Zinc Dimethacrylate-Reinforced Thermoplastic Vulcanizates Based on Chlorinated Polyethylene Rubber/Ethylene-Vinyl Acetate Copolymer

A chlorinated polyethylene rubber (CPE)/ethylene-vinyl acetate copolymer (EVA) (weight ratio = 70/30) thermoplastic vulcanizate (TPV) was prepared by dynamic vulcanization, with the TPV being reinforced by various amounts of zinc dimethacrylate (ZDMA). The effects of ZDMA content on the mechanical and morphological properties of the TPVs were investigated. Experimental results indicated that dynamically vulcanized CPE/EVA blends without ZDMA showed an elastomeric behavior when the CPE/EVA weight ratio ranged from 90/10 to 50/50. The mechanical properties of dynamically vulcanized CPE/EVA blends were enhanced remarkably by the incorporation of ZDMA, especially when the ZDMA content was 5 phr. The fracture surface morphology of the reinforced CPE/EVA TPVs was relatively rough and drawn fibers could be found clearly. There were many ZDMA particles dispersed on the etched surface of the reinforced CPE/EVA TPVs with diameters of below about 10 μm. Energy dispersive X-ray spectrometer (EDS) results showed that the ZDMA particles were coated with CPE, the ZDMA particles being surrounded by a large number of small crosslinked CPE particles with diameters of 1 μm.     

Dynamically Vulcanized Cis-1,3-Butadiene Rubber/Ethylene-Vinyl Acetate Copolymer/High- Impact Polystyrene Blends Compatibilized by Styrene-Butadiene-Styrene Block Copolymer

Compatibilized Cis-1,3-butadiene rubber (BR)/ethylene-vinyl acetate copolymer (EVA)/high-impact polystyrene (HIPS) thermoplastic blend vulcanizates (TPVs) were prepared by dynamic vulcanization, with TPVs being compatibilized by styrene-butadiene-styrene (SBS) block copolymer. The effects of SBS compatibilizer on mechanical, dynamic mechanical, and morphological properties of TPVs were investigated systematically. Experimental results indicated that the dynamically vulcanized BR/HIPS blends did not show an elastomeric behavior when the BR/HIPS blend ratio ranged from 30:70 to 70:30. However, the dynamically vulcanized BR/EVA/HIPS blends compatibilized with SBS showed obvious elastomeric behavior; thus SBS had a good compatibilization effect on BR/EVA/HIPS TPVs. The fractured surface morphology of compatibilized BR/EVA/HIPS TPV was relatively smooth, the interface interaction was strong, and there was no obvious micro-phase separation. BR particles were dispersed evenly in the etched surfaces of BR/EVA/SBS/HIPS TPV. A rubber process analyzer revealed that the storage modulus decreased significantly with increasing strain and the incorporation of compatibilizer SBS in TPVs weakened the Payne effect; the loss modulus showed a pronounced peak and tanδ increased continuously with increasing strain.     

Dynamically Vulcanized Nitrile Butadiene Rubber/Acrylonitrile-Butadiene-Styrene Terpolymer Blends Compatibilized by Styrene-Butadiene-Styrene Block Copolymer

Thermoplastic vulcanizates (TPVs) based on nitrile butadiene rubber (NBR)/ acrylonitrile-butadiene-styrene (ABS) blends were prepared by dynamic vulcanization, and then compatibilized by styrene-butadiene-styrene block copolymer (SBS). The effects of SBS compatibilizer on mechanical properties, Mullins effect, and morphological properties of the TPVs were investigated systematically. Experimental results indicated that SBS had an excellent compatibilization effect on the dynamically vulcanized NBR/ABS TPVs. The tensile strength increased from 9.4 to 15.8 MPa and the elongation at break went through a maximum value when the dosage of SBS was only 1 phr. Mullins effect results showed that the compatibilized NBR/ABS TPV had relatively lower residual deformation and internal friction loss than the NBR/ABS TPV, indicating the improvement of elasticity. Morphology studies showed that the vulcanized NBR particles were dispersed evenly in the TPVs and the dimensions of NBR particles were decreased remarkably with the incorporation of SBS compatibilizer.     

