Received: 14 November 2020 Revised: 29 December 2020 Accepted: 7 January 2021

DOI: 10.1002/pat.5227

RESEARCH ARTICLE

Well dispersion of poly(acrylonitrile-butadiene-styrene) in

isotactic polypropylene mediated by incorporation of graphene
and the elevated toughness

Jingru Liu | Lingchen Zhang | Zhou Fang

Jiangsu Key Laboratory of Environmentally

Friendly Polymeric Materials, School of Polymers with benzene rings in structures including polystyrene (PS) and
Materials Science and Engineering, Jiangsu
poly(acrylonitrile-butadiene-styrene) (ABS) could function as rigid organic particles
Collaborative Innovation Center of
Photovoltaic Science and Engineering, and macromolecular β nucleating agents to toughen isotactic polypropylene (iPP),
Changzhou University, Changzhou, China
and the toughening effect mainly depends on their dispersibility in iPP matrix. In this
Correspondence work, a third component of graphene (G) was introduced into the iPP/PS and
Jingru Liu, Jiangsu Key Laboratory of
iPP/ABS blends, respectively, to mediate the dispersibility of these polymers in the
Environmentally Friendly Polymeric Materials,
School of Materials Science and Engineering, iPP via melt blending. Selective dispersion of graphene in these immiscible blends has
Jiangsu Collaborative Innovation Center of
been investigated with SEM, DSC, and a rheometer. It was interesting to obtain a
Photovoltaic Science and Engineering,
Changzhou University, Changzhou 213164, more favorable dispersion of ABS in the iPP/ABS/G blend compared with the
China.
iPP/ABS blend, and the corresponding toughness showed a prominent improvement
Email: [email protected]
accompanied with an elevation in rigidity. The underlying mechanism for the
Funding information
improved dispersion of ABS in the iPP/ABS/G blends has been discussed in detail.
Priority Academic Program Development of
Jiangsu Higher Education Institutions, Grant/ However, because of a better affinity of the graphene to the PS than the iPP matrix,
Award Number: PAPD
graphene could only locate in the PS phase, resulting in poor compatibilization for
the iPP/PS blend followed by the deterioration of mechanical properties.

KEYWORDS
dispersibility, graphene, isotactic polypropylene (iPP), poly(acrylonitrile-butadiene-styrene)
(ABS), polystyrene (PS), toughness

1 | I N T RO DU CT I O N realization of toughening iPP via melt blending with these polymers

with benzene rings comes from two contributions. For one thing, the
Toughening of isotactic polypropylene (iPP) has always been an incorporation of rigid organic particles brings about the change of
important research direction in the field of polymer materials.1,2 The local stress state, which provides the condition for the shear yield of
main methods include adding rubber or elastomers, β nucleating the iPP matrix through debonding and cavitation. For another, these
agents, and rigid particles. However, the introduction of elastomers polymers also have an impact on the crystallization behavior of iPP.
with low modulus and strength will reduce the rigidity of iPP.3 The Especially, a certain amount of β crystals could be induced during qui-
“soften” characteristic of β-iPP also brings about an obvious decline in escent melt crystallization. Su et al believed that the benzene rings in
rigidity and strength resulting from the incompact packing pattern of these polymers may serve as a crystal growth surface, inducing the
β-crystal.4-7 Toughening iPP with rigid organic particles could effec- helix chains of iPP to orient and epitaxially crystalize on it.13,14
8
tively solve this problem. Recently, we utilized a small amount of For polymeric β nucleating agents, the β nucleation efficiency
polystyrene (PS)9 or poly(acrylonitrile-butadiene-styrene) (ABS)10-12 mainly depends on their dispersibility in iPP matrix, and the toughen-
(mass fraction less than 4%) to melt blend with iPP, and found that ing effect of rigid organic particles is also closely related to their dis-
the toughness of the blends was improved remarkably in contrast to persibility.15-18 It should be emphasized that the stronger the
that of the iPP matrix, accompanied with an elevation in rigidity. The interfacial interaction between two phases, the better the

