polymers

Article
Synergetic Toughening Effect of Carbon Nanotubes
and β-Nucleating Agents on the Polypropylene
Random Copolymer/Styrene-Ethylene-Butylene-
Styrene Block Copolymer Blends
Peng-Gang Ren 1, * , Jin Wang 1 , Qian Fan 2 , Song Yang 2 , Zhi-Qiang Wu 2 , Ding-Xiang Yan 3, *
and Yan-Hui Chen 2, *
1 School of Materials Science and Engineering, Xi’an University of Technology, Xi’an 710048, China;
18149219745@163.com
2 Department of Applied Chemistry, School of Science, and Shaanxi Key Laboratory of Macromolecular
Science and Technology, Northwestern Polytechnical University, Xi’an 710072, China;
fanqian1211@mail.nwpu.edu.cn (Q.F.); 19802013040@163.com (S.Y.); xg1593572468@163.com (Z.-Q.W.)
3 College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China
* Correspondence: rengpg@126.com (P.-G.R.); yandingxiang@scu.edu.cn (D.-X.Y.);
yanhuichen@nwpu.edu.cn (Y.-H.C.)




Received: 1 December 2018; Accepted: 23 December 2018; Published: 26 December 2018


Abstract: Polypropylene random co-polymer (PPR)/styrene-ethylene-butylene-styrene (SBS) block

copolymer blends with high toughness and favorable tensile properties were successfully obtained
by blending with traces of multi-wall carbon nanotubes (MWCNTs) and β-nucleating agents
(β-NAs). β-NAs can effectively induce the ductile β-form crystal in the PPR matrix. Although the
addition of MWCNTs was reported to be only benefit for the tensile strength of PPR and relatively
disadvantageous for the toughness, the obviously synergistic toughening effect in PPR/SBS blends
was found when MWCNTs and β-NAs coexisted. The notched izod impact strength of PPR/30 wt %
SBS blend with MWCNTs and β-NAs increased from 11.3 to 58.9 kJ/m2 ; more than 5-fold increment
compared with pure PPR. Meanwhile, the tensile strength retention of this PPR blend is still above
72.2%. The micro-morphology indicated that the MWCNTs can act as bridges between SBS particle
and PPR matrix, effectively transferring the stress and absorbing impact energy among SBS particles.

Keywords: polypropylene random copolymer; styrene-ethylene-butylene-styrene block copolymer;

multi-wall carbon nanotubes; β-nucleating agents; synergetic toughening

1. Introduction
Polypropylene random co-polymer (PPR), a co-polymerized propylene with a little amount of
other olefins, is widely used in packaging, film, and other applications. Since the crystallization
ability of propylene sequence is disrupted by the random insertion of a small amount of olefin units,
PPR exhibits lower crystallinity with respect to propylene homopolymer (PPH), but is still considered
a semi-crystalline polymer. The decreased crystallinity endows PPR with satisfied comprehensive
performance, such as flexibility, transparency, and toughness compared with PPH [1–3]. However,
the glass transition temperature (Tg ) of PPR did not decrease significantly by the random insertion of
co-units. Hence, the impact resistance of PPR is still unappeasable for some strict applications such as
outdoor materials used in severe cold area [4].
Several crystalline forms exist in PP, including monoclinic α-form, trigonal β-form and
orthorhombic γ-form, among which the β-form exhibits excellent toughness due to its loose stacking

Polymers 2019, 11, 29; doi:10.3390/polym11010029 www.mdpi.com/journal/polymers

Polymers 2019, 11, 29 2 of 16

structure [5–7]. Large amounts of β-form crystallites are usually formed in the presence of β-nucleating
agents (β-NAs). Therefore, blending β-NAs with PPR is widely used to improve the toughness
of PPR [4–7]. Although plenty of self-toughened β-form crystallites were generated effectively
in a β-nucleated blend system, the toughening effect is still less than satisfactory [8]. To further
broaden the application of PPR, blending with different kinds of elastomers has been frequently
adopted due to its operative convenience and high efficiency, such as blending with ethylene-octene
copolymer (POE) [9], ethylene–propylene diene terpolymers (EPDM) [10], and butadiene–styrene block
copolymers (SBS) [11]. However, the improvement in impact strength usually sacrifices the tensile
properties of PPR blends, due to poor interfacial adhesion and weak elastomer strength. Fortunately,
the rigid nano-fillers [12], such as carbon nanotube (CNT) [13–16], crystal whisker, and calcium
carbonate (CaCO3 ) [17] were reported to display obvious strength enhancement effects on the polymer
matrix, while being unexpectedly beneficial for their toughness. Naturally, combining two or more of
above modifiers is consequentially proposed to improve the comprehensive performance of PPR.
The synergetic effects of β-NAs and elastomers on the impact performance of PPH has been
proved by previous research. For example, Ma et al. [18] demonstrated that the notched impact
strength of PPH markedly increased with the addition of β-NAs and EPDM. However, the most
used β-NAs exhibit unsatisfactory toughening effect on PPR because the structural regularity and
stereo-regularity of PPR are inferior to that of PPH. Even so, some nucleating agents were still found to
be highly efficient β-NAs for PPR [19,20]. Recently, Feng et al. [21] verified that, with the introduction
of high β-nucleating efficiency of CaPim and olefin block copolymer (OBC), the PPR blends showed
not only great enhancement of toughness but also the brittle-ductile transition at a low OBC content.
The results revealed that combining the β-NAs and other modifiers was an efficient method to improve
the toughness of PPR. Unfortunately, many studies only focused on the influence of binary modifiers
on the toughness of PPR. Few works considered the toughness of PPR blends affected by ternary
modifiers, i.e., the coexistence of elastomers, β-NAs, and rigid nano-fillers, especially to achieve the
balance of toughness and strength of the PPR [22].
In the present work, the synergetic toughening and reinforcing effect of β-NAs, elastomers, and
rigid nano-fillers on the PPR was investigated. The most common styrene-ethylene-butylene-styrene
(SBS) and multi-wall carbon nanotubes (MWCNTs) were chosen as the toughener and enhancer,
respectively. The aryl amide compounds (TMB-5) was chosen as β-NAs, due to its high nucleating
efficiency, low cost, and commercial usage. The results indicated that ternary modifiers showed
a significant synergetic toughening effect on the PPR blends, especially under high temperatures.
Compared with pure PPR, the impact strength of ternary modifiers (β-NA + MWCNTs + SBS)/PPR
blend with 30 wt % SBS content at 20 ◦ C increased from 11.3 to 58.9 kJ/m2 ; more than five-fold
increment. Meanwhile, the retention rate of tensile strength is as high as 72.2%. The combination of
β-NAs, SBS elastomers, and MWCNTs displayed an outstanding enhancing effect on the PPR matrix.

2. Experimental

2.1. Materials
The PPR was supplied by China Petroleum and Chemical Corporation (Nanjing, China), which has an
ethylene content of 7.0 mol % and a melt flow rate of 3 g/10 min (230 ◦ C, 2.16 kg), Mn = 8.5 × 104 g mol−1 ,
Mw = 26.3 × 104 g mol−1 , and polydispersity index (Mw /Mn ) = 3.08. Detailed GPC (gel permeation
chromatography) information of PPR can be found in Figure S1 (Supporting Information). SBS (trade
name: D1101), a ternary thermoplastic rubber grafted by maleic anhydride, was purchased from
Kraton Co. (Houston, TX, USA). Multi-wall carbon nanotubes (MWCNTs, trade name: TNM5) were
obtained from Chengdu Organic Chemicals Co. Ltd. (Chengdu, China). Some technical parameters
are as follows: Purity: >98%, OD: 20–30 nm, ID: 5–10 nm, Length: 10–30 µm, SSA: >110 m2 /g. SEM
and TEM images of TNM5 can be obtained from Figure S2 (Supporting Information). β-NAs (trade
name: TMB-5) were purchased from Fine Chemical Institute of Shanxi, Taiyuan, China.
Polymers 2019, 11, 29 3 of 16

2.2. Sample Preparation

The moderate amounts of PPR particles, SBS, β-NAs, and MWCNTs powders were firstly blended
by extrusion (SHJ-20 twin-screw extruder) at temperature profile of 160–195 ◦ C from the hopper
(160 ◦ C) to the die (195 ◦ C); the screw speed is 80 r/min. After dried at 80 ◦ C for 2 h, the extruded
granules were injection-molded into the standard dumbbell samples using an injection-molding
machine HTF90W1 (Ningbo Haitian Plastic Machine Group Co. LTD, Ningbo, China) at an injection
temperature profile of 190 to 200 ◦ C from the hopper to the nozzle. The component and designation
of all the blends are listed in Table 1. PPR blends are coded as CxBySz. Where the letter C, B and S
represent the MWCNTs, β-NAs and SBS fillers, respectively. The number x, y and z are contents of
corresponding fillers.