Dynamically Vulcanized Styrene-Butadiene Rubber/Ethylene-Vinyl Acetate Copolymer/High Impact Polystyrene Blends Compatibilized by Styrene-Butadiene-Styrene Block Copolymer

Thermoplastic vulcanizates (TPVs) based on styrene-butadiene rubber (SBR)/ethylene-vinyl acetate copolymer (EVA)/high-impact polystyrene (HIPS) blends were prepared by dynamic vulcanization, and the TPVs was compatibilized by styrene-butadiene-styrene block copolymer (SBS). The effects of SBS compatibilizer on mechanical, dynamic mechanical, and morphological properties of the TPVs were investigated systemically. Experimental results indicate that SBS had a good compatibilization effect on the SBR/EVA/HIPS TPVs. The tensile strength went through a maximum value at a compatibilizer resin content of 6 phr, and the elongation at break and tear strength increased with increasing SBS content. Morphology study shows that the vulcanized SBR particles were dispersed in the HIPS matrices. A rubber process analyzer reveals that the elastic modulus increased with increasing frequency and the incorporation of EVA in the TPVs led to the obvious decrease of elastic modulus; however, the further addition of compatibilizer SBS affected the elastic modulus less. The tan δ decreased continuously with increasing frequency. The addition of SBS in the TPVs led to enhanced hysteresis behavior and relatively high tan δ.     

Comparison of Mechanical Properties and Rheological Behavior of Trans-Polyisoprene/Polypropylene and Ethylene Propylene Diene Rubber/Polypropylene Thermoplastic Vulcanizates

The degree of dynamic vulcanization, mechanical properties, rheological behavior, and the ageing-resistant performance of trans 1,4-polyisoprene (TPI)/polypropylene (PP) and ethylene propylene diene rubber (EPDM)/PP thermoplastic vulcanizates with a blend ratio of 60/40 were investigated comparatively. The results showed that TPI had fully dynamically vulcanized when mixed with PP in the Hakke mixer chamber (175°C, 60 rpm) while EPDM had only partly dynamically vulcanized due to its saturated main chain backbone. With increased sulfur content, the torque at the end of the curing curves of the two thermoplastic vulcanizates (TPVs) increased in the curing characteristics measuring process as the degree of crosslinking increased. Comparing the two blends, TPI/PP-TPVs were possessed of a better mobility, a little lower tensile strength and tear strength, a little higher 100% modulus and hardness, and much lower elongation at break. EPDM/PP-TPVs had better ageing-resistant characteristics due to EPDM's saturated main chain backbone.     

Polyvinylidene Fluoride/Acrylonitrile Butadiene Rubber Blends Prepared Via Dynamic Vulcanization

Dynamically vulcanized blends based on polyvinylidene fluoride (PVDF)/acrylonitrile butadiene rubber (NBR) were prepared and characterized. The mixing torque and dynamic rheology analyses showed that the NBR phase increased the viscosity of the blends. Scanning electron microscopy (SEM) results showed that the NBR phase was in the form of spherical particles dispersed in the PVDF phase during dynamic vulcanization. Comparing PVDF-rich and NBR-rich blends, the size of the rubber particles in the NBR-rich blends were larger than those in PVDF-rich blends. Differential scanning calorimetry (DSC) results showed that the addition of the NBR phase reduced the PVDF crystallinity and T_m. Thermal gravimetric analysis (TGA) results showed that the dynamically vulcanized PVDF/NBR blends had a higher residual char mass than the neat PVDF and NBR. For PVDF-rich blends, the PVDF can be highly toughened by NBR; the Izod impact strength of the PVDF/NBR (70/30) blend was 77.5 kJ/m², which was about six times higher than that of pure PVDF. For rubber-rich blends, the PVDF component was beneficial to the mechanical properties of the blends, which can be used as thermoplastic elastomers.     

