCO3, (f) tensile strain at break of PP/CTM composites, (g) flexural modulus of PP/CTM composites, (h) Izod notched impact strength of PP/CTM
composites measured at 23 8C, (i) Izod notched impact strength of PP/CTM composites measured at 0 8C. [Color figure can be viewed at wileyonlineli-
brary.com]

tensile stress, while the spherulites of PP are also distorted dur-
ing this process.37 Finally, fracture occurs when the deformation
reaches a certain degree. In addition, the yield strength of PP/
CTM composites can be considered to reflect the incipient stage
of debonding. From their stress-strain curves, a relatively obvi-
ous strain-hardening effect can be observed in S1003/CTM
composites, fracturing under long strain. The tensile strength is
equal to the break strength except for the S1003/CTM (40/60)
composite. However, the stress of the 001 G/CTM composites
decreases distinctly after yielding, and the tensile strain at
breaking is relatively low.
The tensile strength and tensile yield strength results of the
composites are shown in Figure 6(c,d). Generally, the tensile
strength of 001 G/CTM composites is higher than that of
S1003/CTM composites. The tensile strengths of neat 001 G and
S1003 are 51.80 and 48.15 MPa, respectively. The tensile
strength of neat PP is dependent on MW and MWD. In the
tensile process, spherulites are likely to transform into fibril
structures, including the intercrystalline region.38 With increas-
ing MW, the concentration of tie molecules increases as well,
which would limit the flow of fibril structures and decrease the
draw ratio.39 The high concentration of tie molecules gives
001 G better interconnectedness than S1003. The tensile
strength and the tensile yield strength of 001 G/CTM are higher
than those of S1003/CTM, implying the better interconnected-
ness of 001 G. There is a decrease in tensile strength and tensile
yield strength with the addition of CTM in both composites. It
was found that the interface adhesion has great influence on the
tensile strength of the rigid particle-filled PP.40 The debonding
of rigid particles is likely to occur during the tensile process.

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ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 7. The impact-fractured surfaces of PP/CTM composites measured at 23 8C. (a) S1003, (b) 001 G, (c) S1003/CTM (70/30) composite, (d) 001 G/
CTM (70/30) composite, (e) S1003/CTM (40/60) composite, (f) 001 G/CTM (40/60) composite. [Color figure can be viewed at wileyonlinelibrary.com]
The cavities created by debonding decrease the tensile strength
of the system as well as the yield strength. Moreover, the intro-
duction of PE and additive, which have lower tensile and yield
strength than the PP matrix, also decreases the tensile and yield
strength of the composites.
A formula was developed by Pukanszky et al.41,42 to investigate
the effect of filler particles on the yield strength of the matrix.
According to the semi-empirical formula, the relative yield
strength of a heterogenetic composite can be conveniently
obtained as follows:
ry 112:5
rr 5 5exp ðBÞ (4)
ry0 12
where rr is the relative yield strength, ry and ry0 are the yield
strength of the composite and the matrix, and u is the volume
fraction of the filler. B is the parameter reflecting the interfacial
adhesion and load-bearing capacity of the filler.
Figure 6(e) shows the linear plots of ln rr against u, and B is
calculated as the slope. The values of r2 (a parameter to evaluate
the fit of a linear regression) of S1003 and 001 G composites
are 0.9974 and 0.9954, respectively. The curves of both PP
WWW.MATERIALSVIEWS.COM 45515 (9 of 16)
composites show good linear relationships, indicating the fine
dispersion of rigid particles and the absence of aggregates.43 The
B values of the S1003 and 001 G composites are 1.85 and 1.78,
respectively. Yin and coworkers44 found that B of PP/Mg(OH)2
composite was 1.44, and it increased to 1.92 with the addition
of POE. The B value of the S1003 composites is slightly higher
than that of the 001 G composites, implying better interfacial
adhesion in the S1003 composites. The CaCO3 particles in
CTM are covered by PE and other additives, as shown in Figure
1. The coating layer can improve the compatibility and interfa-
cial adhesion between the CaCO3 particles and the matrix, as
proven by the transformation of Tg of PP to low temperature in
DMA measurements. Tg of the S1003 composites is lower than
that of the 001 G composites, as shown in Table VI, which
reflects the better interfacial adhesion of S1003 composites and
the higher value of B.