2020 © 2021 John Wiley & Sons Ltd wileyonlinelibrary.com/journal/pat Polym Adv Technol. 2021;32:2020–2029.
LIU ET AL. 2021

dispersibility of the dispersed phase.19-21 In addition, the interfacial 5 μm, and an average thickness of 8 to 12 nm. Polystyrene (PS),
interaction also has a strong influence on the reinforcing effect of tradename PG-383, with melt flow index of 2.2 g (10 min)−1 (200
C,
rigid particles on iPP. Since both PS and ABS are immiscible with iPP, 5 kg), was purchased from Chimei Industrial Co. Ltd (Zhenjiang,
it is difficult to achieve uniform dispersion in iPP matrix. Therefore, China). Its weight-average molecular weight is 4.5 × 105 g mol−1 and
enhancing the interfacial interaction between two phases is a key fac- the polydispersity index is 2.48. Poly(acrylonitrile-butadiene-styrene)
tor for toughening iPP with these polymers containing benzene rings, (ABS), trademarked as PA-707K, with melt flow index of 2.1 g
without deterioration of strength and rigidity. (10 min)−1 (200
C, 5 kg), was purchased from Chimei Industrial
In order to enhance the interfacial interaction between two Co. Ltd (Taiwan, China). The weight-average molecular weight of
phases of polymer blend, the most common and effective method is styrene-acrylonitrile resin (SAN) is 1.56 × 105 g mol−1 and the poly-
to introduce block or graft copolymers as a compatibilizer. A consider- dispersity index is 1.92.
able amount of work has shown that these compatibilizers can signifi-
cantly improve the toughness of the blends. Unfortunately, they also
bring about the deterioration of tensile strength and modulus due to 2.2 | Sample preparation
their relatively low molecular weight.22-28 In recent years, some func-
tional inorganic nanofillers, including clay and silica nanoparticles, The weight ratio between iPP and ABS (or PS) is set to 96:4 in this
have also been developed for regulating phase morphology and com- work. The graphene loading varies from 0.1% to 0.7% by weight. For
patibilizing immiscible blends.29-35 On the one hand, inorganic convenience, binary and ternary blends were abbreviated as iPP/PS,
nanoparticles can adsorb polymer chains to achieve compatibilization iPP/ABS, iPP/xG, iPP/PS/xG, iPP/ABS/xG, respectively, where
owing to their large specific surface area. On the other hand, immisci- x indicates the mass fraction of graphene. The preparation of the
ble polymer chains could be intercalated into some inorganic fillers blends was conducted using a torque rheometer (XSS-300, Shanghai
with layered structure simultaneously, and hence the phase separation Kechuang Xiangsu Machinery Equipment Co. Ltd, China) with a set-
is limited, resulting in reduction in the size of the dispersed phase ting temperature of 180
C. The rotor speed was 60 rpm and the melt
followed by realization of compatibilization. It should be mentioned blending time was 7 minutes. For comparison, pure iPP also under-
that nanofillers may be selectively distributed in the dispersed phases, went the same procedure. The obtained blends were pulverized with
matrix or interface, depending on their characteristics. a small high-speed pulverizer, and then the blend powders were injec-
Graphene, a new kind of functional nanofiller with two- tion molded in a miniature injection molding instrument (HAAKE
dimensional lamellar structure, has attracted considerable attention MiniJet II, Thermo Fisher) to produce the dumbbell-shaped tensile
owing to its excellent comprehensive performance.36-44 The research specimens (ISO 527-2-5A) and the impact specimens with “V”
on graphene-filled polymer nanocomposites has always been a hot notches (ISO 180/179). The melting temperature was 185
C, the
spot in materials field.45-49 To the best of our knowledge, the majority mold temperature was 40
C, the holding pressure was 0.6 MPa, and
of studies have focused on polymer/graphene nanocomposites with the holding time was 10 seconds.
high performances. Only a few reports are available on the com-
patibilizing role of graphene in immiscible blends.50,51 In this paper,
graphene was selected to mediate the dispersion state of the PS and 2.3 | Characterization
ABS in the iPP matrix via melt blending. For one thing, the six-
membered ring structure of graphene has self-similarity with the iPP 2.3.1 | Mechanical properties measurements
macromolecular chains. For another, there is π–π interaction between
the six-membered rings in graphene and the phenyl groups in PS and The tensile strength and elongation at break, as well as flexural modu-
ABS. The aim of this work was to investigate the compatibilizing role lus, were conducted on a universal testing machine (CMT-6503, MTS
of graphene in these immiscible blends, and further elevate the tough- Industrial Systems Co. Ltd, China) according to ISO 527 and
ening effect of polymers containing benzene rings on iPP. 178, respectively. The Izod notched impact strength measurements
were carried out using an impact tester (XJUD-5.5, Chengde Jinhe
Instrument Manufacturing Co. Ltd, China) according to ISO 180.
2 | EXPERIMENTAL

