Effects of partial replacement of silicone rubber with flurorubber on properties of dynamically cured poly(vinylidene fluoride)/silicone rubber/flurorubber ternary blends

Blends of poly(vinylidene fluoride) (PVDF), silicone rubber (SR) and flurorubber (FKM) were prepared via peroxide dynamic vulcanization. The effect of FKM loading on the morphology, mechanical properties, crystallization behavior, rheology and dynamic mechanical properties of the PVDF/SR/FKM ternary blends was investigated. A “network” was observed in the PVDF/SR binary blends, which disappeared in the ternary blends, but a core-shell-like structure was formed. The mechanical properties were significantly improved. The Izod impact strength of PVDF/SR/FKM blend with 19 wt% FKM was 18.3 kJ/m², which was 3–4 times higher than the PVDF/SR binary blend. The complex viscosity and storage modulus of the PVDF/SR/FKM blends decreased with increasing FKM content, hence the processability was improved. The increase of FKM content seemed to show a favorable effect on the crystallization of the PVDF component. It promoted the nucleation process of PVDF, leading to increased polymer crystallization rate and higher crystallization temperature. The glass-rubber transition temperature of the PVDF phase moved to a lower temperature.     

Influence of size reduction of crosslinked rubber particles on phase interface in dynamically vulcanized poly (vinylidene fluoride)/silicone rubber blends

In this paper, the influence of rubber particle size on the phase interface in dynamically vulcanized poly(vinylidene fluoride)/silicone rubber (PVDF/SR) blends without any modifier is discussed through the studies of specific surface of crosslinked SR particles, crystallization behavior and crystal morphology of the PVDF phase, interfacial crystallization, melt rheological behavior and mechanical properties of blends. A series of decreased average particle size was successfully obtained by control of rotor rate. It was found that properly high rotor rate helped to achieve a reduced particle size and a narrowing size distribution. The reduced SR particle size enlarged the PVDF/SR interface which has a positive effect on the interfacial crystallization and the melt rheological behavior. At high SR content, the negative effect of the poor interface interactions played the dominate role on determining the mechanical properties. However, the blend exhibited a unique stiffness-toughness balance at the PVDF/SR = 90/10. We hope that the present study could help to lay a scientific foundation for further design of a useful PVDF/SR blend with promoted properties to partly replace the high-cost synthetic fluorosilicone materials.     

Novel fluorosilicone thermoplastic vulcanizates prepared via core‐shell dynamic vulcanization: Effect of fluororubber/silicone rubber ratio on morphology,crystallization behavior,and mechanical properties

Recently, we have reported a novel core‐shell dynamic vulcanization method to prepare poly(vinylidene fluoride) (PVDF)/fluororubber (FKM)/silicone rubber (SR) thermoplastic vulcanizates (TPVs) with cross‐linked rubber core‐shell particles. However, the shell thickness on the properties has not been studied in detail. Herein, these PVDF‐based TPVs different FKM‐shell thickness were prepared by changing FKM/SR ratios. The effect of FKM‐shell/SR‐core ratio on morphology, crystallization, and mechanical properties of the ternary TPVs was studied. The results showed that the FKM shell had more positive effect on interfacial‐induced crystallization behavior than the SR core due to its better compatibility with PVDF. When the FKM/SR ratio was <1, FKM was not enough to encapsulate SR completely, which resulted in the formation of imperfect core‐shell structure. However, when the FKM/SR ratio was >1, perfect core‐shell structure was formed. Therefore, the mechanical properties improved with increasing FKM content; especially, a remarkable improvement was observed when FKM/SR ratio was >1. This study could provide more information for the design of TPVs with core‐shell structure.     