Figure 6(f) shows the tensile strain at break of the PP/CTM
composites. The strains at break of neat 001 and S1003 are
178% and 486%, respectively. The composite 001 G has a high
MW and a wide MWD, and S1003 is the opposite. The more
nonuniform structures in the 001 G specimens may reduce the
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 7. (Continued). [Color figure can be viewed at wileyonlinelibrary.com]
deformation ability during the tensile process, while S1003 is
designed for filaments with a high draw ratio. With increasing
CTM content, the strain at break of the 001 G/CTM composites
decreases gradually. However, that of S1003/CTM composites
shows no obvious changes until 50 wt % CTM. Then, a drastic
decrease in strain at break occurs when the CTM content is 60
wt % (CaCO3 content 5 44.58 wt %). Composites containing
high concentrations of CaCO3 particles tend to fracture at low
strain because of the large amount of cavities formed in the
matrix. These cavities are likely to be the stress concentration
points, and thus fractures begin first at these flaws. When the
CTM content reaches 70 wt % (CaCO3 content 5 52.01 wt %),
the two composites have similar strain at break.
As shown in Figure 6(g), the flexural modulus of the compo-
sites is increased with the addition of CTM. The improvement
of the flexural modulus is expected upon the addition of rigid
particles.13,45 The flexural modulus is usually used to evaluate
the ability of the material to resist deformation. The increase in
flexural modulus demonstrates that the incorporation of rigid
particles is able to enhance the stiffness of the system. For
instance, the flexural modulus values of the composites doped
with 70 wt % CTM increase by 38.8% (S1003) and 18.2%
(001 G). High-MW 001 G tends to have better stiffness, and
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thus the flexural modulus of 001 G/CTM composites is higher
than that of S1003/CTM composites below 40 wt % CTM.
Above 40 wt % CTM, the flexural modulus values of the two
composites tend to be similar.
Figure 7(h) presents the effect of CTM content on the Izod
notched impact strength (IS) of the composites measured at
23 8C. The IS of the 001 G composites is much higher than that
of the S1003 composites. The IS of neat 001 G is 14.26 kJ m22,
which is 3.8 times greater than that of S1003 (3.72 kJ m22).
High-MW 001 G contains a high concentration of tie mole-
cules, resulting in dense chain entanglements, which leads to
the higher IS of 001 G.46,47 The IS of S1003/CTM composites
increases slightly until 60 wt % CTM. A drastic improvement
occurs at 70 wt % CTM, i.e., an IS of 41.23 kJ m22, which is
11.1 times greater than that of neat S1003. The IS of 001 G/
CTM composites has a different tendency. When the CTM con-
tent is below 50 wt %, a relatively sharp improvement in IS
occurs. The maximum IS is 77.97 kJ m22 at 50 wt % CTM,
which is 5.5 times greater than that of neat 001 G. After that
point, the IS declines somewhat.