2.1 | Materials 2.3.2 | Differential scanning calorimetry

Isotactic polypropylene (iPP), trademarked as T30S, was supplied by The crystallization and melting behaviors were investigated using a
China Petrochemical Corporation (Beijing, China) with melt flow index differential scanning calorimeter (Q20, TA Instruments) under nitro-
of 3.2 g (10 min)−1 (230
C, 2.16 kg). Its weight-average molecular gen atmosphere. A sample of about 8 mg was first heated to 210
C
−1
weight is 2.4 × 10 g mol
5
and the polydispersity index is 4.06. and maintained for 5 minutes to eliminate previous thermal and
Graphene (G) was a product of Nanjing JCNANO Technology Co. Ltd mechanical history. Then the sample was cooled to 100
C at a rate of
(Nanjing, China), with purity higher than 95%, and a diameter of 2 to 10
C min−1 to avoid β-to-α recrystallization.10 Finally, it was reheated
2022 LIU ET AL.

to 210
C at the same scanning rate. The first cooling and second be ascribed to the dual roles of rigid organic particles and macromo-
heating scans were recorded. lecular β nucleating agent of PS and ABS.9-13
A careful examination reveals that the elevation on mechanical
properties of ABS toward iPP is lower than that of PS toward iPP. For
2.3.3 | Scanning electron microscopy example, the impact strength of iPP/PS and iPP/ABS blends are
7.2 kJ m−2 and 6.5 kJ m−2, respectively, as presented in Figure 1D.
The tensile and impact fractured surfaces were observed using a field This may be attributed to the more favorable dispersibility of PS in
emission scanning electron microscope (JSM 6700, JEOL, Japan) at an the iPP matrix, which is beneficial to the elevation of β nucleation effi-
accelerating voltage of 5 kV. Prior to characterization, all the speci- ciency and toughening effect. Interestingly, when incorporating a
mens were gold-sputtered on the fractured surface. The diameter of small amount (0.1–0.7 wt%) of graphene, the mechanical properties of
PS or ABS dispersed phase was calculated using the method described iPP/PS/G blends decreased, while those of the iPP/ABS/G blends
in our previous work.9 were greatly improved, especially the fracture toughness. With the
increase in graphene loading, the mechanical properties of iPP/ABS/G
blends first elevate and then fall off. In particular, the elongation at
2.3.4 | Steady rheological properties break and impact strength of the iPP/ABS/0.3G blend reach 948%
and 8.3 kJ m−2, 541% and 152% higher than those of pure iPP,
The steady rheological properties were investigated with a rotary rhe- respectively. On further increasing the graphene loading, aggregation
ometer (RS6000, Thermo Electron) using a parallel plate (diameter of of graphene may result in increased size of the dispersed phase,
25 mm) under dry nitrogen atmosphere. The gap was fixed at 1 mm. followed by a decrease in mechanical properties. The iPP/ABS/G
The shear rate from 0.0398 to 100 s−1 was performed at 210
C. blends showed obvious cold-drawn phenomenon during the
stretching process. Since cold-drawn is related to the orientation and
slippage of macromolecular chains in amorphous regions and lamellae
3 | RESULTS AND DISCUSSION in crystal regions, which is the characteristic of quasi-tough materials,
the appearance of cold-drawn reveals that the introduction of
3.1 | Mechanical properties graphene could promote the brittle-ductile transition of the iPP/ABS
blend.
The results of the mechanical properties of pure iPP and the blends In order to further understand the fracture behavior of the
are shown in Figure 1. It could be seen that the mechanical properties iPP/ABS blends under tensile stress before and after adding graphene,
of iPP with the addition of 4% PS or ABS were significantly improved the tensile fracture surface was characterized by using SEM, as shown
in contrast to those of pure iPP, especially the toughness. This should in Figure 2. It could be found from Figure 2A that the particles of ABS

(A) (B)
45 1500
iPP/PS/G iPP/PS/G
iPP/ABS/G iPP/ABS/G
Flexural modulus (MPa)
Tensile Strength (MPa)

