Effects of AN-contents and shear flow on the miscibility of PC/SAN blends

The miscibility of polycarbonate (PC) with styrene-co-acrylonitrile random copolymer (SAN) has been systematically investigated as functions of acrylonitrile content and shear flow. Various AN-contents ranged from 11 to 74 wt% and different simple shear flow values up to 90 s⁻¹ have been used to explore the effect of both material and proceeding parameters on the miscibility of PC and SAN blends. The finest phase dispersion of the SAN particles was observed at AN=25 wt% for PC/SAN=70/30 blends under the same processing condition using scanning electron microscope (SEM). The obtained morphologies indicated that PC and SAN could form a partial miscibility blend and the maximum miscibility occurred at AN=25 wt%. This observation was supported by considering the shifts in the glass processes of the two rich phases of the blend using the dynamical mechanical analysis (DMA) measurements. The optimum interaction of the two components at AN=25 wt% calculated from ellipsometric technique was found to be the only responsible parameter for the high miscibility of the blend. The viscoelastic properties of the pure polymer components were found to play a minor role in the obtained morphologies. The effect of simple shear flow on the morphology of PC/SAN-25=70/30 blend has been also investigated using a special shear apparatus of parallel plate geometry. It has been found that the dispersed phase of SAN was elongated and broken-up in the direction of flow with weaker contrast at high shear rates. The shear rate was found to enhance the miscibility of SAN (dispersed phase) in the PC matrix to a great extent as seen in the weak contrast of the two phases observed by transmission electron microscope (TEM).     

Changes in the interfacial properties of PC/SAN blends with compatibilizer

Block copolymers of polycarbonate‐b‐poly(methyl methacrylate) (PC‐b‐PMMA) and tetramethyl poly(carbonate)‐b‐poly(methyl methacrylate) (TMPC‐b‐PMMA) were examined as compatibilizers for blends of polycarbonate (PC) with styrene‐co‐acrylonitrile (SAN) copolymer. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) technique and an asymmetric double cantilever beam fracture test. The average diameter of dispersed particles and interfacial tension of the PC/SAN blends were reduced by adding compatibilizer to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing interfacial adhesion with compatibilizer. TMPC‐b‐PMMA copolymer was more effective than PC‐b‐PMMA copolymer as a compatibilizer for the PC/SAN blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2649–2656, 2003     

Effects of tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) copolymers containing various amounts of acrylonitrile on the interfacial properties of polycarbonate and poly(styrene‐co‐acrylonitrile) blends

Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry     

The effects of PC‐PMMA block copolymer on the compatibility and interfacial properties of PC/SAN blends

Block copolymers of polycarbonate (PC) and polymethylmethacrylate (PMMA), PCb‐PMMA, were examined as compatibilizers for blends of PC with styrene‐co‐acrylonitrile (SAN) copolymer. PC‐b‐PMMA was added to blends of PC with SAN containing various amounts of AN. The average diameter of the dispersed particles was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) test and an asymmetric double cantilever beam fracture test. The average particle size and interfacial tension of the PC/SAN blends reached a minimum value when the SAN copolymer contained about 24 wt% AN. A maximum in the adhesion energy was also observed at the same AN content. Interfacial tension and particle size were further reduced by adding PC‐b‐PMMA to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing the interfacial adhesion by the addition of PC‐b‐PMMA. The addition of PC‐b‐PMMA copolymer was more effective at improving the interfacial properties of PC/SAN blends than was varying the AN content of the SAN copolymers. The interfacial properties of the PC/SAN blends were optimized by adding a block copolymer and using an SAN copolymer that had minimum interaction energy with PC.     

