“Mechanism of the self-reinforcement of cross-linked NR generated through the strain-induced crystallization”

The author proposed new models and concept for the self-reinforcement of NR. The first model indicates that general rubber vulcanizate consists of the heterogeneous structure, partially continuous cross-linked phase (75%) and continuous uncross-linked phase (25%). In addition, the author proposed other new models and concept for the strain-induced crystallization in vulcanized NR, in which the strain-induced crystallization takes place in the uncross-linked phase in cross-linked rubber. In the uncross-linked phase under large extension, molecular flow and orientation occur due to the very high compressive, shear and tensile stresses generated by the surrounding hard cross-linked phases, which makes the strain-induced crystallization possible in the uncross-linked phase. As macroscopic extension increases, the crystallization spreads over the whole uncross-linked phases, thus the uncross-linked phase changes its character from original soft rubber to the strong super network consisting of a bundle of extended molecules interconnected at the crystals. The characteristic phenomena observed in the stress-strain relation of NR such as the stress-upturn, high tensile strength and large stress-softening (Mullins effect) can be reasonably explained using these models and concepts.     

Dynamic mechanical properties of polystyrene/low density polyethylene blends

The dynamic mechanical properties of polystyrene/low density polyethylene blends and of polystyrene/polyethylene/di-block polystyrene-polyethylene copolymer blends have been investigated in the temperature range −160°C to +100°C. It is shown that anomalies in the low temperature shear modulus data of polystyrene-polyethylene blends are a consequence of non-adhesion between the components. From similar data of blends containing a partial di-block PS-PE copolymer it appears that only very small amounts of copolymer are needed to ensure adhesion between the polystyrene and polyethylene phase. Further it is shown that for modulus considerations of the blends, LDPE together with partial PS-PE copolymer can be treated as a single phase. In some cases the presence of copolymer causes formation of a continuous network throughout the polystyrene matrix, as reflected by a low value for the shear modulus of these blends. Phase reversal of polystyrene-polyethylene blends results in an increase of the loss modulus at 40°C which is ascribed to an increased friction caused by phase entanglements. This increase is more pronounced if an excess of polyethylene is present which is again a consequence of non-adhesion between the components.     

Controllably crazed polystyrene: Morphology and permeability

The effects of n-heptane and heat treatment on the structural and transport properties of polystyrene films (biaxially oriented and unoriented) were studied to determine whether these treatments improve the film as selective barriers for separation of molecules differing only slightly in size and shape. n-Heptane treatment of biaxially oriented polystyrene produces a sandwich structure composed of expanded, crazed, surface layers surrounding an apparently unaffected central core. The crazed layers contain a continuous network of interconnected channels. The core provides the total resistance to gas permeation, hence, the overall effect of n-heptane treatment is fabrication of a thinner more permeable membrane. By restricting the stress-cracking treatment to one face of the film, it should be possible to make high flux, anisotropic membranes—a type of membrane which is required for successful development of membrane separation processes. n-Heptane treatment of cast, annealed polystyrene results also in a crazed polymer, but the crazing is in the form of spherical voids, and the films, even with a residual uncrazed core, are too weak to be useful as separation membranes. The crazing process in both types of polymer specimens is characteristic of case II non-Fickian diffusion in which the kinetics are apparently controlled by polymer relaxation processes. Sorption of isopentane into cast, annealed polystyrene does not cause visible crazing but the kinetics are again non-Fickian. Desorption of isopentane into n-heptane-treated polystyrene releases the appreciable residual n-heptane in the film which could not be removed by long-term exposure to vacuum. Analysis of D(0) values for isopentane in n-heptane treated films indicates that the polymer surrounding the visible voids in the film is essentially unaltered polystyrene with only a small fraction of the voids being interconnected by open channels.     