Mechanical Properties and Rheological Behavior of Dynamically Vulcanized Trans-Polyisoprene/Polypropylene Blends

The degree of dynamic vulcanization, mechanical properties, rheological behavior, and the ageing-resistant performance of thermoplastic vulcanizates (TPVs) based on Trans 1,4-polyisoprene/polypropylene (TPI/PP) blends with the blend ratios of 70/30, 60/40, and 50/50 were investigated. The results showed that TPI fully dynamically vulcanized in the Haake mixer chamber when mixed with PP, and the specimen with the blend ratio 70/30, for the same sulfur content in all samples, had the lowest cross-linking degree of the TPI phase. The shear viscosity of TPI/PP-TPVs dropped as the shear rate increased and the specimen with the blend ratio 70/30 had a relatively greater shear viscosity in the region of shear rates less than 1000 s^?1. With the antiageing agent Vulkanox 4020 NA (Bayer) added, all the TPI/PP-TPVs showed good ageing characteristics, and the specimen with the blend ratio 70/30 possessed the best mechanical properties.     

Damping Properties of Blends Based on EVM

The mechanical and damping properties of blends of ethylene-vinyl acetate rubber (VA content >40% wt) (EVM)/ethylene-propylene-diene copolymer (EPDM) and EVM/nitrile butadiene rubber (NBR), both with 1.4 phr BIPB (bis (tert-butyl peroxy isopropyl) benzene) as curing agent, were investigated by dynamic mechanical analysis (DMA). The effect of added polyvinyl chloride (PVC), amido donor N-cyclohexyl-2-benzothiazole sulfonamide (CZ), and dicumyl peroxide (DCP) as a substitute curing agent, on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range (EDTR) from 41.1°C for EVM/NBR to 62.4°C. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its EDTR to 64.9°C. CZ had no obvious influence on the EVM/EPDM blends cured with BIPB. However, a small content of CZ enlarged the tan δ peak of EVM/NBR = 80/20 in both height and width, but at the cost of a deterioration of mechanical performance.     

Properties of blends of poly(vinyl chloride) and chlorinated polyethylene. I. Optical methods of characterization of PVC multiphase systems

Hitherto it has not been possible to produce a microscopic image with adequate resolution of the high-impact two-phase system poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE) due to inadequate phase contrast. With the aid of various chemical staining methods and through ion etching, a way has been found for studying the microstructure of the PVC/CPE system by light microscopy and electron microscopy. These independent visualization techniques and scanning electron micrographs of fracture surfaces show, as the morphology with optimal mechanical and rheological properties, networklike distribution of the rubber phase and, imbedded in this, a PVC phase consisting of primary particles.     

Stress whitening and yielding mechanism of rubber-modified PVC

Structure-property relationships were investigated for blends of grafted rubbery polymers with PVC. Increasing grafting levels as well as higher blending temperatures improved the dispersion of the graft copolymers in PVC, lowered the impact strength, and reduced stress whitening. Presuming a mechanistic connection between impact strength and stress whitening, the causes of whitening due to mechanical deformations were studied by a variety of methods. Electron microscopy of stress-whitened zones revealed a large number of cavities formed by rupture of rubber particles, which correlated with the extent of whitening. Density measurements and quantitative evaluations of the volume increase due to the cavities in the stress-whitened zones were in agreement and proved that crazing did not significantly contribute to either volume dilation or stress-whitening. Light scattering studies indicated the existence of reflecting planes oriented at an angle of 55 to 64° to the direction of the applied stress, depending on the particle size of the modifier in the blends. The orientation of the scattered light could not be attributed to the cavities in the rubber particles because of their smallness (< 0.5 μm). An explanation was finally found by transmission light microscopy at various resolving powers. It was demonstrated that the ruptured rubber particles were accumulated in bands which corresponded to shear bands in the PVC matrix. Thus it was concluded that the rubber particles improved the impact strength of PVC by initiating shear bands and not by generating crazes.     

