Influence of a core/shell rubber phase on the morphology and the impact resistance of a PC/SAN blend (75/25)

At 75/25 concentration ratio, bisphenol a polycarbonate (PC)/styreneacry-lonitrile copolymer (SAN) blend has poor impact resistance compared to PC/ABS. A rubber phase methacrylate-butadiene-styrene (MBS) of core/shell type was dispersed in PC/SAN blend. The morphology of the unmodified and modified blend was investigated. The influence of the acrylonitrile ratio in the SAN on the microstructure was studied. It clearly shows that core/shell resides at the interface between PC and SAN. It seems that core/shell particles enhance the adhesion between the different phases. Their presence influences the interface mobility; i.e., the coalescence of the dispersed phase observed in pure PC/SAN is considerably reduced when the MBS particles are added. The impact resistance of the samples was correlated with the morphology.     

MBS粒子尺寸对PVC／MBS共混物性能及形变机理的影响

通过乳液聚合方法制备了两种不同粒径（分别为270nm和80nm）的甲基丙烯酸甲酯/丁二烯/苯乙烯（MBS）核壳改性剂，与聚氯乙烯（PVC）进行熔融共混，得到了PVC／MBS共混物。对PVC／MBS共混物力学、光学等方面的性能及其形变机理分别进行了考察。结果表明：PVC／MBS共混物的脆-韧转变温度（BDT）和拉伸性能均随着MBS粉料粒径的增加而增加；但是光学测试则表明MBS粒子对改善PVC基体的光学性能的效果却随MBS粉料粒径的增加而降低；透射电镜（TEM）的分析表明大粒径的MBS粉料能促使橡胶粒子产生空洞化，而由小粒径的MBS粉料制备的PVC／MBS共混物没有观察到橡胶粒子空洞化的产生。     

Synergistic effect of dual rubber system in toughening styrene maleic anhydride copolymers

Styrene maleic anhydride (SMA) copolymers were toughened by blending with two distinctly different rubber modifiers: styrene‐butadiene‐styrene (SBS) block copolymer and methacrylated butadiene‐styrene emulsion‐made graft copolymer (MBS). The modifiers were used both individually and in combination for the examination of their roles in toughening SMA. SMA was miscible with poly(methylmethacrylate) shell of MBS, whereas it was partially miscible with the polystyrene (PS) phase of SBS. When 40–50% of SBS was used in blends, the PS phase of SBS became immiscible with SMA. SBS did not improve the Izod impact strength of SMA appreciably. A prominent synergistic toughening effect was experimentally observed when SBS and MBS were used in combination in brittle SMA. This effect may be attributed to the fact that the large SBS particles initiate crazes and small MBS particles with good adhesion to SMA matrix improve the ligament thickness, which may play a critical role in craze growth and termination. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2260–2267, 2003     

Enthalpic effects on interfacial adhesion of immiscible polymers compatibilized with block copolymers

The influence of enthalpic interactions on interfacial adhesion between immiscible polymer matrices and reinforcing block copolymer segments has been studied using the transmission electron microscopic (TEM) methodology of Creton et al. We examined the behaviour of four statistical styrene-acrylonitrile (SAN) copolymers, each having different acrylonitrile (AN) content, blended with polystyrene (PS) as the minor component, and reinforced by three poly(methyl methacrylate-b-styrene) (PMMA-b-PS) block copolymers of differing molar masses, viz. 20000, 65000 and 680000 g mol⁻¹. These observations were compared with similar experiments on poly(methyl methacrylate) (PMMA) blended with PS and reinforced by PMMA-b-PS. Emulsification was observed with all three PMMA-b-PS copolymers. Crazes were formed in the SAN matrices and a statistical evaluation of interfacial failures was performed on the discrete PS domains that lay within the crazes. For the two block copolymers of higher molar mass, optimal reinforcement of the interfaces was observed independent of the SAN composition. With the 20000 block copolymer, however, the pattern of the interfacial failure depended strongly on the SAN composition. Specifically, it was observed that the fraction of the discrete particles that suffered interfacial failure, and led to the creation of large voids in the crazes in these blends, increased with increased AN content of the SAN matrix. Thus, we found that the fraction of discrete PS particles that produce large voids in crazes of blends containing SAN33 is always higher than in blends containing SAN15, when reinforced with the 20000 PMMA-b-PS. We infer that the critical molar mass required of a mechanically reinforcing copolymer depends on the short-range (attractive and repulsive) interactions between the blend components in the interfacial region. The TEM method could not, however, distinguish between reinforced and neat PMMA/PS blends, all of which showed strong adhesion. This is attributed to the comparatively diffuse interface in the PMMA/PS system, a consequence of the relatively weak repulsion between these two polymers.     