Relation between phase structure and peel adhesion of poly(styrene-isoprene-styrene) triblock copolymer/tackifier blend system

The effect of tackifier on the adhesive properties of a model pressure-sensitive adhesive tape was investigated. For this purpose, a model system consisting of poly(styrene-isoprene-styrene) triblock copolymer as the base polymer and a typical aliphatic petroleum resin as the tackifier was prepared. The tackifier content ranged from 10 to 60 wt%. The tackifier used has a good compatibility with polyisoprene, whereas it has a poor compatibility with polystyrene. The 180° peel adhesion was measured. The peel adhesion increased with the tackifier content, while the degree of increase became more significant above 40 wt%. The pressure sensitivity appeared obviously and the maximum peel adhesion was obtained without heating above 40 wt%. The phase structure was determined using pulse ¹H-NMR, transmission electron microscopy and dynamic mechanical analysis. A phase structure in which spherical polystyrene domains with a mean size of about 20 nm were dispersed in the polyisoprene continuous phase was observed. It was found that the tackifier-rich phase of the order of nanometers in size was formed in the polyisoprene matrix and the concentration increased with the tackifier content. The tackifier-rich phase seemed to develop the cohesive strength and, thus, it increased the peel adhesion.     

Correlation between the porous structure of polystyrene and its discolouring ability

Porous polystyrene was prepared according to the following methods by variation of the production parameters: (A) Method based on the suspension polymerization using a nonsolvent of the polymer. (B) Method based on the dissolution of polystyrene in a solvent and then precipitation using a nonsolvent of the polymer. The molecular weight of the polymer, its structure using Hg-porosimetry, and the microscopic pattern of the polymer grains were determined. The ability of the produced polystyrene to discolour aqueous solutions of different dyes (mainly methylene blue) was also examined. From the correlation between porous structure and discolouring ability in comparison with corresponding discolouring examination of other adsorptive agents (activated carbon) the importance of the following parameters was found out and evaluated: (a) total value of pore volume or pore volume distribution, (b) intermediate part of pore distribution 10000 – 100 Å for the adsorption of the given dyes, (c) shape of pores, which are different in method A and B (the comparison of produced polystyrene by different production parameters should be done only by independent methods and not between A and B method). It also resulted that it is necessary to introduce appropriate groups into the molecules of the porous polystyrene in order to increase the adsorption rate of an ionic or a polar substance. In conclusion, by appropriate choice of the production parameters of porous polystyrene a product with the desired characteristics of porosity could be produced.     

Structure and thermal property of intumescent char produced by flame‐retardant high‐impact polystyrene/expandable graphite/microencapsulated red phosphorus composite

This paper is aimed to illustrate the structure and thermal property of intumescent char produced by flame‐retardant polymers containing expandable graphite (EG). For this purpose, high‐impact polystyrene (HIPS) flame retarded by EG individually or in combination with microencapsulated red phosphorus (MRP) was prepared. The results indicate that the intumescent char from HIPS/EG/MRP composite, which contains a small amount of phosphorus element and more oxygen element, is much more compact and continuous than that from HIPS/EG composite with identical loading of flame retardant due to binding effect of phosphoric acid and its derivatives. The intumescent char produced by HIPS/EG/MRP composite exhibits much enhanced thermal and thermo‐oxidative stability as well as thermal‐insulating effect, which can withstand destruction of heat and oxygen effectively and thus provide a good fire‐proof barrier. The temperature beneath this intumescent char is decreased significantly in case of action by flame. By comparison, the porous and loose intumescent char generated by HIPS/EG composite has poor thermo‐oxidative endurance, and most of it can be consumed in air at high temperature without effective protection for the polymer. This has resulted in remarkable increase in flame retardancy of the HIPS/EG/MRP composite.     