Table 1. Sample codes and ingredients of all the Polypropylene random co-polymer (PPR) blends.

Samples PPR (wt %) SBS (wt %) TMB-5 (wt %) MWCNTs (wt %)

PPR 100 0 0 0
C0 B0.1 S0 100 0 0.1 0
C0 B0.1 S10 90 10 0.1 0
C0 B0.1 S20 80 20 0.1 0
C0 B0.1 S30 70 30 0.1 0
C0.05 B0 S0 100 0 0 0.05
C0.05 B0.1 S0 100 0 0.1 0.05
C0.05 B0.1 S10 90 10 0.1 0.05
C0.05 B0.1 S20 80 20 0.1 0.05
C0.05 B0.1 S30 70 30 0.1 0.05
C0.05 B0 S30 70 30 0 0.05

2.3. Characterization and Testing

2.3.1. Differential Scanning Calorimetry

Crystallization behavior of PPR and its blends was investigated by differential scanning
calorimetry on a TA Q2000 instrument (TA Co. Newcastle, DE, USA). The samples (5–6 mg) were
heated from 40 to 200 ◦ C at a heating rate of 10 ◦ C/min and maintained at 200 ◦ C for 5 min to eliminate
thermal history, then cooled down to 40 ◦ C at a cooling rate of 10 ◦ C/min. The sample was protected
in nitrogen atmosphere during the entire process. The collected data were fitted by TA Universal
Analysis software. The crystallinity of α-crystals (Xα ) and β-crystals (Xβ ) were calculated as follows:

∆Hα
Xα = (1)
∆Hαθ

∆Hβ
Xβ = (2)
∆Hβθ

where ∆Hα θ is the melting enthalpy when the content of α-crystal is 100%, 178 J g−1 . ∆Hβ θ is the
melting enthalpy when the content of β-crystal is 100%, 170 J g−1 [23], ∆Hα and ∆Hβ were obtained
by TA software from DSC curves.

2.3.2. Scanning Electron Microscopy (SEM)

The fracture morphologies of the MWCNTs, PPR, and its blends were observed by using a field
emission scanning electron microscope (FEI Nova NanoSEM 450, Hillsboro, OR, USA) after gold
sputtering. To observe the phase morphology of the SBS elastomer, the samples were cryogenically
fractured after keeping in liquid nitrogen for 1 h. Subsequently, the fractured samples were put in
tetrahydrofuran at room temperature for 12 h to etch the SBS dispersed phase. After sputtering gold,
Polymers 2019, 11, 29 4 of 16

the samples were also observed by using a field emission scanning electron microscope (FEI Nova
NanoSEM 450, Hillsboro, OR, USA) under an acceleration voltage of 20 kV.

2.3.3. X-Ray Characterization

Two-dimensional wide-angle X-ray diffraction (2D-WAXD) and small-angle X-ray scattering
(2D-SAXS) measurements were conducted at the beamline BL16B1 of Shanghai Synchrotron Radiation
Facility (SSRF, Shanghai, China). For WAXD, the mono-chromated X-ray beam with a wavelength of
0.124 nm was focused to an area of 80 × 80 µm2 (length × width), and the sample-to-detector distance
was set as 152.7 mm. The 2D-WAXD images were collected with an X-ray CCD detector (Model SX165,
Rayonix Co. Ltd., Evanston, IL, USA.). In the SAXS measurement, the sample-to-detector distance
was fixed at 1995 mm. To obtain a discernible X-ray scattering intensity, a piece of slice with width
of 6 mm and thickness of 1 mm was carefully machined from the injection-molded parts. 2D-WAXD
and 2D-SAXS signals come from the central part of the sample. 1D-WAXD profiles were obtained
from circularly integrated intensities of the acquired 2D-WAXD patterns. Detailed information can be
obtained from our previous researches [22,24,25].
1D-SAXS profiles were obtained from the circular average of 2D-SAXS patterns, in which
scattering intensity was plotted as a function of the reciprocal space vector, s(|s| = 2 sin θ/λ, where λ
is the wavelength of the incident beam and 2θ the scattering angle). The long period (LB ) that defines
the statistical average of the distance between two lamellae is determined by the position of the first
intensity maximum (sm) in 1D-SAXS profiles by LB = 1/sm [24]. The thickness of crystalline lamella
(Lc ) can be estimated by Lc = Xc (WAXD) × LB, and the thickness of the confined amorphous phase
La = LB − Lc [26,27].

2.3.4. Dynamical Mechanical Analysis

Dynamical Mechanical Analysis (DMA) was carried out with a Q800 DMA instrument (TA
Instruments, Newcastle, DE, USA) at heating rate of 3 ◦ C/min and at a frequency of 1.0 Hz. The testing
range was from −100 ◦ C to 120 ◦ C. Storage modulus and tangent of loss angle would be obtained,
while Tg was taken from the peak temperature of tanδ curve.

2.3.5. Transmission Electron Microscope (TEM)

Transmission electron microscopy (TEM) was performed with a FEI Talos F200X (Hillsboro, OR,
USA) electron microscope. Stable dispersion of the MWCNTs (dispersed in ethanol) was prepared by
ultrasonic treatment. A drop of stable dispersion was placed on a copper grid and then dried before
it was transferred to the sample chamber. The dispersion state of MWCNTs in polymer matrix was
investigated on a ultrathin composite sample with a thickness of 100 nm, which was prepared on an
Ion Beam Thinner (LEICA, RES102, Wetzlar, Germany).

2.3.6. Impact Tests

The notched izod impact tests were conducted according to the standard GB/T 1843-2008 at
temperatures of −20 ◦ C, −10 ◦ C, 0 ◦ C, and 20 ◦ C. At least five samples of 60 mm × 10 mm × 4 mm
were tested and the average values were adopted. These samples were carefully machined with a single
V-notch of 2 mm depth. The notched izod impact strength can be calculated from following equation:

Ec
aiN = ×103 (3)
h × bN

where Ec is the corrected fracture energy of specimens, J; h is the thickness of specimens, mm; bN is the
remaining width of specimens, mm.
Polymers 2019, 11, 29 5 of 16
Polymers 2019, 11 FOR PEER REVIEW 5

2.3.7. Tensile
2.3.7. Tests
Tensile Tests
The tensile
The tensile tests
tests were
were conducted
conducted according
according to to the
the standard
standard GB/T
GB/T 1040-92
1040-92 at
at temperatures
temperatures of of 23
23 °C.
◦ C.
Dumbbell-shaped samples were used to test the tensile property on an SANS (Suns) universal
Dumbbell-shaped samples were used to test the tensile property on an SANS (Suns) universal testing testing
machine (Shenzhen,
machine (Shenzhen, China)
China) with
with gage
gagelength
lengthofof100
100mm
mmat at50
50mm/min.
mm/min. TheThe size
size of
of the
the tensile
tensile sample
sample
was controlled
was controlled by by injection
injection mold
mold with
with150150mmmm(Length)
(Length)×× 1010
mmmm (Width) × 10
(Width) × mm
10 mm (Thickness).
(Thickness).At
least five samples were tested and the average values were adopted.
At least five samples were tested and the average values were adopted.