The Influence of the compatibilizer Characteristics on the interfacial characteristics and phase morphology of aPA/SAN blends

The main objective of this work is study the influence of the methyl mathacrylate maleic anhydride copolymer (MMA-MA) compatibilizer properties such as molecular weight and maleic anhydride content in the characteristics of amorphous polyamide and styrene acrylonitrile copolymer (aPA/SAN) blends, correlating their interfacial characteristics and phase morphology. The blends aPA/SAN, with and without the compatibilizer, prepared were characterized by transmission electron microscopy (TEM) and small angle X-rays scattering (SAXS). The results show that the maleic anhydride concentration has a more significant effect on the blend properties than the molecular weight of the MMA-MA copolymer. Even though the system aPA/SAN is thermodynamically immiscible, it shows morphology of phases with small particles of SAN. The addition of MMA-MA copolymer with high degrees of MA led to an increase of the SAN phase particle size. With SAXS technique, it was possible to determine the interface thickness and the results shows that the characteristics of the interface do not change with the variation of the compatibilizer characteristics. The results observed in this work indicate that the viscosity ratio is very important factor on the formation of the phase morphology.     

A morphological study on the dispersion and selective localization behavior of graphene nanoplatelets in immiscible polymer blends of PC and SAN

In this morphological study the dispersion and localization behavior of 1 wt.% graphene nanoplatelets (GnPs) in melt mixed co-continuous polymer blends of polycarbonate (PC, 59 wt.%) and poly(styrene-acrylonitrile) (SAN, 40 wt.%) were investigated. Through varying the mixing sequence as well as the melt mixing parameters, different states of dispersion and different filler localizations were achieved. Melt mixing in a one-step process resulted in the poorest dispersion of the GnPs in the polymer blend. In this case, the filler could hardly be found localized selectively in one of the polymer components but formed its own component. In two-step mixing processes the GnPs were either premixed in PC or SAN to investigate the assumed filler transfer from the SAN into the PC component. Four different premixtures were prepared which showed that longer mixing time and higher rotation speed resulted in better dispersion of the GnPs in the polymer matrix. If the GnPs were predispersed in PC they could still be found in the PC component after blending with SAN. In the case that the GnPs were premixed in SAN, the filler was detected partially in the SAN or at the blend interface, as well as smaller sized particles were found in the PC component. It could be shown that the size and aspect ratio of the filler play a significant role on the localization of GnPs in melt mixed polymer blends.     

Compatibilisation of heterogeneous acrylonitrile-butadiene rubber/polystyrene blends by the addition of styrene-acrylonitrile copolymer: effect on morphology and mechanical properties

Compatibility of polystyrene (PS) and acrylonitrile-butadiene rubber (NBR) blend is poor, hence technological compatibilisation was sought by the addition of styrene-acrylonitrile copolymer (SAN). The interfacial activity of SAN was studied as a function of compatibiliser concentration by following the morphology of three different blend series, viz. PS/NBR 30/70, 50/50 and 70/30. Incorporation of SAN into PS/NBR blends improved tensile, tear, hardness and impact properties. Addition of SAN beyond the saturation level (critical micelle concentration) adversely affected the ultimate properties. Attempts were made to understand the conformation of the compatibiliser at the interface. The protocol of mixing was varied, and, its effect on the mechanical properties was investigated. The experimental results were compared with the theoretical predictions of Noolandi and Hong.     