Mechanical and Rheological Behavior of Unvulcanized and Dynamically Vulcanized i-PP/EPDM Blends

The mechanical and rheological behavior of dynamically vulcanized PP/EPDM blends is examined and compared with those of unvulcanized blends. The effect of blend ratio and dynamic vulcanization of EPDM rubber on tensile properties and flow are investigated. The mechanical properties of the blends are strongly influenced by the blend ratio. With the increasing of EPDM content the value of yield stress in a solid state decreases with the elastomer volume fractions less than 0.45 for the unvulcanized blends. For the dynamically vulcanized blends the interval of EPDM content, at which the yield peak is seen, is rather limited below 0.25 elastomer volume fractions. It is shown that dynamic vulcanization changes the deformational behavior of PP/EPDM blends. The rheological properties of dynamically vulcanized blends depending on the ratio of the components may be similar to the properties of polymer composites containing the highly disperse structuring filler. The distinction between the rheological behavior of unvulcanized and dynamically vulcanized blends is related to differences of their structures and viscoelastic characteristics of unvulcanized and vulcanized EPDM phase.     

Thermoplastic elastomer based on epoxidized natural rubber/thermoplastic polyurethane blends: influence of blending technique

Epoxidized natural rubber (ENR) and thermoplastic polyurethane (TPU) blends were prepared by simple blend and dynamic vulcanization. The main objective was to prepare a low‐hardness TPU material with good damping and elastic and mechanical properties. It was found that the incorporation of ENR into the blend shows a reduction in Young's modulus, hardness (i.e. <70 Shore A), damping properties (i.e. tan δ < 0.3), and tension set (i.e. <20%) compared with the pure TPU. This indicates the formation of softer TPU materials with superior damping and elastomeric properties. However, incorporation of ENR sacrificed mechanical properties in terms of tensile strength and elongation at break, but these still remain in the range of applicability for industrial uses. It was also found that dynamic vulcanization caused enhancement of mechanical properties, relaxation, damping, rheological properties, and elasticity of the blends. Temperature scanning stress relaxation measurements revealed an improvement in stress relaxation properties and thermal resistance of the dynamically cured ENR/TPU blend. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation and properties of novel fluorosilicone thermoplastic vulcanizate with cross‐linking–controlled core‐shell structure

A new fluorosilicone thermoplastic vulcanizate (TPV) composed of poly(vinylidene fluoride) (PVDF), silicone rubber (SR), and fluororubber (FKM) was successfully prepared through dynamic vulcanization. The morphological structure of the TPVs had core‐shell elastomer particles dispersed in a continuous PVDF matrix. Furthermore, the cross‐linking of core‐shell structure was controlled by adopting different curing agent. The effect of cross‐linking–controlled core‐shell structure on the morphology, crystallization behavior, stress relaxation test, solvent‐resistant properties of the obtained TPVs were investigated. It was found that the shell cross‐link had a significant influence on the crystallinity of the PVDF phase. The core‐shell bicross‐linked TPV was found to provide the lowest rate of relaxation. An obvious stress softening phenomenon was observed in the uniaxial loading‐unloading cycles in tension. The bicross‐linked TPV had good solvent resistant properties. The tensile strength of the bicross‐linked TPV was still 12 MPa even after immersed in butyl acetate for 48 hours.     

Ternary blends based on poly (ethylene-naphthalate)/glass fibers/nitrile rubber: Preparation,properties and effect of dynamic vulcanization

This work studied the possibility of utilizing nitrile rubber (NBR) to modify the impact properties of poly (ethylene-naphthalate) (PEN). The PEN/NBR ratio used changed from 100/0 to 60/40. At the same time, glass fibers (GF), 40% weight of the PEN component, were used to reinforce the blends to compensate for the loss of mechanical properties of PEN by incorporation of NBR. The results showed that the impact strength of the PEN/GF/NBR blend (PEN/NBR = 60/40) was increased up to 27.6J/m, nearly 5 times higher than that of the neat PEN. Meanwhile, the tensile strength and flexural strength were still maintained at as high as 66.1 MPa and 98.2 MPa, respectively. Dynamic vulcanization further improved the mechanical properties of the PEN/GF/NBR blends, which provided routes to the design of new PEN/elastomer blends. Other properties of the PEN/GF/NBR blends were also investigated in terms of morphology of fractured surface, dynamic mechanical behavior, thermal stability and crystallization, by scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively.     