Properties and Structure of Dynamically Vulcanized TPU/EVM Blends

The preparation of dynamically vulcanized TPU (thermoplastic polyurethane)/EVM (ethylene-vinyl acetate copolymer rubber) blends and the effect of two peroxide curing agents, DCP (dicumyl peroxide) and BIPB (bis(tert-butyl peroxy isopropyl)benzene) on the mechanical properties, hot air aging, and oil resistance were investigated. Fourier transform infrared spectroscopy (FTIR), phase-contrast microscopy (PCM), and magnetic resonance crosslink density spectroscopy (MR-CDS) were used to analyze the curing reaction, phase structure, and crosslink density of dynamic vulcanizates. The results showed that the optimum parameters for dynamically vulcanized TPU/EVM by peroxide-DCP or BIPB in a HAAKE rheometer were: mixing temperature 140–150°C and rotor speed 30 rpm. The mechanical properties and oil resistance of these blends were improved by dynamic vulcanization. It was found that BIPB is a better curing agent than DCP for the dynamic vulcanization of TPU/EVM and its optimum content was 0.8 phr in the blend. FTIR spectra showed EVM and TPU could both be cured by peroxide in the blend and the curing reaction occurred at -CH₂- groups that were linked with -C- instead of -O- and -CH₃ groups in the blend. PCM photographs showed that dynamically vulcanized TPU/EVM blends had “sea-island” phase structure when the curing agent content was low and it had “interlocked/co-continuous” phase structure as the curing agent content was increased. The spin-lattice relaxation constant, T_21, measured with MR-CDS proved that the crosslink density of the cured blends increased with increasing curing agent content.     

Thermoplastic Elastomers Based on Ethylene-vinyl Acetate Copolymer and Waste Nitrile Butadiene Rubber Powder Blends Compatibilized by Chlorinated Polyethylene

Thermoplastic elastomers (TPEs) based on ethylene-vinyl acetate (EVA)/waste nitrile butadiene rubber powder (WNBRP) blends compatibilized by chlorinated polyethylene (CPE) were prepared by melt-compounding. The tensile strength and the elongation at break of the EVA/CPE/WNBRP blends were increased significantly compared with those of the EVA/WNBRP blends. The fracture surfaces of the EVA/CPE/WNBRP blends were smooth; moreover, the WNBRP in the etched EVA/CPE/WNBRP blends were inserted in the EVA matrix tightly. DMA results revealed that when the CPE dosage was 5 phr in the EVA/CPE/WNBRP blend, the Payne effect was weakened significantly.     

Styrene Butadiene Rubber/Silicone Rubber Blends Filled With Dough Moulding Compound

Blends of styrene butadiene rubber (SBR)/methyl-vinyl silicone rubber (MVQ) filled with dough molding compound (DMC) were prepared and the effects of various amounts of the SBR, as a compatibilizer of MVQ and DMC, on the mechanical properties and the oxygen index of the DMC filled SBR/MVQ blends were investigated. Dynamic mechanical analysis (DMA) and infrared spectrum analysis (IR) of the DMC/SBR/MVQ blends were also investigated. The results showed that the mechanical properties of the DMC filled MVQ blends were improved when SBR was used as a compatibilizer; the best mass ratio was 60 phr (parts per hundred total rubber) DMC, 25 phr SBR and 75 phr MVQ. The volume electric resistivities of the DMC filled SBR/MVQ blends with various DMC mass ratios were all above 5.8?×?10¹² Ω?m; i.e., the electrical insulating property of the blends was excellent. Compared with the blends without DMC and the blends without SBR, the energy storage modulus and the peak area of the loss factor tan δ of the DMC reinforced SBR/MVQ blends were largest; the addition of DMC and SBR improved the thermal properties of the blends.     