Kinetics-controlled compatibilization of immiscible polypropylene/polystyrene blends using nano-SiO2 particles

Rigid inorganic filler has been long time used as a reinforcement agent for polymer materials. Recently, more work is focused on the possibility that using filler as a compatibilizer for immiscible polymer blends. In this article, we reported our efforts on the change of phase morphology and properties of immiscible polypropylene(PP)/polystyrene(PS) blends compatibilized with nano-SiO₂ particles. The effects of filler content and mixing time on the phase morphology, crystallization behavior, rheology, and mechanical properties were investigated by SEM, DSC, ARES and mechanical test. A drastic reduction of PS phase size and a very homogeneous size distribution were observed by introducing nano-SiO₂ particles in the blends at short mixing time. However, at longer mixing time an increase of PS size was seen again, indicating a kinetics-controlled compatibilization. This conclusion was further supported by the unchanged glass transition temperature of PS and by increased viscosity in the blends after adding nano-SiO₂ particles. The compatibilization mechanism of nano-SiO₂ particles in PP/PS blends was proposed based on kinetics consideration.     

Elastomeric latex domain-interpenetrating polymer networks: Physical and rheological properties

The combination of rubbery and rigid polymers in a multiphase structure using staged emulsion polymerization has yielded materials with properties ranging from reinforced elastomers to high impact plastics. The many different particle morphologies that result from a two-stage latex (TSL) polymerization include core/shell, domain, interpenetrating polymer networks (IPN), and various combinations thereof. The sequence of polymerization, crosslinking, grafting, and composition are among the significant parameters that determine the particle morphology. Elastomeric TSL with soft polyacrylates (PA) as the seed particles and polystyrene (PS) as the second stage, with each stage lightly crosslinked, may yield IPN-microdomain particles. The particle morphology has been elucidated through a combination of microscopy and mechanical property analyses. The significant modulus of elastomeric latex interpenetrating polymer networks (LIPN) results from reinforcement by PS intra-particle microdomains and their significant tensile strength from a strength forming mechanism of PS inter-particle microdomains. The increase in the PA seed crosslinking increases the crosslinked PS (xPS) level of molecular mixing with, and grafting via residual unsaturation to, the crosslinked PA (xPA) network and decreases particle deformnability. At higher xPS concentrations the formation of an xPS-rich shell enhances xPS continuity in the molded material through the partial coalescence of the shells, diminishing the PA continuity, and yielding more PS-like properties. The submicron lightly crosslinked latex particles with these different morphologies flow as a pseudoplastie material through a particle slippage flow mechanism exhibiting neither a Newtonian plateau nor a yield stress at low shear rates. The deformable lightly crosslinked particles with interchangeable PS ties which disintegrate at elevated temperatures retain their identity and regain their shape at the cessation of shear. The LIPN can be processed using standard thermoplastic methods and machinery, with power law constants and shear insensitive flow activation energies that are similar to those of thermoplastics at high levels of shear. Uncrosslinked PS shells around crosslinked PA seed particles, on the other hand, completely coalesce upon molding to form a continuous thermoplastic PS matrix that may essentially flow through molecular deformation.     

Effects of core‐shell particle growth manners on morphologies and properties of poly(vinyl chloride)/(methyl methacrylate–butadiene–styrene) blends

A series of methyl methacrylate‐butadiene‐styrene (MBS) core‐shell particles were synthesized by seeded emulsion polymerization. All the MBS particles are designed with the same defined chemical composition, which is a prerequisite for producing transparent blends with poly(vinyl chloride) (PVC). Three different growth manners of core‐shell particles: agglomeration of small styrene‐butadiene rubbers (SBRs) followed by styrene (ST) and methyl methacrylate (MMA) monomers grafting, agglomeration of small MBS particles and traditional MBS with single SBR rubber core, and ST/MMA shells are used. The effects of growth manners of MBS on the properties and deformation mechanism of PVC/MBS blends are studied. It is found that all the MBS particles can toughen the PVC matrix effectively, but different deformation modes are observed: cavitation in large particles, debonding at the PVC/MBS interface, rubber cavitation, and clusters of voids, respectively. In addition, it is found that the stress‐whitening extent is associated with the deformation modes. J. VINYL ADDIT. TECHNOL., 22:37–42, 2016. © 2014 Society of Plastics Engineers     

Polystyrene/melamine-formaldehyde hollow microsphere composite by self-assembling of latex particles at emulsion droplet interface