3. Results
3. Results and
and Discussion
Discussion

3.1. Notched Izod Impact Performance

The notched izod impact strength of PPR and its blends with various modifiers are shown in
Figure 1. The presence of β-NAs enhanced the impact strength of PPR. Notched izod impact strength
of PPR
PPR increased
increasedfrom from1111toto15.7 15.7 kJ/m
kJ/m 2 with2 with
the addition
the addition of only 0.1 wt0.1
of only % wt β-NAs, improved
% β-NAs, by 42.7%.
improved by
β-NAs β-NAs
42.7%. can induce can PPR
induceto form
PPR to theform
ductile the β-form
ductile crystallites and thusand
β-form crystallites improve the impact
thus improve thestrength
impact
of PPR [1,4,21].
strength of PPRMoreover, the impact
[1,4,21]. Moreover, thestrength
impactof PPR blends
strength markedly
of PPR increased with
blends markedly the increasing
increased with the
SBS elastomer
increasing SBSinelastomer
the presence in of
theβ-NAs,
presence especially
of β-NAs,for the high SBS for
especially loading.
the highWithSBS the addition
loading. ofWith 30 wtthe%
SBS (C0B0.1
addition ofS30
30), wt
the% notched
SBS (Cizod B Simpact
0 0.1 30 ), the strength
notched of β-nucleated
izod impact PPR
strength increased
of from
β-nucleated 15.7PPRto 55.9 kJ/m
increased 2,

showing
from 15.7an toincrement
55.9 kJ/mof 2 , 256%
showing thanan C0increment
B0.1S0. Comparedof 256% with
thanC0CB0.1 S0.1
30, S
the sole addition of MWCNTs
0B 0 . Compared with C0 B0.1 S30 ,
(C0.05sole
the B0S0addition
) reducedofrather MWCNTs than increased
(C0.05 B0 S0the impact rather
) reduced performance of PPR. i.e.,
than increased thethe notched
impact izod impact
performance of
strength
PPR. i.e.,ofthe
PPR slightlyizod
notched decreasedimpact from 11 to 10.1
strength kJ/mslightly
of PPR decreased from 11 to 10.1 kJ/m2 wt
2 in the presence of traces of MWCNTs (0.05 %).
in the
However,ofthe
presence notched
traces izod impact
of MWCNTs (0.05 wt strength of (MWCNTs
%). However, + β-NAs)/PPR
the notched izod impact andstrength
(MWCNTs + β-NAs ++
of (MWCNTs
SBS)/PPR blend
β-NAs)/PPR andare(MWCNTs
superior to+that β-NAsof β-NAs/PPR
+ SBS)/PPR andblend
(β-NAsare+superior
SBS)/PPRtoatthat the ofsame filler contents,
β-NAs/PPR and
respectively.
(β-NAs For example,
+ SBS)/PPR at thethe notched
same fillerizod impact
contents, strength of C
respectively. 0B0.1
For S0 increased
example, thefrom 15.7 izod
notched to 16.4 kJ/m2
impact
with traces of Cof 2 with
strength 0 BMWCNTs
0.1 S0 increased loading
from(C 0.05Bto
15.7 0.1S 0). And
16.4 kJ/mthe corresponding
traces of MWCNTs value ofloading
the C0(C B0.10.05
S30Bblend
0.1 S0 ).
increased
And from 55.9 tovalue
the corresponding 58.9 ofkJ/mthe Cin0 Bthe
2
S presence
blend of MWCNTs.
increased from These
55.9 to results
58.9 kJ/m 2 in the presence
suggest that the
0.1 30
combination
of MWCNTs.of rigidresults
These MWCNTs andthat
suggest flexible β-NAs/SBS modifiers
the combination show an obviously
of rigid MWCNTs and flexible synergistically
β-NAs/SBS
toughening
modifiers effect
show anon the PPR, synergistically
obviously although the sole rigid MWCNTs
toughening filler
effect on thegenerally
PPR, althoughhas a negative
the sole effect
rigid
on the toughness
MWCNTs of PPR. has a negative effect on the toughness of PPR.
filler generally

Izod impact
impact strength
strength of
of various
various polypropylene
polypropylene random
random co-polymer
co-polymer (PPR)
(PPR) blends ◦ C).
Figure 1. Izod
Figure1. blends (20
(20 °C).

The notched izod impact strength of PPR, and its blends at different temperatures, are displayed
The notched izod impact strength of PPR, and its blends at different temperatures, are displayed
in Figure 2. Detailed information of impact strength for PPR and its blends can also be found in
in Figure 2. Detailed information of impact strength for PPR and its blends can also be found in Figure
Figure S3 (Supporting Information). The notched izod impact strength of all samples significantly
S3 (Supporting Information). The notched izod impact strength of all samples significantly increased
increased with the increasing testing temperatures. This is mainly attributed to the volume expansion
with the increasing testing temperatures. This is mainly attributed to the volume expansion and
enhancement of molecular mobility at high temperature, thus weakening the intermolecular forces.
Polymers 2019, 11, 29 6 of 16

Polymers 2019, 11 FOR PEER REVIEW 6

and enhancement of molecular mobility at high temperature, thus weakening the intermolecular
Even so, the trends of impact strength with various fillers are entirely different. The izod impact
forces. Even so, the trends of impact strength with various fillers are entirely different. The izod impact
strength of pure PPR and its blend with a single modifier (i.e., β-NAs/PPR and MWCNTs/PPR)
strength of pure PPR and its blend with a single modifier (i.e., β-NAs/PPR and MWCNTs/PPR) almost
almost linearly rose with the increase in temperature. With the addition of small amounts of SBS
linearly rose with the increase in temperature. With the addition of small amounts of SBS elastomer
elastomer particles (<10 wt %), the impact strength of PPR blends still exhibited a linear relationship
particles (<10 wt %), the impact strength of PPR blends still exhibited a linear relationship versus
versus temperature. When the SBS content exceeded 20 wt %, the impact strength of PPR blends
temperature. When the SBS content exceeded 20 wt %, the impact strength of PPR blends started to
started to deviate from the linear relationship with the increasing testing temperature, especially at
deviate from the linear relationship with the increasing testing temperature, especially at high testing
high testing temperatures. A dramatic rise of impact strength happened when the testing
temperatures. A dramatic rise of impact strength happened when the testing temperature exceeded
temperature exceeded 20 °C. For example, when the testing temperature was raised from 0 to 20 °C,
20 ◦ C. For example, when the testing temperature was raised from 0 to 20 ◦ C,2 the impact strength of2
the impact strength of C0B0.1S30 and C0.05B0.1S30 increased from 11.3 and 11 kJ/m to 55.9 and 58.9 kJ/m ;
C0 B0.1 S30 and C0.05 B0.1 S30 increased from 11.3 and 11 kJ/m2 to 55.9 and 58.9 kJ/m2 ; almost four-fold
almost four-fold and more than five-fold increments, respectively. However, the corresponding
and more than five-fold increments, respectively. However, the corresponding enhancements of PPR,
enhancements of PPR, C0B0.1S0 and C0.05B0S0 are only 83.32 % (from 6 to 11kJ/m2), 121 %2(from 7.1 to
C0 B0.1 S0 and C B S
0.05 0 0 are only 83.3% (from 6 to 11kJ/m ), 121% (from 7.1 to 15.7 kJ/m ) and 98.0%
15.7 kJ/m2) and 98.0 % (from 5.1 to 10.1 kJ/m2), respectively. It is also worth noting that the notched
(from 5.1 to 10.1 kJ/m2 ), respectively. It is also worth noting that the notched izod impact strengths
izod impact strengths of the ternary modifiers (MWCNTs + β-NAs + SBS)/PPR blends were inferior
of the ternary modifiers (MWCNTs + β-NAs + SBS)/PPR blends were inferior to that of the binary
to that of the binary modifiers (β-NAs + SBS)/PPR blends at low temperature (≤0 °C). Nonetheless, it
modifiers (β-NAs + SBS)/PPR blends at low temperature (≤0 ◦ C). Nonetheless, it becomes reversed at
becomes reversed at a high temperature (20 °C). At this time, the ternary modifiers/PPR blends
a high temperature (20 ◦ C). At this time, the ternary modifiers/PPR blends exhibited superior impact
exhibited superior impact strength to binary modifiers/PPR blends (without MWCNTs). Hence, some
strength to binary modifiers/PPR blends (without MWCNTs). Hence, some inherent factors related to
inherent factors related to the toughness of PPR blends need to be further investigated.
the toughness of PPR blends need to be further investigated.