Figure 7(i) presents the IS values of the composites measured at
0 8C. This temperature is below the Tg values of both PPs, as
shown in Table VI. Below Tg, the movement of molecular
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 8. The impact-fractured surfaces of PP/CTM composites measured at 0 8C. (a) S1003, (b) 001 G, (c) S1003/CTM (40/60) composite, (d) 001 G/
CTM (40/60) composite. [Color figure can be viewed at wileyonlinelibrary.com]

chains is frozen and brittle fracture is likely to occur. The IS
tested at 0 8C is obviously lower than that tested at 23 8C. With
increasing CTM content, the IS values of both composites
increase, and the IS of the 001 G/CTM composites is higher
than that of the S1003/CMT composites. For S1003/CTM com-
posites, the IS increases slightly and reaches a maximum at 70
wt % CTM, namely, 6.82 kJ m22, 2.6 times greater than that of
neat S1003 (2.62 kJ m22). The IS of the 001 G/CTM composites
has a similar trend to the S1003/CTM composites until 50 wt
% CTM, and then a drastic improvement of IS occurs at 60 wt
% CTM. The maximum IS is obtained at 70 wt % CTM, i.e.,
50.48 kJ m22, which is 12.0 times greater than that of neat
001 G (4.19 kJ m22). With increasing CTM content, the PE
content increases as well. The Tg of PE is between 2150 8C and
2100 8C,36 which implies that PE has better mobility of molec-
ular chains than PP has at 0 8C. Hence, the increase in PE con-
tent can prevent brittle fracture and improve the IS of
composites at low temperature. However, the improvement is
directly related to the MW of the matrix.
Morphologies of Impact-Fractured Surfaces
To explain the results of the impact tests, the impact-fractured
surfaces of the PP composites were observed by optical micros-
copy (OM) and SEM (Figures 7 and 8). The whole fractured

Figure 9. The cryogenically fractured surfaces of PP/CTM composites. (a) S1003/CTM (70/30) composite, (b) 001 G/CTM (70/30) composite, (c) S1003/
CTM (40/60) composite, (d) 001 G/CTM (40/60) composite.

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ARTICLE WILEYONLINELIBRARY.COM/APP
surface was observed by OM, and the details of two points
marked on the OM images were examined with SEM. The
impact direction is indicated by arrows in the images. The frac-
ture process can be classified into at least two stages, namely,
crack initiation (the region of point A marked in the OM
images) and crack propagation (the region of point B).48 Gener-
ally, as shown in the OM images, the crack initiation zone
formed under a rapid impact rate presents a relatively flat and
smooth surface. Shear deformation is often observed at the
crack propagation zone, and the deformation degree is related
to the PP matrix and the content of CTM. The irregular shape
of the fractured surface, with large protuberances, is likely to
signify a large shear deformation. The heights of the protuber-
ances were measured and are indicated on the OM images. It is
evident from the OM images that the shear deformation is
greatly influenced by the content of CTM, the PP matrix, and
the test temperature.
Figure 7 shows the micrographs of the impact-fractured surfaces
of PP/CTM composites measured at 23 8C. The micrographs of
the neat PPs are shown in Figure 7(a,b). From the OM images
of neat PPs, the skin-core structures are observed in both PPs,
and the thickness of the skin layer is 0.875 mm and 0.685 mm
for S1003 and 001 G, respectively. The skin-core structure of
the injection-molded samples is mainly caused by the differ-
ences in the thermal and flow conditions.49,50 The outer melt
directly contacted the cold mold, experienced high shear and a
high cooling rate, solidified quickly, and thus formed the skin
layer. In contrast, the internal melt underwent low shear and a
low cooling rate, solidified slowly and thus formed the core
layer. These process led to the structural difference between the
skin and core layers. The skin-core structure disappears for the
composites because of the improvement of thermal conductivity
with the addition of CaCO3 particles. Moreover, parabolic
ridges are observed in the OM images for both neat PPs,
whereas the ridges fade away with the addition of CTM. This
difference implies that the presence of CTM changes the stress
state of the PPs during the impact process.51 The fractured sur-
face of neat S1003 is relatively smooth with less obvious shear
deformation, which reveals the characteristics of brittle fracture.