40
1200

35

900
30

25 600
iPP 0G 0.1G 0.3G 0.5G 0.7G iPP 0G 0.1G 0.3G 0.5G 0.7G
(C) (D)
1200 9
iPP/PS/G iPP/PS/G
Izod notched impact strength ( kJ m )
-2

iPP/ABS/G iPP/ABS/G
Elongation at break (%)

900 7

600 5

F I G U R E 1 Mechanical properties
300 3
of pure iPP and the blends. A, Tensile
strength, B, flexural modulus, C,
0 1 elongation at break, D, impact
iPP 0G 0.1G 0.3G 0.5G 0.7G iPP 0G 0.1G 0.3G 0.5G 0.7G strength
LIU ET AL. 2023

F I G U R E 2 SEM micrographs
of the tensile fractured surfaces of
iPP/ABS, A, and iPP/ABS/0.3G, B,
blends

F I G U R E 3 DSC curves of pure iPP and (A) (B)

the blends on the first cooling, A, and the iPP/ABS/0.7G iPP/ABS/0.7G
second heating scan, B iPP/ABS/0.5G iPP/ABS/0.5G
iPP/ABS/0.3G iPP/ABS/0.3G
iPP/ABS/0.1G
iPP/ABS β iPP/ABS/0.1G
iPP/PS/0.7G iPP/ABS
iPP/PS/0.5G iPP/PS/0.7G
iPP/PS/0.3G iPP/PS/0.5G

Endo
Endo

iPP/PS/0.1G iPP/PS/0.3G
iPP/0.7G iPP/PS/0.1G
iPP/0.5G iPP/0.7G
iPP/0.3G iPP/0.5G
iPP/0.1G iPP/0.3G
iPP/PS β iPP/0.1G
iPP iPP/PS
iPP

100 115 130 145 160 130 145 160 175 190
Temperature (°C) Temperature (°C)

dispersed phase in the iPP/ABS blend detach from the iPP matrix, addition of PS, ABS, or graphene increases the Tc value of iPP, and the
indicating poor interfacial interaction between the two components. iPP/G composites show the highest elevation. This result suggests
However, the ternary blend with the addition of graphene demon- that PS, ABS, and graphene all have a good heterogeneous nucleation
strates a completely different fracture morphology from the binary effect on iPP crystallization. When incorporating PS and graphene
one. The iPP/ABS/0.3G blend was selected, and its tensile fracture simultaneously into iPP, the Tc values of obtained ternary blends are
surface is presented in Figure 2B. An obvious layered fibrillation struc- between those of iPP/G and iPP/PS blends, implying that the
ture with severe plastic deformation could be observed. ABS particles graphene in the iPP/PS/G blends is not all distributed in the iPP
with complete shape could no longer be found on the fracture sur- matrix. It could be speculated that the PS component makes graphene
face. This result suggests that the introduction of graphene is benefi- nanosheets selectively disperse, thereby inhibiting the nucleation
cial to enhance the interfacial adhesion between the iPP and ABS, due effect of graphene on the iPP matrix. Interestingly, the Tc value fur-
to the fact that only when the interfacial interaction is high enough ther rises with the addition of ABS and graphene simultaneously. If
can the externally applied stress be transferred from the iPP matrix to graphene is selectively distributed in the ABS dispersed phase, it could
the ABS dispersed phase, followed by the deformation and break-up not perform the function of heterogeneous nucleation. Therefore, we
of ABS particles. can deduce that the graphene in the iPP/ABS/G blends may be dis-
tributed in the iPP matrix or the two-phase interface.
As presented in Figure 3B, iPP shows a single melting peak at
3.2 | Crystallization and melting behavior 163.4
C to α-crystal. However, a new melting peak emerges at 150
C
for both iPP/PS and iPP/ABS blends, indicating that a small amount of
The crystallization and melting behaviors of pure iPP and the blends PS or ABS can induce iPP to form β-crystals. When graphene is added
were further characterized, as demonstrated in Figure 3. Figure 4 into the binary blends, the β-crystal melting peak disappears, implying
exhibits the variations of crystallization temperature Tc for the iPP/G, that the graphene inhibits the β nucleation ability of PS and ABS on
iPP/PS/G, and iPP/ABS/G blends with respect to the graphene con- iPP. For the iPP/PS/G blends, it could be speculated that graphene is
tent. For pure iPP, the crystallization temperature is 111.9
C. The selectively distributed in the PS dispersed phase, resulting in
2024 LIU ET AL.

could be decreased to 2.5 μm with the addition of 0.1% graphene.