Figure 2. Izod impact strength of PPR and its blend at various temperature.
Figure 2. Izod impact strength of PPR and its blend at various temperature.
3.2. Tensile Properties
3.2. Tensile Properties
The tensile properties of PPR and its blends, including stress-strain curves, tensile strength (σ),
The tensile
and tensile properties
modulus (E) areofshown
PPR and its blends,
in Figure including stress-strain
3. Compared with pure PPR, curves,
the tensile
presence strength (σ),
of β-NAs
and tensile modulus (E) are shown in Figure 3. Compared with pure PPR,
slightly deteriorated the tensile strength and modulus of PPR, from 24.1 and 501 MPa to 23.8 and the presence of β-NAs
slightly
494 MPa,deteriorated the tensile
respectively. While strength and modulus
the elongation of PPR,
at break from 24.1increased
significantly and 501 MPa by to 23.8 and
46.2%, from494316
MPa,to
respectively.
462%. It may While the elongation
be explained at break significantly
by the formation increased
of trigonal β-form by 46.2
crystal %, from
induced 316 to 462
by β-NAs, %. is
which It
may be explained by the formation of trigonal β-form crystal induced by β-NAs, which
not as dense as monoclinic α-form crystal, but more flexible than the latter [5–7]. The addition of SBS is not as dense
as monoclinic
remarkably α-form crystal,
decreased but more
the tensile strengthflexible
and than the latter
modulus of PPR [5–7]. The but
blend, addition of SBS remarkably
the elongation at break
decreased the tensile strength and modulus of PPR blend, but the elongation
increased simultaneously, thus making the PPR blend more malleable. Unlike the β-NAs, MWCNT at break increased
simultaneously,
may thus making
induce the nucleation of the
PPRPPR
andblend
formmore malleable.
relatively brittleUnlike
α-formthe β-NAs,
crystal MWCNT
[25]. Combined maywith
induce
its
the nucleation
excellent of PPR
mechanical and formthe
properties, relatively brittle α-form
tensile strength crystalof[25].
and modulus PPRCombined
were slightlywith its excellent
improved with
mechanical
the additionproperties,
of traces ofthe tensile strength
MWCNTs. and strength
The tensile modulusof ofthe
PPR were slightly
ternary improved
modifiers/PPR withwith
blend the
addition of traces of MWCNTs. The tensile strength of the ternary modifiers/PPR
30 wt % SBS contents (C0.05 B0.1 S30 ) was as high as 17.4 MPa, about 72.2% retention rate of pure PPRblend with 30 wt %
SBS contents
(24.1 (C0.05B0.1S30)an
MPa), manifesting was as high as 17.4
outstanding MPa, aboutenhancing
comprehensive 72.2 % retention rate
effect of theofternary
pure PPR (24.1 MPa),
modifiers.
manifesting an outstanding comprehensive enhancing effect of the ternary modifiers.
Polymers 2019, 11, 29 7 of 16
Polymers 2019, 11 FOR PEER REVIEW 7

Figure3.3.Stress-strain
Figure Stress-strain curves (a,b), tensile
tensile strength
strength (c)
(c)and
andtensile
tensilemodulus
modulus(d)
(d)ofofPPR
PPRand
anditsitsblends.
blends.

3.3. Melting
3.3. Melting and
and Crystallization
Crystallization Behavior
Behavior
Since the
Since the crystallization
crystallization behavior
behavior of of PPR
PPR blends
blends have have aa major major impact
impact on on their
their mechanical
mechanical
properties, the melting and crystallization behavior of PPR and
properties, the melting and crystallization behavior of PPR and its blends were investigated, its blends were investigated, as shown as
in Figure 4. A strong peak at about 140 ◦ C in all the samples represents the melting of the monoclinic
shown in Figure 4. A strong peak at about 140 °C in all the samples represents the melting of the
α-form crystal. A small peak at about 125 ◦ C, assigned to trigonal β-form crystal, was only observed
monoclinic α-form crystal. A small peak at about 125 °C, assigned to trigonal β-form crystal, was only
observed in the PPR blends containing β-NAs These
in the PPR blends containing β-NAs modifier. modifier. results
These suggested the β-NAsthe
results suggested canβ-NAseffectively
can
induce β-form nucleation in the presence of other fillers. More
effectively induce β-form nucleation in the presence of other fillers. More remarkably, the melting remarkably, the melting peaks of both
α-formofand
peaks both β-form
α-form crystal
and shifted
β-form to lowershifted
crystal temperaturesto lower with the increasing
temperatures withSBSthe contents
increasing (markedSBS
by the dotted line in Figure 4a,b). This may be explained by the
contents (marked by the dotted line in Figure 4a,b). This may be explained by the restriction of restriction of crystallization behavior
of PPR with the
crystallization existence
behavior of SBS
of PPR with particles,
the existence which ofweakens
SBS particles,the crystallization
which weakens ofthe
both α-form and
crystallization
β-form crystals. Such structural changes were also observed
of both α-form and β-form crystals. Such structural changes were also observed from from the crystallization curves of PPR
the
blends (Figure 4c,d). Compared with PPR (T = 99.2 ◦ C), C B S blend exhibits higher crystallization
c 0 0.1
crystallization curves of PPR blends (Figure 4c,d). Compared with PPR (Tc = 99.2 °C), C0B0.1S0 blend 0
temperature (100.9 ◦ C), indicating the enhanced crystallization effect of β-NAs on the β-form crystal
exhibits higher crystallization temperature (100.9 °C), indicating the enhanced crystallization effect
of PPR. The same conclusion is also obtained fromconclusion
the comparison ◦ C) and
of β-NAs on the β-form crystal of PPR. The same is alsobetween
obtainedCfrom 0.05 B0 S 0 (99.7
the comparison
C0.05 B0.1 SC00.05
(104.7 ◦ C). However,
between B0S0 (99.7 °C) and Cwith the addition of SBS elastomer, the crystallization temperature of
0.05B0.1S0 (104.7 °C). However, with the addition of SBS elastomer, the

crystallization temperature of the PPRSBS

the PPR blends decreases. The more blendselastomer
decreases. contents,
The more the lower crystallization
SBS elastomer contents, temperature
the lower
crystallization temperature of PPR blends. Detailed crystallization parameters are shown in Table of
of PPR blends. Detailed crystallization parameters are shown in Table 2. The total crystallinity 2.
PPRtotal
The increased from 0.19
crystallinity to 0.24
of PPR in thefrom
increased presence
0.19 toof0.24 in thewhich
β-NAs, presence is attributed
of β-NAs, to the formation
which is attributed of
about
to 10% β-form
the formation of crystal,
about 10% whereas
β-form thecrystal,
total crystallinity
whereas theoftotal the PPR decreased
crystallinity withPPR
of the thedecreased
increased
SBS contents.
with the increased Interestingly,
SBS contents. the Interestingly,
crystallinity of the β-form hardlyofchanged
crystallinity whereas
β-form hardly the crystallinity
changed whereas the of
α-form obviously decreased from 0.21 to 0.16 as the SBS content
crystallinity of α-form obviously decreased from 0.21 to 0.16 as the SBS content 0increased increased from 0 (C B S
0.1 0 ) to 30
from %
wt 0
(C 0 B0.1 S3 0 ). This further suggests that the formation of β-form crystal
(C0B0.1S0) to 30 wt % (C0B0.1S30). This further suggests that the formation of β-form crystal is greatly is greatly affected by the β-NAs,
and is scarcely
affected by the influenced
β-NAs, andbyis SBS elastomer.
scarcely influencedOn the by contrary,
SBS elastomer. the α-formOn the crystals
contrary,exhibit theaα-form
strong
dependence on the contents of SBS elastomer. Furthermore,
crystals exhibit a strong dependence on the contents of SBS elastomer. Furthermore, higher 0.05 higher α-form crystallinity of C B 0 S0
α-form
(0.21) compared
crystallinity of Cwith PPR (0.19) and C0 Bwith
0.05B0S0 (0.21) compared 0.1 S0 (0.16)
PPR (0.19)indicateandthat C0Bthe trace amount of MWCNTs are
0.1S0 (0.16) indicate that the trace
beneficial to the production of α-form crystals. However,
amount of MWCNTs are beneficial to the production of α-form crystals. However, both the crystallinity of PPR and both Xβ
the the
in ternary modifiers/PPR blends decrease with the increasing
crystallinity of PPR and the Xβ in ternary modifiers/PPR blends decrease with the increasing SBS SBS content, while the influence of
MWCNTs
content, on α-form
while crystallinity
the influence of MWCNTs is negligible,
on α-form especially at a high
crystallinity SBS loading
is negligible, (as shown
especially at ainhigh
Table SBS2).
It suggests that the trace amount of MWCNTs rarely affects the
loading (as shown in Table 2). It suggests that the trace amount of MWCNTs rarely affects the formation of α-form crystal but inhibits
the formation
formation of the β-form
of α-form crystal
crystal but withthe
inhibits theformation
presence of ofSBS, especially
the β-form at high
crystal withSBSthecontents.
presenceEven of SBS,so,
especially at high SBS contents. Even so, the ternary modifiers/ PPR blends still exhibit higher and
higher impact strength with the increasing SBS content. It is seen here the presence of β-form crystal
Polymers 2019, 11, 29 8 of 16