Morphology and mechanical behaviors of rigid organic particles reinforced polycarbonate

For the purpose of promoting mechanical properties of bisphenol-A polycarbonate (PC) reinforced by rigid organic styrene–acrylonitrile copolymer (SAN) particles, styrene/acrylonitrile/glycidyl methacrylate terpolymer (SAG) was synthesized and applied as compatibilizer for PC/SAN blends. It is found that the phase morphology of PC/SAN/SAG blends is closely related with their mechanical properties. Large continuously distributed SAN phase or spherical dispersed SAN particles with average diameter over 2 μm tend to trigger premature tensile failure of blends due to stress concentration. The incorporation of SAG can simultaneously reinforce and toughen PC/SAN blends by controlling the size and distribution of the dispersed SAN particles. For the blends with fixed PC/SAN ratio, the elongation at break and fracture energy are markedly improved when SAN domain size is reduced by adding appropriate amount of SAG. Typically, for blends with a PC/SAN ratio of 75/25, adding 3 wt% SAG will cause the average diameter of SAN particles to reduce from 2.35 ± 1.20 to 0.74 ± 0.25 μm, meanwhile up to 95% increment in elongation at break and 115% increment in fracture energy is achieved.     

Effects of reactive reinforced interface on the morphology and tensile properties of amorphous polyamide–SAN blends

The effects of reactive reinforced interface on the morphology and tensile properties of amorphous polyamide (a-PA) and styrene-acrylonitrile (SAN) copolymer blend have been investigated using styrene maleic anhydride (SMA) copolymer as a reactive compatibilizer. The anhydride groups of SMA copolymer can react with the amine groups of polyamide and form in situ graft copolymers at the a-PA–SAN interfaces during the blend preparation. The interfacial adhesion strength of the reactive reinforced interface was evaluated quantitatively using an asymmetric double cantilever beam fracture test as a function of SMA copolymer content using a model adhesive joint. The interfacial adhesion strength was found to increase with the content of SMA copolymer and then level off. The morphological observations of a-PA–SAN (80/20 w/w) blends showed that the finer dispersion of the SAN domains with rather narrow distribution was obtained by the addition of SMA copolymer into the blends. The trend of morphology change was not in accord with that of the interfacial adhesion strength with respect to the content of SMA copolymer. However, the results of tensile properties showed very similar behavior to the case of the interfacial adhesion strength with respect to SMA content; that is, there was an optimum level of the reactive compatibilizer beyond which the interfacial adhesion strength and tensile strength did not change significantly. These results clearly reveal that tensile properties of polymer blend are highly dependent on the interfacial adhesion strength. Furthermore, it is suggested that the asymmetric double cantilever beam fracture test using a model interface is a useful method to quantify the adhesion strength between the phases in real polymer blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1925–1933, 1998     

Influence of blend composition on the mechanical properties and morphology of PC/ASA/SAN ternary blends

Bisphenol A polycarbonate/acrylonitrile–styrene–acrylic/styrene–acrylonitrile copolymer (PC/ASA/SAN) ternary blends were prepared over a range of compositions via mixing PC, SAN, and ASA copolymer by melt blending. An analysis was made on the mechanical properties and morphology of the blends. Special care was taken to make comparisons of the morphologies and properties of blends with different SAN content. When a small amount SAN was introduced to PC/ASA blends, the dispersion condition of ASA in the matrix was improved and a better integrated mechanical properties was realized. Further increasing the SAN content led to a decrease of impact strength, which was due to the changing of the morphology of the blends and the inherent brittleness of matrix. The study about the effect of ASA content on the properties of PC/ASA/SAN blends showed that the blend with 20 wt% ASA had good mechanical properties.     

Investigation on the miscibility of the blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of addition of acrylic compatibilizer on the morphology and mechanical behavior of amorphous polyamide/SAN blends