Crystallization behavior and hydrophilicity of poly (vinylidene fluoride) (PVDF)/poly (styrene-<Emphasis Type="Italic">co</Emphasis>-acrylonitrile) (SAN) blends

Poly (styrene-co-acrylonitrile) (SAN) is a hydrophilic non-crystalline copolymer, which is initially used in this paper to improve the hydrophilicity of poly (vinylidene fluoride) (PVDF). Investigation of the crystallization behavior of PVDF/SAN blends showed that the samples presented only α phase regardless of SAN content as cooling from the melt. A double-melting phenomenon was related to the perfection or crystal size of PVDF crystals. As the SAN content is increasing, crystallization of PVDF was limited, leading to a decreased crystallinity and lamellar growth. Besides, the hydrophilicity of PVDF was improved by blending with SAN. The sample containing 70 wt.% SAN performed a similar surface property of the neat SAN owing to the besieging of the PVDF phase by SAN. Observed from the cross section of the blends, PVDF/SAN blends were partially miscible with less than 50 wt.% SAN addition. As the SAN content was more than 50 wt.%, the crystalline PVDF particles clearly dispersed in the amorphous matrix.     

Rheological,mechanical and morphological properties of thermoplastic vulcanizates based on NR‐g‐PMMA/PMMA blends

Graft copolymer of natural rubber and poly(methyl methacrylate) (NR‐g‐PMMA) was prepared using semi‐batch emulsion polymerization technique via bipolar redox initiation system. It was found that the grafted PMMA increased with the increase of methyl methacrylate (MMA) concentration used in the graft copolymerization. The NR‐g‐PMMA was later used to prepare thermoplastic vulcanizates (TPVs) by blending with PMMA through dynamic vulcanization technique. Conventional vulcanization (CV) and efficient sulphur vulcanization (EV) systems were studied. It was found that the CV system provided polymer melt with lower shear stress and viscosity at a given shear rate. This causes ease of processability of the TPVs via extrusion and injection molding processes. Furthermore, the TPVs with the CV system showed higher ultimate tensile strength and elongation. The results correspond to the morphological properties of the TPVs. That is, finer dispersion of the small vulcanized rubber particles were observed in the PMMA matrix. Various blend ratios of the NR‐g‐PMMA/PMMA blends using various types of NR‐g‐PMMA (i.e. prepared using various percentage molar ratios of NR and MMA) were later studied via dynamic vulcanization by a conventional sulphur vulcanization system. It was found that increasing the level of PMMA caused increasing trend of the tensile strength and hardness properties but decreasing level of elongation properties. Increasing level of the grafted PMMA in NR molecules showed the same trend of mechanical properties as in the case of increasing concentration of PMMA used as a blend component. From morphological studies, two phase morphologies were observed with a continuous PMMA phase and dispersed elastomeric phase. It was also found that more finely dispersed elastomeric phase was obtained with increasing the grafted PMMA in the NR molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

Effects of vulcanization accelerator functionalized graphene on the co-vulcanization kinetics and mechanical strength of NR/SBR blends

Rubber blends are widely used for combining the advantages of individual rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process are still a challenge. Herein, high resolution pyrolysis gas chromatography-mass spectrometry (PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene-butadiene rubber (SBR) in their blends filled with graphene. It is shown that the crosslinking rate of NR chains (k_NR) was much lower than that of SBR chains (k_SBR) in the unfilled blends and blends with untreated graphene. Interestingly, the gap between k_SBR and k_NR was narrowed effectively in the blends with vulcanization accelerator grafted graphene, showing a better co-vulcanization of NR and SBR. In addition, the vulcanization accelerator grafted graphene was uniformly dispersed in rubber matrix and endowed rubber blends with higher mechanical strength and thermal conductivity did the untreated graphene.     