In Situ Dynamic Vulcanization of Poly(Vinyl Chloride)/Acrylonitrile-butadiene Rubber Blends

Poly(vinyl chloride) (PVC)/acrylonitrile-butadiene rubber (NBR) blends can be obtained through a dynamic vulcanization process as a melt-processible thermoplastic elastomer which produces parts that look, feel and perform like vulcanized rubber with the advantage of being processible as a thermoplastic material. In this study, a vulcanized thermoplastic was obtained by in situ dynamic vulcanization of PVC/NBR blends using a sulphur/ tetramethylthiuram disulphide (TMTD) and mercaptobenzothiazyl disulphide (MBTS) curative system during processing at the melt state. The blends were melt-mixed using a Haake Rheomix 600. The curing behavior of NBR was then investigated by a Monsanto rheometer. The thermal analyses were performed and the cross-linking at different mixing times was calculated using DSC. FT-IR was also performed for characterization of the blends. The cross-link densities of the samples were measured by a swelling method. The degree of cure increases with the mixing time. The cross-linking formation was verified through the formation of C─ S bonds in the blends.     

CORRELATION AMONG MORPHOLOGY,INTERFACE, AND MECHANICAL PROPERTIES: EXPERIMENTAL STUDY

The effect of the disperse phase and the diffuse interface between phases on the tensile and impact strengths of polypropylene (PP)/poly(ethylene terephthalate) (PET) (75/20 by weight) blends compatibilized with maleic anhydride–grafted PP derivatives and on the tensile modulus of poly(vinyl chloride)/polystyrene (PVC/PS) nanoparticle blends compatibilized with polystyrene/poly(vinyl acetate) (PS/PVAc) block copolymers were investigated experimentally. The weight fraction of the diffuse interface between the PP and PET phases in the PP/PET blends was determined by modulated differential scanning calorimetry (MDSC). A correlation between the diffuse interface content and mechanical properties was found. With increasing diffuse interface weight fraction, the impact and tensile strengths of the PP/PET blends increased. There is a brittle-tough type transition in these PP/PET blends. With increasing diffuse interface content in the PVC/PS nanoparticle blends in which the particle size was fixed at about 100 nm, the tensile modulus also clearly increased.     

Vulcanization and Thermal Properties of Silicone Rubber/Fluorine Rubber Blends

With the rapid development of automobile, aviation, aerospace, machinery and other fields, rubber products used in these fields required to meet higher requirements. Fluorine rubber (FKM) and silicone rubber (MVQ) have excellent performance in some areas. However, the FKM is poor in low-temperature resistance and processing performance, limiting its applicability. Although the MVQ has a wide range of temperature and excellent processing performance, but its mechanical properties and oil resistance are not good. In this work, the MVQ/FKM blends were prepared by two different mechanical blending methods. The effects of the mixing process, mass ratio, curing system and conditions of the blends were studied. The chemical compositions of the blends were analyzed by infrared spectroscopy (IR). The compatibility and the thermal properties of the blends were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. The results showed that the mechanical properties, compatibility and thermal stability of the blends were the best when they were prepared by kneading the FKM and MVQ individually in a two-rool mill roll, then mixing them together homegeneously with an MVQ/FKM mass ratio of 10/90, curing system of (4 phr, 1/9) dicumyl peroxide (DCP)/N, N-Dicinnamylidene-1, 6-hexanediamine (3^# Vulcanizer), first curing conditions at 170?°C under 10?MPa for 30?min and post curing conditions at 200?°C for 6?hours at 1 atmospheric pressure.     

Thermoplastic Elastomers Based on Natural Rubber/Polypropylene Blends: Effect of Blend Ratios and Dynamic Vulcanization on Rheological,Thermal, Mechanical,and Morphological Properties

Thermoplastic elastomers (TPEs) based on natural rubber (NR)/polypropylene (PP) with different blend ratios were prepared and studied. The TPEs were obtained by dynamic vulcanization of NR/PP using a sulfur (S)/N-tert-butyl-2-benzothiazolesulphenamide (TBBS) and tetramethylthiuram disulphide (TMTD) curative system during processing in the melt state in an internal mixer equipped with cam rotors. Rheological, thermal, mechanical, dynamic, and morphological properties of the TPEs prepared were investigated. Based on this study a mechanism for the NR crosslinking was proposed where the sulfur vulcanization occurs through radical substitution in the forms of polysulfide bridges. The dynamic vulcanization process increases the stiffness of the NR phase in the TPEs and modifies the rheological and thermal behavior of the system compared to the behavior of the basic material PP. The crosslinked NR particles restrict the spherulitic growth and the regular arrangement of the spherulites of PP phase, decreasing the crystallinity degree. On the other hand, a reduction of mobility of the chain segments was also observed and, consequently, an increase of the T_g values. NR/PP TPEs with high content of NR showed superior mechanical performance compared to the uncrosslinked NR/PP blends in terms of tensile strength, Young's modulus and hardness. An increase of approximately 320% in Young's modulus values was obtained for the NR70/PP30 TPE compared to NR70/PP30. Morphological studies revealed the formation of large aggregates of NR domains in NR/PP TPEs which increased in size with an increase of the rubber content.     