The fractured surface of 001 G is rougher than that of S1003
and shows several corrugated ridges, reflecting that crack propa-
gation is hindered. The details of regions A and B of neat PPs
are observed by SEM. In region A, the SEM images are similar
for both neat PPs. In region B, the surface of S1003 shows a
large undulation, which is characteristic of brittle fracture, while
the 001 G surface shows fern-like structures. The fern-like struc-
tures of 001 G are caused by the dense entanglements among
molecular chains and contribute to the higher IS.
For PP/CTM (70/30) composites [Figures 7(c,d)], the fractured
surfaces are rougher than the neat PPs, especially for 001 G
composites. The shear deformation is obvious at the right edge
of the fractured surfaces, and the heights of the protuberances
are 0.334 mm and 0.728 mm for S1003 and 001 G composites,
respectively. The cavitations can be found on the SEM images
of the composites. In region B of the 001 G composite, the
wave-like deformation is clearly seen. The formation of cavita-
tions can release high plastic constraints and induce shear
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deformation during the impact process. Cavitations and shear
deformation have been considered the dominant toughening
factors in rigid particle-toughened polymers by many research-
ers.5,52 The massive shear deformation of the 001 G composite
can absorb a lot of energy during the impact process. It is
reflected by the higher IS of the 001 G composite.
For PP/CTM (40/60) composites [Figure 7(e,f)], the shear
deformation is further intensified in both PP composites. The
deformation range of the 001 G composite covers almost half of
the fractured surface, far exceeding that of the S1003 compo-
sites. The heights of the protuberances of S1003 and 001 G
composites are 0.465 mm and 1.193 mm, respectively. The mor-
phologies in the crack initiation region (region A) of S1003 and
001 G composites are similar. However, the 001 G composite
shows more irregular shear deformation than the S1003 com-
posite in the crack propagation region (region B), which implies
greater toughness of the 001 G composite.
In general, the morphology of the composites is relatively flat in
region A (crack initiation). The morphology is completely dif-
ferent in the region B (crack propagation), which is the main
region generating the shear deformation. Distinct differences in
region B can be found between S1003 and 001 G composites.
These differences embody the greater toughness of 001 G com-
posites than S1003 composites.
The testing temperature has a great influence on the toughness
of a polymer, as well as on the fractured surfaces. At low tem-
perature, the mobility of polymer chains is frozen, and thus
shear deformation is difficult to form.53 Only a small amount
of energy is absorbed during the impact process, and brittle
fracture tends to occur. Figure 8 shows the OM and SEM
micrographs of the fractured surfaces of the neat PPs and PP/
CTM (40/60) composites measured at 0 8C. The surfaces frac-
tured at 0 8C are smoother than those fractured at 23 8C. The
results of IS agree with the fractured surface observations very
well. Qiu and coworkers54 found that the interfacial bonding
has a positive improvement on IS at low temperature. As shown
in Figure 8, most of the CaCO3 particles remain on the frac-
tured surfaces, which display good interfacial bonding between
CaCO3 particles and the matrix.
The OM images of neat S1003 and 001 G measured at 0 8C
[Figure 8(a,b)] are similar, but they are flatter than those mea-
sured at 23 8C [Figure 7(a,b)]. The several corrugated ridges in
neat 001 G measured at 23 8C fade away. However, the fern-like
structure is also observed by SEM in region B. On the other
hand, a distinct crack curve is found in region B of S1003,
which is a feature of brittle fracture.
Compared with the fractured surface of the S1003/CTM (40/60)
composite [Figure 8(c)], the fractured surface of the 001 G com-
posite [Figure 8(d)] is irregular with the height of the protuber-
ances equal to 0.795 mm. No difference in region A between the
S1003 and 001 G composites is apparent. However, in region B,
the difference is obvious. High-MW 001 G contains more tie mol-
ecules and has dense entanglements between molecular chains.
These differences are reflected by the larger shear formation of the
001 G composite than that of the S1003 composite.
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 10. Log-normal size distribution of CaCO3 particles in PP/CTM
composites. [Color figure can be viewed at wileyonlinelibrary.com]
In a word, the MW of the matrix has a great influence on the
morphology of the impact-fractured surfaces at low tempera-
ture. A high MW matrix with dense entanglements of chains
will promote the shear deformation of the composites, leading
to more energy absorption during the impact process.