线形低密度聚乙烯／废胶粉热塑弹性体动态硫化性能研究

利用动态硫化法制备了线形低密度聚乙烯(LLDPE)/废胶粉(GTR)热塑弹性体。重点研究了两种交联剂:硫和过氧化二异丙苯(DCP)对共混物性能的影响。加入一定量的苯乙烯-丁二烯-苯乙烯(SBS)共聚物作为增容剂。结果表明,经过DCP动态硫化后的共混物的力学性能比简单共混的共混物有明显的提高,而加入硫磺体系对共混物力学性能影响不大甚至有所下降。通过红外光谱、热分析(DSC)和扫描电镜(SEM)对共混物的热行为和表面形态研究表明,加入DCP交联剂使LLDPE、SBS和胶粉之间发生了交联反应,从而增加了胶粉颗粒与LLDPE间的界面相容性,使其热塑性弹性体的力学性能得以提高。     

硅橡胶/氟橡胶并用胶的制备及力学性能

硅橡胶和氟橡胶作为国防、航天等重要领域的耐热材料一直被人们青睐,但其有着各自地优缺点且价格昂贵,本文尝试将这两种橡胶制成并用胶以解决氟橡胶不耐低温和加工性差的问题,以期增大其使用温度范围。采用机械共混法制备硅橡胶/氟橡胶并用胶,研究了硅橡胶和氟橡胶的混炼工艺、并用比、共硫化体系和硫化条件对并用胶力学性能的影响。结果表明,当硅橡胶/氟橡胶的质量比为10∶90,共硫化体系为3~#硫化剂/过氧化二异丙苯(DCP),一段硫化温度为170℃、硫化压力为10MPa、硫化时间为30min,二段硫化温度为200℃、硫化时间为6h时,并用胶的力学性能达到最好。     

Reactively compatibilized and dynamically vulcanized thermoplastic elastomers based on high-density polyethylene and reclaimed rubber

Melt blending was employed to prepare thermoplastic elastomer (TPE) of reclaimed rubber (RR) and high density polyethylene (HDPE). Mechanical properties of TPE samples were improved in different methods including dynamic vulcanization and reactive blending (reactive compatibilization) during melt mixing in an internal Haake mixer. The physical and mechanical properties of the TPE blends were investigated by the dynamic mechanical analysis (DMA) and tensile tests. The thermal behavior was characterized by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The phase morphology of the blends was studied by scanning electron microscopy (SEM). Experimental results showed that, both static and dynamic mechanical properties of reactively-compatibilized and dynamically-vulcanized samples improved significantly compared with the virgin samples. The effect of dynamic-vulcanization and reactivecompatibilization on the mechanical properties revealed that the Young’s modulus and storage modulus increased with both improvement methods. SEM results showed that, dynamic-vulcanization and reactivecompatibilization methods improved the distribution of RR particles in HDPE matrix. Although both methods improved the thermal and mechanical properties of the HDPE/RR blends, dynamic-vulcanization was more effective and promising approach due to the higher properties of HDPE/RR blends prepared by this method.     

Morphology and non-isothermal crystallization of dynamically vulcanized PP/EPDM blends in situ compatibilized via magnesium dimethacrylate

Polypropylene/ethylene-propylene-diene rubber (PP/EPDM) blends in situ compatibilized by magnesium dimethacrylate (MDMA) were fabricated via peroxide-induced dynamic vulcanization. Scanning electron microscope observation indicated that the size of cross-linked EPDM particles decreased with incorporation of MDMA. Polarizing Optical Microscope (POM) analysis suggested that the spherulite size of PP phase decreased sharply with incorporation of MDMA during dynamic vulcanization. The Pseudo-Avrami, Ozawa and Mo's models were applied to analyze the non-isothermal crystallization kinetics of the composites. The analyzed data indicated that the crosslinked EPDM particles and homopolymerized MDMA acted as heterogeneous nucleating agents, which enhanced the crystallizability and decreased the spherulite size of the PP phase. In addition, the non-isothermal crystallization activation energy (ΔE) was calculated through the Kissinger and Friedman methods, and the ΔE value was found increase with incorporation of MDMA.     