123 Incorporating 0.3% graphene brings about a remarkable decrease in
Crystallization Temperature Tc (°C)

the ABS domain size to 0.8 μm. According to the principle that the
smaller the dispersed phase particles, the better the toughness of the
120 blend,53 and the decrease in the size of ABS dispersed phase in the
iPP/ABS/G blend is beneficial to the elevation of toughness, as
proved by the mechanical properties measurements. A careful exami-
117
nation reveals that some ABS particles in the iPP/ABS/G blends are
iPP/G elliptical or elongated. It is well known that, the higher the interfacial
114 interaction of the blend, the easier it is for the dispersed phase to
iPP/PS/G
deform into elongated shape instead of smaller droplets during melt
iPP/ABS/G
blending.54 The SEM observations clearly demonstrate the favorable
111 compatibilization effect of graphene on the iPP/ABS blend. Some
0 0.1 0.3 0.5 0.7
recent studies in the literature also demonstrated the improved dis-
Graphene content (%)
persion of nucleating agents in iPP by using graphene.55,56 The ABS

F I G U R E 4 Variations of crystallization temperature Tc for the dispersed phase of iPP/ABS/0.3G blend is the smallest and the distri-
iPP/G, iPP/PS/G, and iPP/ABS/G blends with respect to the graphene bution is more uniform. On further increasing the graphene loading,
content aggregation of graphene results in increased size of the dispersed
phase again, indicating that the compatibilization effect of graphene is
also related to its concentration. In addition, some tiny cavities could
unfavorable dispersibility of the PS dispersed phase followed by sig- be observed from the impact fractured surfaces. This can be attrib-
nificantly reduced β nucleation efficiency. In the case of the uted to the interfacial debonding of ABS particles from the iPP matrix
iPP/ABS/G blends, if graphene is distributed in the iPP matrix, the β when the blends were subjected to impact force. The formation of
nucleation efficiency of ABS will not be affected. Therefore, it could cavitation can absorb energy, which is thought to be one of the
be inferred that the graphene is located at the interface between the toughening mechanisms of rigid organic particle toughened iPP mate-
ABS and iPP phases. Due to strong α nucleation effect, graphene will rials. With the addition of graphene, the fractured surfaces of
induce iPP to crystallize under higher crystallization temperature, iPP/ABS/G blends become coarser, implying more plastic deformation
which is higher than the peak crystallization temperature of iPP/ABS occurred during the fracture.
blends, leading to inhibition of β crystals induced by ABS, which can In order to further investigate the compatibilizing mechanism of
be observed from the DSC crystallization curves of iPP blends.52 graphene in the iPP/ABS/G blends, the tensile fractured surface of
iPP/ABS/0.3G blend after etching was observed by SEM, as pres-
ented in Figure 6. The tensile fractured surface was etched in dic-
3.3 | Phase morphology and selective distribution hloromethane in order to remove ABS phase from the iPP matrix. It
of graphene can be seen that the graphene nanosheet still adheres to the phase
interface after etching. When the iPP/ABS/G blend is subjected to
In general, the addition of nanofillers may give rise to morphology tensile force, the graphene at the interface slips during the stress pro-
changes as well as variation of domain size of the dispersed phase. cess, which could absorb plenty of energy. Even if the crack propa-
Figure 5 shows the SEM micrographs of impact fractured surfaces of gates along the two-phase interface, graphene could pull both ends of
iPP/PS and iPP/ABS blends with different graphene contents. A sea- the crack to prevent crack propagation owing to its ultra-high
island morphology could be observed for all the blends, indicating that strength, followed by improved mechanical properties of the blends.
neither PS or ABS is miscible with iPP. In the blends without
graphene, the spherical PS or ABS is dispersed in the iPP matrix. The
particle size of the PS dispersed phase in the iPP/PS blend is smaller 3.4 | Steady rheological behavior
than that of the ABS dispersed phase in the iPP/ABS blend.
With the addition of a small amount of graphene, the size of the Steady rheological behavior could further reveal the dispersion of the
dispersed phase of the iPP/PS/G blend is larger than that of the graphene in different systems, and the corresponding results are pres-
iPP/PS blend, as presented in Figures 5A0-A4. This phenomenon indi- ented in Figure 7. Figure 7A demonstrates the apparent viscosity (ηa)
cates that the graphene tends to be dispersed in the PS phase. Conse- as a function of shear rate obtained for the iPP/G composites. It can
quently, it could not improve the compatibility of the iPP/PS blend. be seen that the composites demonstrated lower ηa values in contrast
Graphene has a strong effect on the domain size of ABS dis- to pure iPP, and the ηa value of the composites first falls off and then
persed phase, as demonstrated in Figures 5B0-B4. The SEM micro- increases with respect to graphene content. This is in agreement with
graph of the blank iPP/ABS blend shows that the average diameter of earlier works by Li et al.57 They believed that the incorporation of
ABS dispersed phase is 3.0 μm. The diameter of the ABS domains graphene brought about the decrease in viscosity of iPP due to the
LIU ET AL. 2025