the ternary
Polymers 2019, modifiers/
11 FOR PEER PPR
REVIEWblends still exhibit higher and higher impact strength with the increasing8
SBS content. It is seen here the presence of β-form crystal enhances the toughness of the PPR blends,
enhances
but is not the
thetoughness
determinedof factor.
the PPRTaking
blends,anbut is not the
example, determined
lower contentfactor. Taking
of β-form an example,
crystal in C0.05 Blower
0.1 S30
content of β-form crystal in C 0.05B0.1S30 still exhibit higher impact strength compared with C0B0.1S30.
still exhibit higher impact strength compared with C0 B0.1 S30 .

Figure 4.
Figure The melting
4. The melting (a,b)
(a,b) and
and crystallization
crystallization (c,d)
(c,d) curves
curves of
of PPR
PPR and
and its
its blends.
blends.

Table 2. Crystallization parameters of the PPR and its blends from DSC results.
Table 2. Crystallization parameters of the PPR and its blends from DSC results.
α-form β-form
Samples T c /◦ C α-form β-form Total X c
Samples Tc/ C
o
T m /◦ C Xα T m /◦ C Xβ Total Xc
Tm/°C Xα Tm/°C Xβ
PPR PPR 99.2 99.2141.1 141.1 0.19
0.19 0.19 0.19
C0 B0.1 S0 100.9 140.6 0.15 125.5 0.09 0.24
C0B0.1S0 C B 100.9 140.6 140.2 0.15 125.5 0.10 0.09 0.31 0.24
0 0.1 S10 100.3 0.21 124.2
C0B0.1S10 C0 B0.1 100.3
S20 98.9140.2 139.2 0.21
0.18 124.2
123.0 0.11 0.10 0.29 0.31
C0B0.1S20 C0 B0.198.9 S30 98.6139.2 138.5 0.18
0.16 123.0 0.10 0.11 0.26
122.0 0.29
C0B0.1S30 C B S
0.05 98.6
0 0 99.7138.5 141.1 0.21
0.16 122.0 0.10 0.21 0.26
C0.05 B0.1 S0 104.7 140.0 0.18 125.5 0.12 0.30
C0.05B0S0 99.7 141.1 0.21 0.21
C0.05 B0.1 S10 101.7 139.2 0.17 124.1 0.08 0.25
C0.05B0.1S0 C0.05 B104.7
0.1 S20 99.1140.0 138.5 0.18
0.17 125.5 0.07 0.12 0.24
122.5 0.30
C0.05B0.1S10 C0.05 B101.7S
0.1 30 98.1139.2 138.2 0.17
0.16 124.1
121.1 0.06 0.08 0.22 0.25
C0.05B0.1S20 Note: 99.1 138.5 0.17 122.5 0.07
Tc : crystallization temperature; Tm : melting temperature; Xc: crystallinity. 0.24
C0.05B0.1S30 98.1 138.2 0.16 121.1 0.06 0.22
To furtherNote:
explore the crystal structure
Tc: crystallization and composition
temperature; of PPR blends,
Tm: melting temperature; 2D-WAXD measurement
Xc: crystallinity.
was adopted here. The 2D-WAXD patterns are shown in Figure 5. The overall crystallinity (Xc ), relative
To further explore the crystal structure and composition of PPR blends, 2D-WAXD
measurement was adopted here. The 2D-WAXD patterns are shown in Figure 5. The overall
crystallinity (Xc), relative amount of the β-form crystal (Kβ) and β-crystallinity (Xβ) can be calculated
from 1D-WAXD (as shown in Figure S4 (Supporting Information)). The Kβ is obtained from equation
(4) Tuner-Jones et al. [28]:
Polymers 2019, 11, 29 9 of 16

amount of the β-form crystal (Kβ ) and β-crystallinity (Xβ ) can be calculated from 1D-WAXD (as shown
in Figure S4 (Supporting Information)). The Kβ is obtained from Equation (4) Tuner-Jones et al. [28]:
Polymers 2019, 11 FOR PEER REVIEW 9
Aβ (110)
Kβ = (4)
Aβ (110) + Aα (110) + Aα (040) + Aα (130)
Aβ (110)
Kβ = (4)
where Aβ (110) represents the Aβ (110)
area + Aα β(110)
of the (110) + reflection
Aα (040) + Apeak;
α (130) α
A (110), Aα (040), and Aα (130)
represent the area of the α (110), α (040), and α (130) reflection peaks, respectively. Meanwhile,
where
the Aβ (110)ofrepresents
crystallinity the area
β-form crystal (Xβof thegiven
) was β(110)byreflection
Equationpeak;
(5): Aα (110), Aα (040), and Aα (130)
represent the area of the α (110), α (040), and α (130) reflection peaks, respectively. Meanwhile, the
crystallinity of β-form crystal (Xβ) was givenXby equation (5):
β = K β Xc (5)
Xβ=KβXc (5)
The corresponding data of Kβ and Xβ are shown in Table 3. The crystallinity of the PPR increased
Thefrom
slightly corresponding
0.35 to 0.36data
(C0of KβSand
B0.1 Xβ are shown in Table 3. The crystallinity of the PPR increased
0 ) in the presence of β-NAs. While the total crystallinity of the
slightly from 0.35 to 0.36 (C 0B0.1S0) in the presence of β-NAs. While the total crystallinity of the PPR
PPR decreased with the SBS contents increasing. Only 0.28 crystallinity was obtained for the PPR
decreased
blend with with
30 wtthe
% SBS
SBS contents
contentsincreasing.
(C0 B0.1 S30 ),Only 0.28crystallinity
but the crystallinity of
was obtained
β-form for thefrom
increased PPR 0.05
blendto
with 30 wt % SBS contents (C 0B0.1S30), but the crystallinity of β-form increased from 0.05 to 0.09. With
0.09. With the addition of MWCNTs, the total crystallinity of PPR and the Xβ of C0.05 B0.1 S0 decreased
the additionfrom
respectively of MWCNTs, the total
0.35 and 0.09 crystallinity
to 0.26 and 0.05 atof30
PPR
wtand the loading.
% SBS Xβ of C0.05The
B0.1Sresults
0 decreased respectively
are in consistence
from 0.35 and 0.09 to 0.26 and 0.05 at 30 wt % SBS loading. The results are in
with the DSC data. In addition, the β-form crystal was only formed in the blends containing the consistence with the
β-NAs.
DSC data. In addition, the β-form crystal was only formed in
This confirmed that β-NAs effectively induce PPR to form β-form crystal. the blends containing the β-NAs. This
confirmed that β-NAs effectively induce PPR to form β-form crystal.