Amorphous polyamide (aPA)/acrylonitrile‐styrene copolymer (SAN) blends were prepared using methyl methacrylate‐maleic anhydride copolymer MMA‐MA as compatibilizer. The aPA/SAN blends can be considered as a less complex version of the aPA/ABS (acrylonitrilebutadiene‐styrene) blends, due to the absence of the ABS rubber phase in the SAN material. It is known that acrylic copolymer might be miscible with SAN, whereas the maleic anhydride groups from MMA‐MA can react in situ with the amine end groups of aPA during melt blending. As a result, it is possible the in situ formation of aPA‐g‐MMA‐MA grafted copolymers at the aPA/SAN interface during the melt processing of the blends. In this study, the MA content in the MMA‐MA copolymer and its molecular weight was varied independently and their effects on the blend morphology and stress–strain behavior were evaluated. The morphology of the blends aPA/SAN showed a minimum in the SAN particle size at low amounts of MA in the compatibilizer, however, as the MA content in the MMA‐MA copolymer was increased larger SAN particle sizes were observed in the systems. In addition, higher MA content in the compatibilizer lead to less ductile aPA/SAN blends under tensile testing. The results shown the viscosity ratio also plays a very important role in the morphology formation and consequently on the properties of the aPA/SAN blends studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of matrix SAN in ABS/PMMA blends

The effect of the molecular weight and acrylonitrile (AN) content of the styrene–acrylonitrile copolymer (SAN) on the morphology, mechanical properties, and rheological properties of acrylonitrile–butadiene–styrene terpolymer/poly(methyl methacrylate) (ABS)/PMMA (60/40 by weight) blends were studied. When the AN content of matrix SAN (32%) was close to that of graft SAN (30%) AN, rubber particles existed separately. However, with matrix SAN having 35% AN, rubber particles showed tendency to agglomerate each other. With increasing molecular weight of matrix SAN, impact strength, ultimate elongation, and abrasion resistance of the blend generally increased. Yield strength increased with molecular weight at a constant AN content of matrix SAN, and it decreased with the decrease of AN content in spite of the increasing molecular weight of SAN. Melt properties, rather than the morphological and mechanical properties, were more sensitive to the AN content, rather than the molecular weight of matrix SAN. © 1994 John Wiley & Sons, Inc.     

Formation of co‐continuous PLLA/PC blends with significantly improved physical properties by reactive comb polymers

A kind of reactive comb (RC) polymer, which is constituted by poly(methyl methacrylate) backbone and side chains and a few epoxide groups that distribute randomly along the backbone, has been applied as compatibilizers for the thermodynamically immiscible poly(l ‐lactide) (PLLA)/polycarbonate (PC) blend (50/50, wt/wt). Phase morphology and physical properties of the compatibilized PLLA/PC blends are characterized by scanning electron microscopy, transmission electron microscopy, and tensile tests. It has been found that the morphologies of the PLLA/PC blends are significantly ameliorated with the addition of RC polymers. A type of PLLA/PC blend with stable co‐continuous morphology has been achieved by the incorporation of more than 3 wt % of RC polymers. The mechanical tests showed that the co‐continuous PLLA/PC blends have an excellent stiffness‐toughness balance with high modulus and significantly improved ductility. Especially, the elongation at break of the PLLA/PC blend compatibilized by 10 wt % of RC polymers is 10 times higher than that of neat PLLA, in which the blend exhibits a cocontinuous lamellar microstructure. Furthermore, the PLLA/PC blends with cocontinuous morphology exhibit dramatically improved thermal stability as compared to neat PLLA when the temperature is over the T_g of the PLLA phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46047.     

Light scattering materials with tunable optical properties by controlling refractive index of the dispersed phase

Traditionally, the morphologies of the dispersed phase in Polycarbonate (PC)/poly(styrene‐co‐acrylonitrile) (SAN) blends were strongly influenced if AN content in SAN changed significantly even under constant processing conditions. This would hinder the pure research intended to study the effect of the refractive index difference between the polymer host and the polymeric dispersed particles on the optical properties tough. Therefore, we respectively prepared different PC/SAN light diffusion sheets with four types of SAN containing different AN content ranging just from 20 to 25 wt %, a narrow range that sufficiently ensures the relatively stable morphology of different SAN in PC matrix. The results suggest that the refractive index of SAN increases with an decreasing AN content, thus narrowing the refractive index difference between PC and SAN and producing PC/SAN(70/30) light diffusion sheets with an increasing transmittance and decreasing haze. The interesting phenomenon is further analyzed using Mie scattering theory. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44156.     