F I G U R E 5 SEM micrographs of the

impact fractured surfaces of iPP/PS and
iPP/ABS blends with different graphene
contents. A, iPP/PS, A1, iPP/PS/0.1G, A2,
iPP/PS/0.3G, A3, iPP/PS/0.5G, A4,
iPP/PS/0.7G, B, iPP/ABS, B1,
iPP/ABS/0.1G, B2, iPP/ABS/0.3G, B3,
iPP/ABS/0.5G, B4, iPP/ABS/0.7G

interlayer slipperiness resulting from low friction between graphene The results of steady rheological properties of iPP/ABS/G ternary
nanosheets. With a further rise in the content, aggregation of blends are displayed in Figure 7B. If the graphene is distributed in the
graphene results in increasing steric hindrance of iPP chains, followed iPP matrix, the apparent viscosity of the blends should decrease
by the elevation of apparent viscosity. accordingly. However, it is found that, in contrast to pure iPP and the
2026 LIU ET AL.

apparent viscosity of the matrix, thereby increasing the apparent vis-

cosity of the ternary blends. It should be emphasized that the increase

Graphene in viscosity will bring about the rise in shear force during the blending
process, which makes the ABS dispersed phase particles more likely
to deform. This conclusion is consistent with the SEM test results.
A comparison between Figure 7B,C shows that the iPP/PS/G blends
exhibit relatively lower apparent viscosity compared with the iPP/ABS/G
samples. This difference could be attributed to the different dispersion
of graphene in the ternary blends. In the iPP/ABS/G blends, graphenes
are located at the interface, which induces the increase in the viscosity
of the blends apparently. However, in the case of the iPP/PS/G blends,
graphene nanosheets are selectively dispersed in the PS phase due to
the relatively stronger interaction between PS and graphene. As a result,
the addition of graphene has no effect on the rheological properties of
F I G U R E 6 SEM micrograph of tensile fractured surface of
iPP/ABS/0.3G blend after etching the iPP matrix, and consequently, the effect of graphene on ηa of the
iPP/PS/G ternary blends is inconspicuous.

3.5 | Underlying mechanism of improved

dispersion of ABS in iPP matrix mediated by
incorporation of graphene

The selective distribution of graphene in different systems can be

quantitatively analyzed from the perspective of thermodynamics by
calculating the wetting coefficient (ωa)58:

γ G −B −γ G− A
ωa = ð1Þ
γ A− B

where γ G-B, γ G-A, and γ A-B represent the interfacial tension between
graphene and dispersed phase B (PS or ABS), graphene and continu-
ous phase A, and dispersed phase B and continuous phase A, respec-
tively. When ωa > 1, graphene will preferentially distribute in the
continuous phase iPP; when ωa < −1, graphene will preferentially dis-
tribute in the dispersed phase; when −1 < ωa < 1, graphene will dis-
tribute at the two-phase interface.
The interfacial tension to be used in Equation (1) can be calcu-
lated using the surface tension of the components. Two calculation
methods, harmonic-mean equation and geometric-mean equation,59
could be used, as shown in Equations (2) and (3), respectively.
Harmonic-mean equation is valid for the systems with low sur-
face energy:

!
γ d1 γ d2 γp γp
γ 1−2 = γ 1 + γ 2 − 4 + p 1 2p ð2Þ
γ1 + γ2 γ1 + γ2
d d

and geometric-mean equation has no special requirements for the sur-

F I G U R E 7 Apparent viscosity ηa as a function of shear rate obtained
for the iPP/G, A, iPP/ABS/G, B, and iPP/PS/G, C, blends, as well as the face energy:
comparison of ηa values of the blends at a shear rate of 0.1 s−1
qffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffi
γ 1− 2 = γ 1 + γ 2 −2 γ d1 γ d2 + γ p1 γ p2 ð3Þ
iPP/ABS blend, the iPP/ABS/G blends have higher apparent viscosity
when the graphene content is lower than 0.5%. This phenomenon where γ i represents the surface tension of component i, and γ id and γ ip
could also be explained by the selective dispersion of graphene. The denote the dispersive and polar parts of the surface tension of com-
graphene located at the interface could significantly increase the ponent i, respectively.
LIU ET AL. 2027