Figure 5. 2D-WAXD patterns of the PPR and its blends (Color bar represents Diffraction Intensity).
Figure 5. 2D-WAXD patterns of the PPR and its blends (Color bar represents Diffraction Intensity).
Table 3. The crystallization data of PPR and its blends calculated from the WAXD.

Table 3. The crystallization data of PPRXand its blends

Samples K calculated
X from the WAXD.
c β β

Samples PPR Xc 0.35 – Kβ – Xβ

PPR C0 B0.1 S0.35
0 0.36 0.12 -- 0.05 --
C0 B0.1 S10 0.31 0.24 0.08
C0B0.1S0 0.36 0.12 0.05
C0 B0.1 S20 0.29 0.28 0.08
C0B0.1S10 C0 B0.1 S300.31 0.28 0.24
0.31 0.09 0.08
C0B0.1S20 C0.05 B0 S00.29 0.33 – 0.28 — 0.08
C0B0.1S30 C B S
0.05 0.1 0.28
0 0.35 0.26
0.31 0.09 0.09
C0.05B0S0 C0.05 B0.1 S0.33
10 0.31 0.26 -- 0.08 ---
C0.05 B0.1 S20 0.30 0.26 0.08
C0.05B0.1S0 0.35 0.26 0.09
C0.05 B0.1 S30 0.26 0.17 0.05
C0.05B0.1S10 0.31 0.26 0.08
C0.05B0.1S20 0.30 0.26 0.08
Furthermore, the
C0.05 B0.1crystal
S30 lamellar parameters
0.26 were obtained
0.17 from the 2D-SAXS
0.05 measurements
(as shown in Figure 6). The 1D-SAXS curves integrated from 2D-SAXS are shown in Figure S5
Furthermore, the crystal lamellar parameters were obtained from the 2D-SAXS measurements
(as shown in Figure 6). The 1D-SAXS curves integrated from 2D-SAXS are shown in Figure S5
(Supporting Information). Detailed information including the long period (LB), the thickness of
crystalline lamella (Lc) and the thickness of the confined amorphous phase (La) are listed in Table 4.
As a result of the loose lamellar structures of β-crystals, all the β-nucleated PPR samples show higher
Polymers 2019, 11, 29 10 of 16

(Supporting Information). Detailed information including the long period (LB ), the thickness of
crystalline lamella (Lc ) and the thickness of the confined amorphous phase (La ) are listed in Table 4.
Polymers 2019, 11 FOR PEER REVIEW 10
As a result of the loose lamellar structures of β-crystals, all the β-nucleated PPR samples show higher
LB than the non-nucleated ones. The increase in SBS also increased La , verifying the immersion
LB than the non-nucleated ones. The increase in SBS also increased La, verifying the immersion of SBS
of SBS molecular chains into PP lamellae. The presence of MWCNTs in the β-nucleated PPR/SBS
molecular chains into PP lamellae. The presence of MWCNTs in the β-nucleated PPR/SBS blends
blends further weakened the lamellar regularity, as evidenced by the further enlarged La . This is
further weakened the lamellar regularity, as evidenced by the further enlarged La. This is also
also consistent with the decreased crystallinity in the β-nucleated PPR/SBS blends with MWCNTs,
consistent with the decreased crystallinity in the β-nucleated PPR/SBS blends with MWCNTs, as
as shown
shown in in Tables
Tables 2 and
2–3. This3. behavior
This behavior is favorable
is favorable due todue
thetotoughness
the toughness of PPR/SBS
of PPR/SBS blendsblends and
and the
the enhanced mobility space of molecular chains
enhanced mobility space of molecular chains of PPR. of PPR.

Figure 6. 2D-SAXS patterns of the PPR and its blends (Color bar represents Scattering Intensity).
Figure 6. 2D-SAXS patterns of the PPR and its blends (Color bar represents Scattering Intensity).
Table 4. The parameters of lamellar structures of PPR and its blends.
Table 4. The parameters of lamellar structures of PPR and its blends.
Samples S (1/nm) LB (nm) Lc (nm) La (nm)
Samples S (1/nm)
PPR LB (nm)
0.0802 12.5 Lc (nm)
4.4 8.1 La (nm)
C0 B0.1 S0 0.0788 12.7 4.6 8.1
PPR C0 B0.10.0802
S10 0.0774 12.5 12.9 4.4
4.0 8.9 8.1
C0 B0.1 S20 0.0732 13.7 4.0 9.7
C0B0.1S0 C0 B0.10.0788
S30 0.0710 12.7 14.1 4.6
3.9 10.2 8.1
C0.05 B0 S0 0.0798 12.5 4.1 8.4
C0B0.1S10 0.0774
C0.05 B0.1 S0 0.0785
12.9 12.7
4.0
4.4 8.3
8.9
C0.05 B0.1 S10 0.0769 13.0 4.0 9.0
C0B0.1S20 0.0732 13.7 4.0 9.7
C0.05 B0.1 S20 0.0703 14.2 4.3 9.9
C0B0.1S30 C0.05 B0.1 S30
0.0710 0.0700 14.1 14.3 3.7
3.9 10.6 10.2

C0.05B0S0 0.0798 12.5 4.1 8.4

3.4. Phase Morphology
C0.05B0.1S0 0.0785 12.7 4.4 8.3
In order to investigate the toughening mechanism of modifiers on the PPR matrix, SEM images of
PPR and its C blends were
0.05B0.1S 10 obtained,
0.0769as shown in Figure
13.0 7. Plastic 4.0
deformation in a small
9.0 area is observed
in the pure PPR, displaying a typical brittle fracture. The comparatively rough fractured surface
of C0 B0.1 S0 C 0.05B0.1S20
reveals 0.0703
that the ductile 14.2
fracture occurs 4.3
in the β-NAs/PPR 9.9
blend due to the formation
of β-form crystal induced
C0.05B0.1S30 by β-NAs.
0.0700 Similar to pure
14.3 PPR, brittle
3.7 fracture happens
10.6 in the C0.05 B0 S0
blend, indicating that the addition of MWCNTs does not improve the toughness of the PPR. When the
SBS elastomer
3.4. Phase particles were added, a mass of half-bare SBS elastomer particles and the subsidence
Morphology
holes existed in the C0 B0.1 S30 and C0.05 B0.1 S30 blends besides the irregular fracture surface. The crack
In order
deflection andtothe investigate
pullout ofthethe
toughening
elastomermechanism of modifiers
particles occur on thewhich
upon impact, PPR matrix, SEM images
are favorable for the
of PPR and its blends were
dissipation of the impact energy. obtained, as shown in Figure 7. Plastic deformation in a small area is
observed in the pure PPR, displaying a typical brittle fracture. The comparatively rough fractured
surface of C0B0.1S0 reveals that the ductile fracture occurs in the β-NAs/PPR blend due to the formation
of β-form crystal induced by β-NAs. Similar to pure PPR, brittle fracture happens in the C0.05B0S0
blend, indicating that the addition of MWCNTs does not improve the toughness of the PPR. When
the SBS elastomer particles were added, a mass of half-bare SBS elastomer particles and the
subsidence holes existed in the C0B0.1S30 and C0.05B0.1S30 blends besides the irregular fracture surface.
 Polymers 2019, 11 FOR PEER REVIEW 11

The crack deflection and the pullout of the elastomer particles occur upon impact, which are favorable
Polymers 11, 29
2019,dissipation
for the of the impact energy. 11 of 16