Submicron scale particle aggregates with defined shape were prepared by self-assembling of sulphonated polystyrene latex particles at the interface of emulsion droplets. Several parameters were considered during the preparation, including the sulphonation time of the polystyrene latex particles, the composition of the oil phase, and the zeta potential of the sulphonated latex particle. To further improve the mechanical stability of the particle aggregates, a hard composite layer was formed by addition of melamine-formaldehyde (MF) prepolymer into the emulsion. The prepolymer was crosslinked onto the particles surface of sulphonated PS particle aggregates. The crosslinking reaction was catalysed by the acidity of sulfogroup. After evaporating off solvent, PS/MF hollow microsphere composites were obtained as mechanically stable dry material. The hollow microsphere composite was characterized by TGA, FTIR, optical microscopy, scanning and transmission electron microscopy.     

Role of organically modified layered silicate as an active interfacial modifier in immiscible polystyrene/polypropylene blends

The role of organically modified layered silicate as a compatibilizer for immiscible polystyrene (PS) with polypropylene (PP) or polypropylene grafted with maleic anhydride (PP-g-MA) blends was investigated. Scanning electron micrographs (SEM) revealed efficient mixing of the polymers in the presence of organically modified layered silicate. X-ray diffraction (XRD) patterns and transmission electron microscopic (TEM) observations showed that silicate layers were either intercalated or exfoliated, depending on their interactions with the polymer pair, and were located at the interface between the two polymers. The compatibilizing action of the organically modified layered silicate resulted in a decrease in interfacial tension and particle size and in a remarkable increase in mechanical properties of the modified immiscible blends.     

MBS树脂的合成及表征

采用适时补皂、种子乳液聚合方法合成粒径大、分布窄的SBR胶乳。该胶乳接枝St—MMA共聚单体合成MBS树脂。研究了SBR粒径大小度其分布、MBS玻璃化转变温度以度其微观形态。实验结果表明，MBS树脂具有两个玻璃化转变温度，分别为MBS树脂的橡胶相和树脂相的玻璃化转变温度。且MBS树脂呈现规整的核壳结构。     

Effect of reduced graphene oxide functionalization by sulfanilic acid on the mechanical properties of poly(styrene‐co‐acrylonitrile)/reduced graphene oxide composites

The sulfonation of reduced graphene oxide (SRGO) by the aryl diazonium salt of sulfanilic acid was focused to examine the enhancement effect on the mechanical properties of poly styrene‐acrylonitrile (SAN). The SAN was prepared by surfactant‐free emulsion copolymerization using a cationic initiator. By mixing sulfonated RGO (SRGO) into the SAN polymer matrix, positively‐charged SAN particles were attracted to the negatively‐charged surfaces of SRGO sheets via electrostatic interactions. The storage modulus of SAN‐SRGO increased to 46% at 4 wt% SRGO loading. This improvement is attributed to strong interactions between sulfonated groups on the surface SRGO and the nitrile groups of SAN. POLYM. COMPOS., 44–50, 2016. © 2014 Society of Plastics Engineers     

Phase morphology and thermomechanical analysis of poly(styrene‐co‐acrylonitrile)/ethylene–propylene–diene monomer blends: Uncompatibilized and reactively compatibilized blends with two mixing sequences

The phase morphology developing in immiscible poly(styrene‐co‐acrylonitrile) (SAN)/ethylene–propylene–diene monomer (EPDM) blends was studied with an in situ reactively generated SAN‐g‐EPDM compatibilizer through the introduction of a suitably chosen polymer additive (maleic anhydride) and 2,5‐dimethyl‐2,5‐di‐(t‐butyl peroxy) hexane (Luperox) and dicumyl peroxide as initiators during melt blending. Special attention was paid to the experimental conditions required for changing the droplet morphology for the dispersed phase. Two different mixing sequences (simple and two‐step) were used. The product of two‐step blending was a major phase surrounded by rubber particles; these rubber particles contained the occluded matrix phase. Depending on the mixing sequence, this particular phase morphology could be forced or could occur spontaneously. The composition was stabilized by the formation of the SAN‐g‐EPDM copolymer between the elastomer and addition polymer, which was characterized with Fourier transform infrared. As for the two initiators, the blends with Luperox showed better mechanical properties. Scanning electron microscopy studies revealed good compatibility for the SAN/EPDM blends produced by two‐step blending with this initiator. Dynamic mechanical thermal analysis studies showed that the two‐step‐prepared blend with Luperox had the best compatibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Experimental determination of interface widths in binary polymer blends from free volume measurements