T A B L E 1 Surface tension data of the

Components γ (mN m−1) γ d (mN m−1) γ p (mN m−1) Reference
components cited in this work
iPP 19.3 19.3 0 Ghadami et al60
PS 37.6 37.3 0.3 Zakiyan et al61
ABS 34.0 30.7 3.2 Wu59
G 40.8 40.5 0.3 Mohamadi et al62

T A B L E 2 Interfacial tensions as
Samples iPP-PS iPP-ABS G-iPP G-PS G-ABS
calculated using harmonic-mean and
−1
geometric-mean equations Based on harmonic-mean equation (mN m ) 6.02 5.90 7.82 0.13 3.85
Based on geometric-mean equation (mN m−1) 3.24 4.62 4.18 0.07 2.32

Based on the above experimental and theoretic calculation

results, a schematic diagram for the selective dispersion of
graphene in the iPP/ABS/G blends was drawn, as exhibited in
Figure 8. The graphene nanosheets could absorb some ABS chains
on their basal planes through π-π interactions. Meanwhile, there is
a hydrophobic interaction between the conjugated structure of
graphene and the long alkane chains of iPP, which is similar to π-π
stacking interaction.63 As a result, graphene nanosheets tend to
locate at the interface between the ABS and iPP phase, enhancing
the interfacial interaction and improving their compatibility. Com-
pared with the iPP/ABS binary blend, the ternary blend shows a
remarkable elevation of mechanical properties, especially the
toughness.
In the case of iPP/PS/G blends, graphene could only locate in the
PS phase, resulting in increasing size of the PS dispersed phase.
Graphene has little effect on the reduction in interfacial tensions,
leading to poor compatibilization for the iPP/PS blend followed by the
deterioration of mechanical properties.

F I G U R E 8 Schematic diagram of the selective dispersion of 4 | CONC LU SIONS

graphene in the iPP/ABS/G blends
Polymers with benzene rings in structures including polystyrene
(PS) and poly(acrylonitrile-butadiene-styrene) (ABS) have the potential
The values of surface tension of the components used in this to act as macromolecular β-nucleating agents and rigid organic parti-
work are listed in Table 1. The interfacial tension between the two cles for isotactic polypropylene (iPP), and their dispersibility in iPP
components could be calculated by substituting the data in Table 1 matrix plays an important role in the toughening effect. In this work, a
into Equations (2) and (3), and the results are summarized in Table 2. third component of graphene was introduced into the iPP/PS and
As a consequence, for the iPP/PS/G blends, ωa is −1.28 based on iPP/ABS blends, respectively, and its selective dispersion in these
harmonic-mean equation and −1.27 based on geometric-mean equa- blends was investigated with SEM, DSC, and a rheometer. Graphene
tion. For the iPP/ABS/G blends, ωa is 0.67 based on harmonic-mean nanosheets tend to locate at the interface between the ABS and iPP
equation and 0.40 based on geometric-mean equation. These results phases, enhancing the interfacial interaction and improving their com-
suggest that graphene should selectively distribute in PS phase for the patibility. Compared with the iPP/ABS binary blend, the ternary blend
iPP/PS/G blends and at the interface between the ABS and iPP showed a remarkable elevation of mechanical properties, especially
phases for the iPP/ABS/G blends. Although graphene shows good the toughness. However, because of a better affinity of the graphene
affinity for polymers with benzene rings, however, in this work, PS to the PS than the iPP matrix, graphene could only locate in the PS
has more potential to interact with graphene in contrast to ABS. This phase, resulting in poor compatibilization for the iPP/PS blend
can be proved by the state of the minimum interfacial tension of the followed by the deterioration of mechanical properties. This work
iPP/PS/G blends when the equilibrium state is reached, as demon- may open up a new prospect for graphene to be applied as a novel
strated in the above theoretic calculations. compatibilizer.
2028 LIU ET AL.

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