Figure 7. The impact fractured surface of the PPR and its blends (at 20 ◦ C).
Figure 7. The impact fractured surface of the PPR and its blends (at 20 °C).
The SEM images of the fracture surface of PPR blends etched by tetrahydrofuran are shown in
The SEM images of the fracture surface of PPR blends etched by tetrahydrofuran are shown in
Figure 8a,b. Small and oval SBS particles appear in the PPR blend with high SBS contents, which may
Figure 8a,b. Small and oval SBS particles appear in the PPR blend with high SBS contents, which may
be caused by high shear stress during the mixing process as a result of the increased viscosity of matrix.
be caused by high shear stress during the mixing process as a result of the increased viscosity of
Figure 8c,d showed that the average size of the SBS particles is as small as about 0.3–0.5 µm in both
matrix. Figure 8c,d showed that the average size of the SBS particles is as small as about 0.3–0.5 μm
C0 B0.1 S30 and C0.05 B0.1 S30 . Compared with that of C0 B0.1 S30 , the SBS particles are more uniformly
in both C0B0.1S30 and C0.05B0.1S30. Compared with that of C0B0.1S30, the SBS particles are more uniformly
distributed in C0.05 B0.1 S30 . The addition of trace amounts of MWCNTs contributed to the dispersion
distributed in C0.05B0.1S30. The addition of trace amounts of MWCNTs contributed to the dispersion of
of SBS particles in PPR matrix. Small and uniform SBS elastomer particles are conductive to the
SBS particles in PPR matrix. Small and uniform SBS elastomer particles are conductive to the
homogeneity of matrix and thus results in increased toughness [29]. Smaller rubber particles in the
homogeneity of matrix and thus results in increased toughness [29]. Smaller rubber particles in the
PPR matrix are tougher and more ductile than those with larger particles, because the rubbery phase
PPR matrix are tougher and more ductile than those with larger particles, because the rubbery phase
with smaller size is more efficient in promoting crazing and/or shear yielding [30–32]. From the
with smaller size is more efficient in promoting crazing and/or shear yielding [30–32]. From the
enlarged SEM and TEM images of C0.05 B0.1 S30 in Figure 8e,f, well-dispersed MWCNTs are mainly
enlarged SEM and TEM images of C0.05B0.1S30 in Figure 8e,f, well-dispersed MWCNTs are mainly
distributed in the interface between SBS particles and PPR matrix. Although most portion of the
distributed in the interface between SBS particles and PPR matrix. Although most portion of the
MWCNTs embed in the interior of the SBS particle, one end of it is tightly inserted into the PPR
MWCNTs embed in the interior of the SBS particle, one end of it is tightly inserted into the PPR
matrix. The interfacial interaction between SBS particles and PPR matrix is enhanced obviously
matrix. The interfacial interaction between SBS particles and PPR matrix is enhanced obviously with
with the aid of MWCNTs-bridging connection. The connection probability between SBS particles
the aid of MWCNTs-bridging connection. The connection probability between SBS particles therefore
therefore increased due to the increment of the effective interaction radius of MWCNTs/SBS particles.
increased due to the increment of the effective interaction radius of MWCNTs/SBS particles. In
In addition, such interface interaction helps dispersion of SBS particles in PPR matrix.
addition, such interface interaction helps dispersion of SBS particles in PPR matrix.
Polymers 2019, 11, 29 12 of 16
Polymers 2019, 11 FOR PEER REVIEW 12

Figure 8. SEM micrographs of of PPR blends with 30 wt % SBS after etched bytetrahydrofuran (a,b);
Figure
SBS size8.distribution
SEM micrographs of Sof PPR
of C0 B0.1 blends with 30 wt % SBS after etched bytetrahydrofuran (a,b);
30 (c) and C0.05 B0.1 S30 (d); enlarged SEM (e) and TEM (f) image of
CSBS size distribution of C0B0.1S30 (c) and C0.05B0.1S30 (d); enlarged SEM (e) and TEM (f) image of
0.05 B0.1 S30 .
C0.05B0.1S30.
3.5. Glass Transition Temperatures
3.5. Glass Transition
To further Temperatures
investigate the toughening mechanism of PPR blends, the DMA measurement was
conducted. The storage
To further modulus
investigate curves versus
the toughening temperature
mechanism canblends,
of PPR be found
theinDMA
Figure S6 (Supporting
measurement was
Information). The tanδ of PPR and its blends are shown in Figure 9. For pure PPR,
conducted. The storage modulus curves versus temperature can be found in Figure S6 (Supporting two distinct peaks
can be observed. One peak at about ◦ C, corresponding to β-relaxation of PP phase, is related to the
15 blends
Information). The tanδ of PPR and its are shown in Figure 9. For pure PPR, two distinct peaks
glass transition
can be observed. temperature
One peak at (Tabout
g ) of the15 unconstrained
°C, correspondingPPRto amorphous phase,
β-relaxation of PPwhile
phase,theisother peak
related at
to the
about 75 ◦ C represents the α-relaxation of the PPR phase, which is related to the T of rigid amorphous
glass transition temperature (Tg) of the unconstrained PPR amorphous phase, gwhile the other peak
region between
at about 75 °CPPR lamellae.
represents theIt α-relaxation
is clear that with thePPR
of the increase of SBS
phase, whichparticles, the β-relaxation
is related to the Tg of peakrigid
of PPR downshifts to a low temperature, along with the obviously enhanced intensity
amorphous region between PPR lamellae. It is clear that with the increase of SBS particles, the β- of this peak,
relaxation peak of PPR downshifts to a low temperature, along with the obviously enhanced intensity
of this peak, whether the PPR blends contain binary or ternary modifiers. Some SBS molecules
Polymers 2019, 11,
Polymers 2019, 29 PEER REVIEW
11 FOR 13 of 16
13

penetrate into the PPR matrix and form large amorphous regions, resulting in the increased motion
whether the PPR blends contain binary or ternary modifiers. Some SBS molecules penetrate into the
of PPR molecules and thus the improved toughness of PPR matrix. In addition, a closer inspection
PPR matrix and form large amorphous regions, resulting in the increased motion of PPR molecules and
revealed the β-relaxation peak of ternary modifiers/PPR blends moved to a lower temperature
thus the improved toughness of PPR matrix. In addition, a closer inspection revealed the β-relaxation
compared with the binary modifiers/PPR counterparts. This should be ascribed to the presence of
peak of ternary modifiers/PPR blends moved to a lower temperature compared with the binary
MWCNTs.
modifiers/PPR counterparts. This should be ascribed to the presence of MWCNTs.