The effects of blending small amounts of homopolystyrene on the mechanical properties of a low styrene content styrene-butadiene-styrene block copolymer

Tensile, cyclic, and tear properties were compared for several styrene-butadiene-styrene (SBS) triblock copolymers, KRATON D2104, D1101 and D1102, and blends of D2104 with monodisperse polystyrene of various molecular weights. D2104 is expected to have a morphology of polystyrene spheres in a polybutadiene continuous matrix. The mechanical properties of D2104 were compared to the properties of SBS materials which have higher styrene contents and exhibit cylindrical or lamellar morphologies. Blending the D2104 with polystyrene (molecular weights ranging from 2000 to 51,000) to 24 and 28 wt % total styrene content showed that the tensile strength obtained for a blend was dependent on the molecular weight of the polystyrene added. Cycle testing of the D2104-polystyrene blends showed that with increasing polystyrene content the softening effect increases with increasing strain. This indicates that the degree of phase continuity of the polystyrene domains may be changing from a spherical morphology to a cylindrical morphology similar to that of pure SBS with 28 wt % styrene content. Tear test results for the blends were also observed to be similar to the results for pure SBS of the same total polystyrene content.     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

高透明抗冲聚苯乙烯中试研究

在连续本体聚苯乙烯中试装置上对高透明抗冲聚苯乙烯树脂进行了研究。结果表明,中试产品冲击性能与增韧剂相当,比小试产品稍差。小试产品、中试产品及增韧剂具有相似的互穿网络结构。     

The mechanism of extender action by potassium persulfate in the suspension polymerization of styrene

The contribution by potassium persulfate to suspension stability in the bead polymerization of styrene which is stabilized by hydroxyl apatite (tricalcium phosphate) powders has been studied. Potassium persulfate, when used in lieu of an anionic surfactant as the extender, causes the formation of polystyrene sulfate in the aqueous phase. This anion-active polymer adsorbs on the surface of the hydroxyl apatite crystals and thus alters their wetting characteristics, causing them to become more effective suspension stabilizers. Polystyrene sulfates of molecular weights ranging from 2000 to 100,000 have been synthesized, characterized, and shown to be effective hydroxyl apatite extenders. The capability of polystyrene sulfate to adsorb onto hydroxyl apatite crystals is not strongly dependent upon the molecular weight of the polymeric ester. The tolerance of the system to high molecular weight polystyrene sulfate is relatively high since excess extender is taken up by dissolving in the monomer phase. The tolerance for water-soluble polystyrene sulfate, on the other hand, is low because excess extender of this type engages in double-layer adsorption on hydroxyl apatite, which renders the latter too hydrophilic to permit effective suspension stabilization. Use of a water-soluble polymerization inhibitor in the suspension polymerization system has no effect on suspension stability when sodium dodecylbenzene sulfonate or preformed polystyrene sulfate is used as the extender; however, suspension stability is destroyed when the inhibitor is used with persulfate, because it prevents the formation of polystyrene sulfate. Potassium persulfate is therefore more accurately described as a precursor of the active extender, which is the mono- or disulfate ester of polystyrene.     

透明高抗冲聚苯乙烯树脂的工业化试验

在5kt／a高抗冲聚苯乙烯树脂装置上,以1,1-双(叔丁基过氧基)环己烷为引发剂、苯乙烯为单体、丁二烯-苯乙烯嵌段共聚物(简称K树脂)为增韧剂,采用自由基聚合工艺生产了透明高抗冲聚苯乙烯(HT-IPS)树脂,考察了HT-IPS树脂的微观结构、相对分子质量及其分布、流变性能、接枝反应程度、物理机械性能和光学性能,讨论了影响HT-IPS树脂结构及性能的因素。结果表明,HT-IPS树脂具有微观相分离结构,聚丁二烯链段为分散相、聚苯乙烯链段为连续相;HT-IPS树脂的流动性能略差于高抗冲聚苯乙烯树脂,且随着K树脂用量的增加,其流动性能变差,K树脂用量应控制在15份以下;在聚丁二烯链段的主链和侧链均发生了接枝反应,HT-IPS树脂具有较高的弯曲强度、弹性模量和拉伸强度,其光学性能、流变性能良好,但冲击强度较低,扯断伸长率较小。     

Synergetic Effects of Graphene Oxide and Clay on the Microstructure and Properties of HIPS/Graphene Oxide/Clay Nanocomposites