Interfaces in binary polymer blends play a pivotal role in moulding their physical properties. We observe a diffused interface in immiscible and partially miscible binary polymer blends for which the methods of preparation characterize the interface widths. The interface widths for three binary blends of PVC/PS, PS/PMMA, and PVC/SAN are in the maximum range of 2.15, 5.04 and 6.24 nm respectively. We establish a correlation between hydrodynamic interaction and the Flory–Huggins interaction parameter which is consistent with self-consistent mean field theory and the usual constructed density profile across the interface. Our approach is based on the hydrodynamic interaction which is derived from free volume data measured by positron lifetime spectroscopy.     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

ABS树脂的增韧研究

通过双螺杆挤出机,采用熔融共混的方法制备了本体与乳液复配,不同基体SAN的丙烯腈(AN)含量及摩尔质量的丙烯腈-丁二烯-苯乙烯(ABS)树脂。研究了不同橡胶粒径及分布,基体SAN的AN含量及摩尔质量对ABS树脂韧性的影响。研究发现:本体与乳液掺混的ABS树脂具有显著的协同增韧作用,且在同等橡胶含量时,乳液法橡胶质量分数在60%左右时,可以最大幅度地提高ABS的冲击强度。另外,SAN树脂的AN含量及其摩尔质量对ABS的韧性也有显著的影响。在一定的AN含量及摩尔质量范围内,ABS树脂的冲击强度随着AN含量和摩尔质量的增加而呈现上升趋势。     

A new insight into interface widths in binary polymer blends based on ortho‐positronium lifetime studies

The interface widths in two immiscible polymer blend (Poly vinyl chloride (PVC)/Polystyrene (PS)) and PVC/Ethylene Vinyl Acetate (EVA) are determined experimentally using hydrodynamic interaction approach through free volume measurement by positron annihilation lifetime spectroscopy. For comparison, the same study is performed in a miscible blend (Styrene Acrylonitrile (SAN)/Poly Methyl Methacrylate (PMMA)). The interfacial width (Δl) is evaluated from the hydrodynamic interaction (α) based on Kirkwood–Risemann theory and friction coefficient from Stokes equation. Friction at the interface of a binary blend evidences how close the surfaces of the polymer chains come or stay apart which in turn depends on the type of force/interaction at the interface. In this work, we define interface width from a different perspective of Flory–Huggins interaction approach. Measured composition dependent interface widths in the three blends studied clearly demonstrate the sensitivity of the present method. In miscible blend, high friction at the interface results in stronger hydrodynamic interaction and hence smaller interface widths (0.36–1.97 Å), whereas weak or no interaction in immiscible blends produce wider widths (2.81–25.0 Å). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology and mechanical properties of ABS blends prepared from emulsion‐polymerized PB‐g‐SAN impact modifier with AIBN as initiator

A series of PB‐g‐SAN impact modifiers (polybutadiene particles grafted by styrene and acrylonitrile) are synthesized by seed emulsion copolymerization initiated by oil‐soluble initiator, azobisiobutyronitrile (AIBN). The ABS blends are obtained by mixing SAN resin with PB‐g‐SAN impact modifiers. The mechanical behavior and the phase morphology of ABS blends are investigated. The graft degree (GD) and grafting efficiency (GE) are investigated, and the high GD shows that AIBN has a fine initiating ability in emulsion grafting of PB‐g‐SAN impact modifiers. The morphology of the rubber particles is observed by the transmission electron microscopy (TEM). The TEM photograph shows that the PB‐g‐SAN impact modifier initiated by AIBN is more likely to form subinclusion inside the rubber particles. The dynamic mechanical analysis on ABS blends shows that the subinclusion inside the rubber phase strongly influences the T_g, maximum tan δ, and the storage modulus of the rubber phase. The mechanical test indicates that the ABS blends, which have the small and uniform subinclusions dispersed in the rubber particles, have the maximum impact strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007