Figure 9. The loss factor (tanδ) of the PPR and its blends as a function of temperature.
Figure 9. The loss factor (tanδ) of the PPR and its blends as a function of temperature.
3.6. Toughening Mechanism
3.6. Toughening Mechanism
On the basis of the analysis above, the β-NAs can induce more ductile β-form crystals to increase
On the basis
the toughness of of
thethePPRanalysis
matrix.above,Thethe β-NAsβ-form
ductile can induce more
crystal ductileand
blunted β-form crystals to
diminished theincrease
stress
the toughness of the PPR matrix. The ductile β-form crystal blunted
intensity at a propagating crack tip. Therefore the main crack growth was restrained in the original and diminished the stress
intensity at a propagating crack tip. Therefore the main crack growth
direction and will propagate in a scattered way when encountering the β-form crystal (as shown in was restrained in the original
direction
Figure and
10a). Thewill propagatemechanism
toughening in a scattered way when
of elastomer onencountering the β-form
plastics is usually crystal
attributed to the(as formation
shown in
Figure 10a). The toughening mechanism of elastomer on plastics is usually
of matrix shear zone and crazing, plastic deformation, crack deflection, and particle pullout [31,33,34]. attributed to the formation
of matrix
For the PPRshear zone and
blends crazing,SBS
containing plastic deformation,
elastomer systems, crack deflection,
plastic and particle
deformation occurs pullout
at the[31,33,34].
crack tip
For the PPR blends containing SBS elastomer systems, plastic deformation
when the initiative microcrack encounters the SBS elastomer particles, and thus causes dis-bonding occurs at the crack tip
when the initiative microcrack encounters the SBS elastomer particles,
between SBS particles and PPR matrix. Therefore, some SBS elastomer particles are pulled out from and thus causes dis-bonding
between
the matrixSBS particles
under impact and loadPPR matrix.
(Figure 7) Therefore,
and the crack some canSBSbe elastomer
deviated from particles are pulled
the original out from
propagation
the matrix under impact load (Figure 7) and the crack can be deviated
path. This results in greater impact energy consumed and improved toughness of PPR (as shown in from the original propagation
path. This
Figure 10b).results in greater
The addition ofimpact
MWCNTs energy
alone consumed
can onlyand improved
increase toughness
the strength of PPR
of PPR, and(as mayshown in
be not
Figurefor
good 10b).
the The additionThis
toughness. of MWCNTs
is mainly alone can only
attributed to the increase the strength
α-nucleation effect of
of PPR,
MWCNTs and may and be not
stress
good for the toughness. This is mainly attributed to the α-nucleation
concentration derived from the existence of MWCNTs. However, the MWCNTs, acting as bridges, effect of MWCNTs and stress
concentration
can effectively derived
connect the from the existence
isolated of MWCNTs.
SBS elastomer particlesHowever,
and transferthe the
MWCNTs,
stress amongacting SBSas particles.
bridges,
Combining the positive impact of MWCNTs on the dispersion of SBS particles, large amountsSBS
can effectively connect the isolated SBS elastomer particles and transfer the stress among of
particles. Combining
homo-dispersed the positive
SBS particles impact
will work of MWCNTs
together to withstand on the
the impact
dispersion
loads.ofTherefore,
SBS particles, large
an obvious
amounts oftoughening
synergistic homo-dispersed effect isSBS particles
found in the will
ternary work together
hybrid to withstand
systems. the impact
The synergistic loads.
toughening
mechanism is shown in Figure 10c. At low SBS contents, only a few SBS particles can be connectedThe
Therefore, an obvious synergistic toughening effect is found in the ternary hybrid systems. by
synergisticdue
MWCNTs toughening
to the large mechanism
distance withinis shown them. inTheFigure
number 10c. ofAtthe
low SBS contents,SBS
interconnected only a few gets
particles SBS
particles can
increased withbethe connected
increasingby SBSMWCNTs due to the
content, resulting in large distance within
more absorption of thethem.
impactThe number
energy. of the
Therefore,
interconnected SBS particles gets increased with the increasing
the ternary modifiers (MWCNTs + β-NAs + SBS) with high SBS contents in the PPR matrix exhibit SBS content, resulting in more
absorption
better of the impact
toughening efficiencyenergy.
than Therefore,
those withthe lowternary modifiers
SBS contents. In(MWCNTs
addition, since+ β-NAs + SBS) with
the β-relaxation
of PPR occurs at about 15 C, the relatively obvious toughening enhancement of PPR blendslow
high SBS contents in the PPR
◦ matrix exhibit better toughening efficiency than those with SBS
is only
contents. In addition, since
observed at high temperatures (>15 C). the β-relaxation
◦ of PPR occurs at about 15 °C, the relatively obvious
toughening enhancement of PPR blends is only observed at high temperatures (>15 °C).
Polymers 2019, 11 FOR PEER REVIEW 14
Polymers 2019, 11, 29 14 of 16

Figure 10. Schematic diagram of toughening mechanism of PPR blends (a) β-NAs/PPR; (b) SBS/PPR;
(c) ternary (MWCNTs + β-NAs + SBS)/PPR.
Figure 10. Schematic diagram of toughening mechanism of PPR blends (a) β-NAs/PPR; (b) SBS/PPR;
4. Conclusions
(c) ternary (MWCNTs + β-NAs + SBS)/PPR.

The notched izod impact of PPR slightly improved with the addition of β-NAs due to the
4. Conclusion
formation of ductile β-form crystals. Although the toughness of the PPR was significantly enhanced
The notched
by combining β-NAs izod impact
with of PPR slightly
SBS elastomer, improved
the tensile strengthwith the addition
is seriously of β-NAs
deteriorated in the due to the
presence
formation
of of ductile
SBS elastomer, β-form crystals.
especially Although
at the high the toughness
filler content. Relyingof the
on PPR was significantly
the bridge connectionenhanced
effect of
by combining
the MWCNTs β-NAsin the with SBSmodifiers/PPR
ternary elastomer, the tensile strength
((MWCNTs + is seriously
β-NAs deteriorated
+ SBS)/PPR) in theobviously
blend, presence
of SBS elastomer,
synergistically especially
reinforced at the higheffect
toughening filler was
content. Relying The
presented. on the bridgeizod
notched connection
impact effect of the
strength of
MWCNTs
ternary in the ternary
modifiers/PPR modifiers/PPR
blend with 30 wt % ((MWCNTs
SBS increased + β-NAs + SBS)/PPR)
from 11.3 to 58.9 kJ/m 2 ; more
blend, obviously
than
synergistically
five-fold reinforced
increment toughening
compared effect
with pure PPR was presented.
matrix, while Thethe notched izod impact
tensile strength strength
retention of
is still
ternary72.2%.
above modifiers/PPR
Moreover,blend with 30 wt efficiency
the toughening % SBS increased
is morefrom 11.3at
obvious tohigh
58.9 temperature
kJ/m ; more than
2 ◦
(>15five-fold
C) due
increment
to compared
the β-relaxation of with pure PPR
PP occurring atmatrix,
about 15 ◦ C. These
while the tensile strength
findings retention
provide is still above
a significant guidance 72.2%.
for
Moreover, the toughening efficiency is more obvious at high
fabricating high toughness PPR simultaneously with favorable tensile strength.temperature (>15 °C) due to the β-
relaxation of PP occurring at about 15 °C. These findings provide a significant guidance for
Supplementary
fabricating high Materials:
toughness ThePPR
following are availablewith
simultaneously online at http://www.mdpi.com/2073-4360/11/1/29/s1,
favorable tensile strength.
Figure S1: GPC informations of PPR used in this study, Figure S2: SEM (a) and TEM (b and c) images of TNM5,
Figure S3: Izod impact strength of PPR and its blend at various temperature (a) 20 ◦ C, (b) 0 ◦ C, (c) −10 ◦ C,
(d) −20 ◦ C, Figure
Supplementary Materials:
S4: 1D-WAXDThe following
of PPR andare
its available onlineS5:at1D-SAXS
blends, Figure www.mdpi.com/xxx/s1, FigureFigure
of PPR and its blends, S1: GPCS6:
The storage modulus
informations of PPR
of PPR used in and its blends.
this study, Figure S2: SEM (a) and TEM (b and c) images of TNM5, Figure S3: Izod
impact strength
Author of PPR P.-G.R.
Contributions: and its and
blend at various
Y.-H.C. temperature
conceptualized (a)whole
the 20 °C,work.
(b) 0 °C,
J.W.(c)
and−10Q.F.
°C, designed
(d) −20 °C, Figure
and S4:
carried
1D-WAXD of PPR and its blends, Figure S5: 1D-SAXS of PPR and its blends, Figure S6: The storage modulus
out the experiments. S.Y. and Z.-Q.W. provided measurement. P.-G.R. and D.-X.Y. wrote this paper. J.W. and Q.F. of
analyzed theblends.
PPR and its experimental data and plotted them. All authors reviewed and approved the manuscript.
Funding: This research P.G.
Author Contributions: was Ren
funded
and by National
Y.H. Natural Science
Chen conceptualized theFoundation
whole work.of J.China
Wang(Grant
and Q.No.
Fan51573147,
designed
51773167, 51473135; 51503170 and 21676217) and the Natural Science Foundation of Shaanxi
and carried out the experiments. S. Yang and Z.Q. Wu provided measurement. P.G. Ren and D.X. Yan wroteProvince, China
this
(Grant No. 2017JQ5065).
paper. J. Wang and Q. Fan analyzed the experimental data and plotted them. All authors reviewed and approved
Acknowledgments:
the manuscript. We would like to thank the Analytical & Testing Center of Northwestern Polytechnical
University for TEM measurement. We also would like to express sincere thanks to the Shanghai Synchrotron
Radiation
Funding: Facility (SSRF,
Please add: Shanghai,
This researchChina), for theby
was funded kind help onNatural
National 2D-WAXD andFoundation
Science 2D-SAXS measurements.
of China (Grant No.
51573147, 51773167, 51473135; 51503170 and 21676217) and the Natural
Conflicts of Interest: The authors declare no conflicts of interest. Science Foundation of Shaanxi Province,
China (Grant No. 2017JQ5065).
Polymers 2019, 11, 29 15 of 16

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