Compatibilization by Olefin Block Copolymer (OBC) in Polypropylene/Ethylene-Propylene-Diene Terpolymer (PP/EPDM) Blends

The compatibilization by olefin block copolymer (OBC) in the blends of polypropylene (PP)/ethylene-propylene-diene terpolymer (EPDM) and the phase morphology of the ternary blends were investigated by rheology, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements. It was found that the PP/EPDM blends exhibited enhanced mechanical properties in the presence of OBC. The addition of OBC had a significant influence on the phase separation behavior of the blends. For the PP/EPDM-50/50 heterogeneous blends, the addition of 15 phr OBC enabled the two-phase morphology to change from a droplet-matrix structure to a co-continuous one. In the temperature range of 150 to 200 °C, OBC was shown to have a better compatibility with PP than EPDM. The changes in viscosity ratio of the dispersed phase to matrix phase caused by adding OBC might be the dominant factor in controlling the coalescence of the dispersed phase domains. For the crystallization behavior of PP/EPDM/OBC ternary blends, OBC was found to have an induction effect on the formation of β-crystals of PP that was not proportional to the volume of OBC addition. In addition, DSC results showed that PP could induce the OBC crystallization and improve the crystallization temperature of OBC. The existence of simultaneous crystallization behavior between PP and OBC was also observed. A possible mechanism of phase evolution induced by crystallization was proposed.     

Damping Properties of Ethylene-Vinyl Acetate Rubber/Nitrile Butadiene Rubber Blends

The damping and mechanical properties of ethylene-vinyl acetate rubber (EVM)/nitrile butadiene rubber (NBR) blends, with BIPB (bis (tert-butyl peroxy isopropyl) benzene) as curing agent, were investigated by DMA. It was proved by mechanical performance, DMA and crosslink density data that a chemical crosslinking reaction occurred between EVM and NBR. A new tan δ peak appeared between 40°C and 60°C in EVM/NBR = 80/20, which we suggest was due to a new molecular chain generated between EVM and NBR. Thus, the effective damping temperature range (EDTR) of EVM/NBR = 80/20 was widened from 31.6°C of EVM and 31.7°C of NBR to 40.7°C. The addition of sulfur, as a curing agent for NBR, greatly raised the height of the damping peak of EVM/NBR blend, but only slightly widened the EDTR at a cost of deterioration of mechanical performance. Zinc diacrylate (Zn (Ac)₂), as a possible graft addition to the blends, enlarged the damping peak of EVM/NBR, especially widening the EDTR of EVM/NBR = 80/20 to 50.9°C, but with a decline of mechanical properties. PVC was partially miscible with EVM/NBR blends and dramatically widened the EVM/NBR = 80/20 EDTR to 62.4°C.     

Morphological,Thermal and Mechanical Properties of Compatibilized Nylon 6/ABS Blends

Super‐tough nylon 6/ABS blends were prepared by using styrene/acrylonitrile/maleic anhydride co‐polymer (SAM) as a compatibilizer. The variations in morphology, mechanical behavior, and crystallinity associated with the reaction of the SAM with the nylon were characterized. The results showed that the addition of SAM to nylon 6/ABS blends enhanced the interfacial adhesion between nylon 6 and ABS, and this led to the decrease of ABS domain size and the improvement of mechanical properties of their blends. Moreover, it could be found that the crystallinity and phase morphology changed with the variation of SAM.