Investigation of the Toughening Mechanism
The cryogenically fractured surfaces of the composites in liquid
nitrogen are shown in Figure 9. The CaCO3 particles are closely
combined with the PP matrix. The MW of the PP matrix has
no obvious influence on the dispersion of CaCO3 particles; the
particles disperse uniformly in both composites. Some voids
appear in the fractured surfaces, and the number of voids
increases with increasing CTM content. Although the samples
were cryogenically fractured in liquid nitrogen, most of the
CaCO3 particles still adhere on the surfaces, exhibiting good
interface adhesion between the filler and the matrix.
To calculate the size distribution of the CaCO3 particles, the
Feret horizontal diameters of approximately 500 particles were
measured in several SEM images (including Figure 9). Generally,
the size distribution of most particles have a tendency toward
large size and hardly complies with the normal distribution.
Therefore, the log-normal distribution has been widely used to
characterize the particle size distribution in polymer compo-
sites.3,55–57 For the log-normal distribution, the frequency (f) is
defined as follows:
 
1 2ðln d2ln dg Þ2
f 5 pffiffiffiffiffi exp (5)
2pln rg 2ln 2 rg
where dg is the average value of particle size, equal to the
median particle size by count; d is the specific value of each
particle size; and rg is the mean standard deviation, represent-
ing the breadth of its distribution. For monodispersity, rg 5 1;
rg > 1 for polydispersity.
The size distributions of CaCO3 particles are shown in Figure
10. The size distribution approximately obeys the log-normal
distribution. The dg value is equal to the particle size at 50% by
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count, and the corresponding rg is equal to the ratio of the
particle size at 84% to that at 50%.3 As shown in Figure 10,
dg 5 1.77 lm and rg 5 1.74.
A drastic improvement in IS with increasing CTM content is
shown in both 001 G and S1003 composites measured at 23 8C.
Wu3,55–57 proposed the critical ligament thickness (sc) as the cri-
terion for the brittle–ductile transition in toughened polymer
blends. With increased number of toughening particles, the inter-
particle distance (s) will decrease. When s < sc, the blend is sig-
nificantly toughened. In the opposite case, the blend is brittle.
This theory has been proven in many studies and is widely used
in both rubber- and filler-toughened systems.58,59 The IS of S1003
composites tested at 23 8C increases abruptly when the CTM con-
tent increases from 60 to 70 wt %, while that of 001 G composites
increases continuously when the CTM content is below 50 wt %,
and a large error value is shown at 30 wt % CTM. This CTM con-
tent may indicate that the interparticle distance of CaCO3 is close
to sc, and thus the critical CTM concentration is considered to be
30 wt %. The critical CTM concentration is different in the two
composites, which implies that the properties of the matrix have
a great influence on sc. The value of sc is not constant for a partic-
ular polymer; different features of the polymer, such as MW, alter
the value of sc. Wu proposed sc as a parameter determining the
appearance of the brittle–ductile transition, and the equation for
sc is as follows3:
 13 
p
sc 5dg 21 (6)
6u
where dg is the average particle size, and u is the volume frac-
tion of the particles.
In Wu’s model, the particle size is considered to be uniform.
However, the particle size has a certain distribution range in
most cases. Liu et al.60 noted that rg has a great effect on the
value of sc. A new formula has been proposed to calculate sc:
 13 
p
sc 5dg exp ð1:5ln 2 rg Þ2exp ð0:5ln 2 rg Þ (7)
6u
Liu et al.60 proved that this modified equation could be effec-
tively applied in composites containing well-dispersed particles
and particle sizes with a log-normal distribution.