Co-continuous polycarbonate/ABS blends

Co-continuous PC/ABS (50/50) blends were studied with a variable polybutadiene (PB) content (0-40%) in ABS. Polycarbonate (PC), styrene-acrylonitrile (SAN) and PB were blended in two steps using a twin screw extruder. Rectangular bars were injection moulded and notched Izod impact tested at different temperatures and in single edge notch tensile tests at 1 m/s and different temperatures. Co-continuous PC/ABS gave a brittle-to-ductile transition temperature lower than expected based on notched Izod results for dispersed ABS in PC. The brittle-to-ductile transition temperature, in the co-continuous PC/ABS blends, decreased with increasing rubber content in SAN. The fracture energies showed an optimum at 15% PB in SAN while at the same time a delamination was seen on the ductile fracture surface, due to failure of the PC/SAN interface. Delamination disappeared when the rubber content in SAN or the temperature was increased. Specimens containing a welding were injection moulded to study the influence of rubber and AN content in the SAN on the interface. Weldline strength of the blends was very poor compared to PC, but improved with increasing rubber content in SAN.     

Visco-elastic properties related to the phase morphology of 60/40 PC/SAN blend

Stress relaxation and dynamic mechanical measurements have been performed on a 60/40 blend of polycarbonate of bisphenol A (PC) and poly (styrene-co-acrylonitrile) (SAN). This paper clearly demonstrates that the phase morphology of an immiscible co-continuous polymer blend is an important parameter in determining visco-elastic behavior. The dynamic mechanical properties are discussed in terms of the visco-elastic form of a Kerner equation as a function of the reciprocal Chalkey parameter, which has been used to quantify the co-continuous phase morphology. The effective volume fraction of the SAN phase has been found to decrease as the phase structure coarsens during annealing above T_g of both SAN and PC. This is probably the result of phase break-up and subsequent inclusion of SAN domains in the PC matrix during the coarsening process, which modifies the structure produced during melt compounding and injection molding.     

Morphology and physical properties of SAN/NBR blends: The effect of AN content and melt viscosity of SAN

To study the effect of dispersed poly(butadiene-co-acrylonitrile) (NBR) rubber size on the physical properties of poly(styrene-co-acrylonitrile) (SAN)/NBR blends, SANs with various melt viscosities and acrylonitrile (AN) contents were examined. The dispersed size of NBR, whose AN content is 30 wt %, was reduced as the melt viscosity of the SAN matrix was increased or as the AN content of the SAN matrix was reduced in the range of 19–32 wt %. As the melt viscosity of the SAN matrix was increased, the damping peak of the NBR phase moved to a higher temperature, and as the AN content of SAN was reduced, the damping peak of the SAN phase moved to a lower temperature. Higher values of impact strength and elongation at break and reduced yield behavior at a low shear rate were observed at a finer dispersion of NBR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 935–941, 1999     

Properties and morphology of some injection-molded polycarbonate-styrene acrylonitrile copolymer blends

A series of blends was prepared with broad concentration ranges of polycarbonate (PC) and styrene-acrylonitrile copolymers (SAN) containing 5.5 and 30 weight percent acrylonitrile (AN). These blends were then injection molded, and their properties were measured and correlated with the morphologies of the blends (as determined by transmission electron microscopy). The toughness properties were shown to be discontinuous and very sensitive to composition of the continuous phase in the blends. The dart impact toughness remained high up to 30–40 weight percent SAN and dropped rapidly above this SAN concentration. The notched Izod toughness fell off rapidly at 10 weight percent SAN and greater. The strength and modulus had a more linear dependence on composition. Results of studies of the T_g by differential scanning calorimetry (DSC) show the presence of two phases over the entire concentration and a small solubility of each phase in the other. The heat distortion temperature under load (DTUL) of the blends approximated a linear additivity curve for the components. As expected, the blends had much better clarity where the refractive indexes more nearly match (in the case of the 5.5 percent AN copolymer).     