In this paper, double-network structure nanocomposite with improved mechanical and thermal properties were prepared using high-impact polystyrene as a matrix phase, clay and graphene oxide as effective reinforcing fillers through a facile solution intercalation method. The structure and morphology of nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction analysis, and the synergetic effects of clay and graphene oxide on the final properties were investigated using tensile, dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA) analysis. Mechanical analysis showed that the combination of graphene oxide and clay exerted a favorable synergistic effect on the tensile modulus and the yield strength of the ternary composite that are greatly improved as compared with neat high-impact polystyrene, high-impact polystyrene/graphene oxide, and high-impact polystyrene/clay binary composites due to the double-network structure formation between the nanofillers as confirmed by the direct morphological observations using transmission electron microscopy and scanning electron microscopy analysis. The viscoelastic behavior showed that storage modulus of ternary composite significantly improvement over than that of the pure matrix, high-impact polystyrene/graphene oxide and high-impact polystyrene/clay while network structure made. TGA and DMTA measurements also demonstrated that thermal stability of high-impact polystyrene matrix modified by graphene oxide and clay slightly enhanced during the creation of dual network structure of graphene oxide and clay. Our data suggest a potential application for the combination of graphene oxide and clay in graphene-based composite materials.     

Phase continuity in polystyrene–nylon 6,10 graft copolymers

Using a modified interfacial polymerization route, a graft copolymer of nylon 6,10 and polystyrene was prepared. First, an aqueous suspension of styrene monomer was encapsulated with nylon 6,10, followed by polymerization of the styrene to form the graft copolymer. When the material was subsequently molded below the crystalline melting point of nylon 6,10 (220°C), modulus–temperature behavior intermediate between polystyrene and nylon 6,10 was observed. However, when this graft copolymer was molded above the melting point of nylon 6,10, behavior more like pure polystyrene was observed. Phase contrast microscopy revealed that material molded below 220°C showed a continuous cellular-phase structure of about 30 microns in diameter, the interior of the cells being composed of polystyrene and the cell walls being composed of nylon 6,10. Phase inversion phenomenon was observed in the graft copolymer as the molding temperature was raised above 220°C. The nylon 6,10 phase became discontinuous, small globules being formed. This behavior is analogous to spheroidization in steel. It is thought that molten nylon 6,10 spheroidizes to attain a lower surface-energy state.     

Extraordinary terahertz absorption bands observed in micro/nanostructured Au/polystyrene sphere arrays

Terahertz (THz) time-domain spectroscopy is carried out for micro/nanostructured periodic Au/dielectric sphere arrays on Si substrate. We find that the metal-insulator transition can be achieved in THz bandwidth via varying sample parameters such as the thickness of the Au shell and the diameter of the Au/dielectric sphere. The Au/polystyrene sphere arrays do not show metallic THz response when the Au shell thickness is larger than 10 nm and the sphere diameter is smaller than 500 nm. This effect is in sharp contrast to the observations in flat Au films on Si substrate. Interestingly, the Au/polystyrene sphere arrays with a 5-nm-thick Au shell show extraordinary THz absorption bands or metallic optical conductance when the diameter of the sphere is larger than 200 nm. This effect is related to the quantum confinement effect in which the electrons in the structure are trapped in the sphere potential well of the gold shell.     

Diffusion study in a novel three-dimensional electrode for direct methanol fuel cells

A three-dimensional electrode formed by depositing Pt on polypyrrole treated polystyrene spheres (denoted as Pt/Ppy/PS) is prepared and characterized by different methods. The Pt/Ppy/PS prepared by using mixed polystyrene spheres of 200 nm-2 μm as support shows best performance for methanol oxidation due to the big and small holes or channels coexistent structure, which causes the difference in pressure inside the electrode and results in the reduction of the liquid sealing effect. The three-dimensional structure makes it easier for the liquid reactant to diffuse into the catalyst layer and the gaseous products evolve out from the catalyst layer. The diffusion behaviours of Pt/Ppy/PS and Pt/C electrodes are characterized by cyclic voltammetry. It is shown that the methanol oxidation on Pt/Ppy/PS electrode is not controlled by concentration polarization at slow scan rates, while the reaction on the traditional Pt/C electrode is diffusion controlled at all scan rates. The electrochemical impedance spectroscopic study (EIS) reveals that the three-dimensional electrode has higher active surface area.     