In this study, the critical CTM content in S1003 and 001 G
composites is considered to be 60 and 30 wt %, respectively;
the corresponding CaCO3 volume fractions are listed in Table
III. The sc of the S1003 composites is calculated to be 1.31 lm
according to eq. (7). Similarly, the sc of the 001 G composites is
2.46 lm. The 001 G composite has higher MW and more tie
molecules. These dense tie molecules effectively delay crack ini-
tiation and propagation under impact load, hence enhancing
the fracture strength; whereas S1003, with a low density of tie
molecules, is likely to induce brittle fracture. Cavitations created
by debonding can cause plastic deformation of the matrix,
which is able to absorb impact energy. The proper adhesion
between rigid particles and the polymer is important during the
impact process.61 The adhesion between CaCO3 particles cov-
ered with the flexible interlayer and PP matrix is improved, as
shown in Figures 5 and 9. However, the modulus of the
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 11. The HDT values of PP/CTM composites. [Color figure can be
viewed at wileyonlinelibrary.com]
interlayer is lower than that of the matrix, reflected by the
decrease in yield strength of the composites, which means the
debonding of rigid particles is likely to occur during the impact
process. With the addition of CTM, cavitations formed by the
debonding of CaCO3 particles enable massive shear deformation
in the ligaments between adjacent particles. When the CTM
content is low, the distance between the particles is large, and s
is large. The volume constraint still exists because of the large s,
which restricts the formation of shear deformation. As a result,
the improvement in impact strength is limited. Once the s
reaches a critical distance (sc) with increasing particle content,
the volume constraint will be fully released, and yielding occurs
easily. Yield occurs prior to fracture with a low volume con-
straint, which causes massive shear deformation and greatly
improves the impact strength. Moreover, the sc of 001 G com-
posites is larger than that of S1003 composites, which means
that the brittle-ductile transition for 001 G composites occurs
easily. A higher content of CTM is needed in S1003 composites
than in 001 G composites to enable the transition to occur.
This result implies that the good toughening effect occurs only
for high MW PP. Lin et al.17 studied the sc of PP/CaCO3
Figure 12. The MFR values of PP/CTM composites. (a) S1003/CTM composites, (b) 001 G/CTM composites. [Color figure can be viewed at wileyonline-
library.com]
WWW.MATERIALSVIEWS.COM 45515 (14 of 16)
nanocomposites with 70 nm particle size. The sc value of high-
MW PP is also larger than that of low-MW PP.
HDT Tests
Figure 11 shows the HDT of the PP/CTM composites. The
HDTs of neat 001 G and S1003 are 101.9 8C and 98.4 8C, respec-
tively. HDT increases until the CTM content is 20 wt %. When
the CTM content is more than 20 wt %, a decline of HDT is
shown in both curves. Moreover, the HDTs of 001 G composites
are higher than those of S1003 composites. The enhancement of
HDT is related to the introduction of CaCO3. The decline of
HDT when CTM content is more than 20 wt % is possibly
attributable to the negative effect of excessive PE and additives
with low heat deflection modulus values. Wong62 also found
that the HDTs of PP/PE binary blends had a linear relationship
with the content of each component. When the CTM content is
60 wt %, the HDTs of the composites are lower than those of
the neat PPs. Although the same specimens and flexural mode
were used, the trend of the HDT tests is different from that of
flexural tests, while the flexural modulus increases continuously
with CTM content. The difference in trends may be related to
the different experimental conditions of the two tests. HDT
tests were conducted in a rising temperature environment, while
flexural tests were carried out at 23 8C. In short, the HDTs of
the composites increase obviously with low contents of CTM
( 20 wt %) because of the enhancement of CaCO3 particles,
whereas the further increase of CTM reduces the HDT of both
PP/CTM composites, which is related to the adverse effects of
PE and additives.