PC/SAN二元共混体系定构化研究

综述了聚碳酸酯／(苯乙烯／丙烯腈)共聚物(PC／SAN)共混体系的加工条件、形态结构与性能之间的密切关系。认为加工条件是影响PC／SAN共混体系性能的外因，而在加工过程中形成并最终保留在制品中的微观形态才是影响PC／SAN体系性能的主要的内因。阐明了在加工过程中对PC／SAN共混体系进行定构的重要性，总结了定构过程中的各种影响因素。     

Miscibility windows in ternary polymer blends of a polyester,polymethacrylate and poly(styrene‐co‐acrylonitrile)

Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (T_g) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry     

Evaluation of compatibility in SAN/EPDM blends by determination of the adhesion parameters

A series of various types (different structures) of ethylene-polypropylene-diene-graft-polystyrene (EPDM-g-PS) copolymers were synthesized and their surface property variations were studied using surface analysis techniques such as surface contact angle measurement. Pre-synthesized graft copolymers were added (5 phr) in styrene-acrylonitrile (SAN)/ethylene-propylene-diene (EPDM) blends composition of 95/5 and 90/10. The adhesion parameters at the interface, that is work of adhesion, the interfacial energy and the coefficient of wetting were calculated and correlated to the differential scanning measurements measurements and SEM micrographs in order to study the effect of graft copolymers on compatibility of SAN/EPDM blends. It is obvious that depending of the graft copolymer’s structure, various interactions between the components in the blend will be established, resulting in better adhesion which implicates improvement of compatibility in blends. Also, from the results, it can be seen that differences in structures of the added compatibilizer are clearly reflected in the adhesion parameters results, making this an acceptable method to determine whether two polymers are compatible. Morphology of the blends with the graft copolymers is significantly finer and the dispersed size is more uniformly distributed in comparison to the neat SAN/EPDM blend. The conditions of the optimal adhesion parameters with compatibilizer location at the interface, predicting by the thermodynamical models, correlated well with the improvement of the morphology and thermal measurements.     

Preparation of EPDM/SAN Dry Blends by Reactive Processing

Reactive blending of the rubber EPDM (a terpolymer consisting of ethylene, propylene and a diene) and the thermoplastic material SAN (a copolymer of styrene and acrylonitrile) is reinvestigated with special attention to EPDM/SAN blends with a 50/50 blend ratio. A resin cure system based on a low molecular weight phenol formaldehyde condensate, which primarily consists of dimethylolphenol and stannous dichloride, is used for compatibilization of EPDM and SAN, as well as for crosslinking of the EPDM phase. The amounts of phenolic resin and SnCl₂ · 2H₂O as well as the EPDM grade and the EPDM/SAN blend ratio are varied. The blends are characterized by stress‐strain measurements, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Unreacted EPDM, unreacted SAN and gel plus graft copolymer are quantitatively determined by fractionation of the blends with a binary solvent mixture which exhibits phase separation at room temperature. Blends prepared from EPDM grades that are amorphous and have a high molar mass exhibit high levels of gel and rather poor mechanical properties. With these blends, gel formation is favored over the formation of EPDM/SAN graft copolymers. Even with low levels of the resin cure system, the formation of gel cannot be avoided. It is therefore not possible to prepare graft copolymers without some gelling. Blends prepared from an EPDM grade with high crystallinity and a low Mooney viscosity exhibit substantially better mechanical properties than blends based on amorphous and higher viscosity EPDM grades. TEM and SEM micrographs reveal good dispersion of the two polymers, as well as good interfacial adhesion between the EPDM and the SAN phase. This electron microscopic evidence, in combination with low gel contents, supports the view that the tendency towards graft copolymer formation and gelling strongly depends on the EPDM grade used. Variation of the EPDM/SAN blend ratio between 5–90 wt.‐% results in blends which cover the product range from toughened thermoplastics to thermoplastic elastomers.

TEM of compatibilized EPDM/SAN blend.