Thermal degradation of polystyrene in different environments

Several aspects of the thermal degradation of polystyrene are highlighted in this communication. The factors involved in determining the ratio of volatile to tar fraction products in the degradation of the pure polymer are examined, leading to the conclusion that the initial melt viscosity plays an important role in determining the balance between intra- and intermolecular transfer. The effect on the degradation of polystyrene of the presence of a second polymer is discussed. For polystyrene-polybutadiene and polystyrene-polyisoprene blends, stabilisation is observed, which is attributed to radical scavenging. The thermal degradation behaviour of polystyrene in the presence of oxygen has been investigated, with and without an antioxidant additive. Products have been characterised for oxidative conditions and the kinetics of degradation have been studied.     

二元溶剂体系对泡沫传输制备聚苯乙烯微球的影响

采用二氯甲烷（DCM）和丙酮（AC）组成二元溶剂体系,考察了二元溶剂体系对制备聚苯乙烯（PS）微球时泡沫的传输和微球性能的影响,并探讨了对应的作用机理。实验结果表明,随着AC质量分数的增加,体系的出泡温度升高,PS微球的平均粒径下降且粒径分布逐渐变窄,微球的结构由多孔逐渐演变为中空。这主要是由于AC对水具有一定的亲和性,会往连续相迁移,改变连续相的表面张力,并在油水界面形成一个AC/DCM的混合液膜层,该液膜层改变了溶剂挥发的过程,最终实现对微球粒径和结构的调控。     

Structure evolution driven by phase separation and the corresponding foaming behavior of polystyrene/poly(methyl methacrylate) blends via a batch foaming process

Morphology evolution of immiscible polymer blends during processing is a common phenomenon, but how it affects the foaming behavior is still unknown. The present work aims to study the effect of morphology evolution of polystyrene/poly(methyl methacrylate) (PS/PMMA) blends driven by phase separation on foaming behavior via a batch foaming process. Morphology evolution of PS/PMMA blends were conducted via thermal annealing using a compression molding machine. Phase contrast optical microscope and scanning electron microscope were used to investigate the morphology evolution and cell structures. The diffusion coefficients were calculated to study the effect of morphology evolution on gas diffusion behavior. It was found that phase domain was increased in size with the annealing and that cell structure was significantly dependent on morphology evolution. The thermal annealing with a long time could dramatically impact cell structures, especially for the blends with a bi‐continuous phase structure or a sea‐island structure with very large phase domains. The diffusion coefficient for the interface was increased with the annealing, which resulted in the generally decreased expansion ratio. Therefore, annealing for a long time at melt states during processing should be avoided for obtaining well‐defined cell structures for immiscible polymer blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46704.     

The effect of chemical treatment of wood and polymer characteristics on the properties of wood–polymer composites

The physical-mechanical properties and the microscopic structure of caixeta (Chrysophyllum viride) and slash pine (Pinus elliottii) impregnated with polystyrene (PS) were investigated. The influences of a pretreatment with hydrogen peroxide (H₂O₂) solutions utilized in the production of the wood–polymer composites (WPC) and the characteristics of polystyrene formed in situ on the properties of WPC were analyzed. The incorporation of polystyrene improved the compression and static bending properties of slash pine and caixeta. The micrographies confirmed that there were distinct but continuous phases of polymer and wood cell wall which granted the composites a better physical-mechanical behavior. The sensibilizing treatment with dilute hydrogen peroxide solution led to an increase in the viscosity average molecular weight (M _v) of polystyrene, and to the graft polymerization of the monomer, which, in turn, enhanced the stress properties of caixeta–polystyrene composites. Concentrated H₂O₂ solutions degraded caixeta wood, decreasing its tensile properties. Lower initiator concentration favoured higher molecular weight of polystyrene formed in pine wood. A fivefold increase in M _v of PS, however, had little effect on the compression properties of pine–polystyrene composites.