MFR Measurements
MFR is an important parameter affecting the processing condi-
tions of a polymer material. A larger MFR value reflects better
rheological and processing properties. Figure 12 shows the MFR
values of PP/CTM composites measured under loads of 2.16
and 5 kg, respectively. The MFR of neat S1003 is much larger
than that of neat 001 G, i.e., the melt viscosity of the former is
lower than that of the latter. MW has a great influence on the
MFR of PP.63 Obviously, high-MW PP 001 G has high melt vis-
cosity. As shown in Figure 12, the MFR of both composites
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45515
ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 13. The shrinkage of PP/CTM composites. [Color figure can be
viewed at wileyonlinelibrary.com]
increases with increasing CTM content and reaches a maximum
at 70 wt % CTM. The content of PE and additives increases
with CTM content. They both decrease the melt viscosity and
increase the MFR of the composites.
Shrinkage Measurements
Figure 13 shows the shrinkage of the injection-molded speci-
mens. Shrinkage is an important parameter for the precision of
a product. The shrinkage of PP, a semi-crystalline resin, results
mainly from thermal contraction during the melt cooling pro-
cess and volume contraction on account of the further perfec-
tion of crystallization after injection molding. As shown in
Figure 13, both PP/CTM composites show a decline in shrink-
age with increasing CTM content. The decrease in shrinkage
with the addition of CTM is mainly caused by two reasons. On
the one hand, CaCO3 is a rigid filler, which reduces thermal
contraction.64 On the other hand, CaCO3 particles have a het-
erogeneous nucleating effect, which accelerates the crystalliza-
tion rate of PP. As a result, the shrinkage is reduced with the
addition of CTM. The shrinkage of 001 G composites is greater
than that of S1003 composites. The difference between S1003
and 001 G composites is related to their MFRs. Compared with
low MFR 001 G, S1003 with good melt flowability fills the
mold cavity more easily at the same injection pressure, causing
S1003 to have low shrinkage. When the CTM content is 70 wt
%, the shrinkage of the two PP composites is similar.
CONCLUSIONS
In this study, the constituent content of CTM is measured by
TG/DSC analysis, and the result shows that the proportions of
CaCO3, PE, and additives in the CTM are 74.3, 19.5, and 6.2 wt
%, respectively. The good linear relationship between the den-
sity of the composites and the vol % of CTM implies the com-
pact structure of the composites and enables the study of the
microstructures and properties of PP/CTM composites. DSC
analysis shows that the addition of CTM decreases the crystal-
linities of both PPs but increases the Tc values, indicating the
heterogeneous nucleating effect of CaCO3 particles. In DMA
measurements, the increase in E0 implies an improvement in the
WWW.MATERIALSVIEWS.COM 45515 (15 of 16)
stiffness of the composites, and the decrease in Tg of the com-
posites implies enhanced miscibility between PP and CTM.
Debonding between the rigid particles and the matrix is likely
to occur under tensile load, which creates cavities and decreases
tensile and yield strength as well as the tensile strain at break of
the composites. However, the Izod notched impact strength of
the composites is greatly improved, accompanied by massive
shear deformation. The morphologies of the impact-fractured
surfaces are dependent on the MW of the matrix. High-MW PP
(001 G) has dense entanglements between molecular chains that
enable considerable shear deformation of the specimen, leading
to greater energy absorption during the impact process. The
size distribution of the CaCO3 particles was obtained by SEM
images of cryogenically fractured surfaces of the composites.
The sc values of the S1003 (1.31 lm) and 001 G (2.46 lm)
composites were calculated according to the critical content of
CTM (60 and 30 wt %). The results imply that sc is related to
the MW of the particular polymer matrix. PE and other addi-
tives in CTM have an adverse influence on HDT and increase
the MFR of the composites. Moreover, shrinkage is reduced by
the presence of CTM.
ACKNOWLEDGMENTS
This work is supported by the Innovation Foundation for Gradu-
ate Students of Jiangsu Province (SJLX16_0295) and the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD).
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