Transparent and ductile poly(lactic acid)/poly(butyl acrylate) (PBA) blends: Structure and properties

Poly(butyl acrylate) was prepared by the free radical polymerization of butyl acrylate as an initiator in the presence of 2,2′-Azoisobu-tyronitrile (AIBN) and the average molecular weight, polydispersity and thermal stability were evaluated. PLA and PBA were melt blended using a Haake Rheometer, and the light transmission, thermal properties, dynamic rheological properties, mechanical properties, phase morphology of blends and toughening mechanism were investigated. Dynamic rheology, SEM and DSC results show that the PLA is partial miscible with PBA. The PBA component improved the crystallization ability of PLA and the crystallinity of PLA increased with content of PBA (<15 wt.%). With the increase of PBA, the tensile strength and modulus of the blend decreased slightly while the elongation at break and toughness were dramatically increased. With the addition of PBA, the failure mode changes from brittle fracture of neat PLA to ductile fracture of the blend. Rheological results revealed the complex viscosity and melt elasticity of the blends decreased with increasing content of PBA and phase segregation occurred at loading above 11 wt.% PBA. UV–vis light transmittance showed that PLA/PBA blends with a high transparency, and the transmittance decreased with the amount of PBA.     

Improving properties of natural rubber/polyamide 12 blends through grafting of diacetone acrylamide functional group

The aim of the present study was to improve the compatibility in blends of natural rubber (NR) and polyamide 12 (PA12) by grafting NR with hydrophilic monomer, diacetone acrylamide (DAAM), via seeded emulsion polymerization. The increase in polarity of NR after grafting modification was confirmed by a considerable increase in the polar component of its surface energy. Blends of graft copolymers of NR and poly(diacetone acrylamide) prepared using 10 wt% of DAAM (NR‐g‐PDAAM10) and PA12 were prepared at a 60/40 blend ratio (wt%) using simple blend and dynamic vulcanization techniques. The mechanical and rheological properties of the resulting blends were subsequently investigated and compared with those of the corresponding blends based on unmodified NR. The results show that dynamic vulcanization led to a significant increase in both mechanical and rheological properties of the blends. It was also observed that the dynamically cured NR‐g‐PDAAM10/PA12 blend had smaller particle size of vulcanized rubber dispersed in the PA12 matrix than observed for the dynamically cured NR/PA12 blend. This is due to the compatibilizing effect of DAAM groups present in NR‐g‐PDAAM10 molecule, which decreases the interfacial tension between the two polymeric phases. Therefore, it can be stated that the interfacial adhesion between NR and PA12 was improved by the presence of DAAM groups in NR molecule. This was reflected in the higher tensile properties observed in the dynamically cured NR‐g‐PDAAM10/PA12 blend. Copyright © 2017 John Wiley & Sons, Ltd.     

Dynamic mechanical properties of isotactic polypropylene/nitrile rubber blends: Effects of blend ratio,reactive compatibilization,and dynamic vulcanization

The effect of blend ratio and compatibilization on dynamic mechanical properties of PP/NBR blends was investigated at different temperatures. The storage modulus of the blend decreased with increase in rubber content and shows two T_g's indicating the incompatibility of the system. Various composite models have been used to predict the experimental viscoelastic data. The Takayanagi model fit well with the experimental values. The addition of phenolic modified polypropylene (Ph-PP) and maleic modified polypropylene (MA-PP) improved the storage modulus of the blend at lower temperatures. The enhancement in storage modulus was correlated with the change in domain size of dispersed NBR particles. The effect of dynamic vulcanization using sulfur, peroxide, and mixed system on viscoelastic behavior was also studied. Among these peroxide system shows the highest modulus. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2309–2327, 1997     

The effect of dynamic vulcanization on the properties of polymer-elastomer blends containing crumb rubber

The influence of dynamic vulcanization on the amount of the sol fraction, the crosslink density, the melt flow index, and the mechanical properties of ternary (isotactic polypropylene-rubber-crumb rubber) and binary (rubber-crumb rubber) blends was studied. Two types of ethylene-propylene-diene terpolymer (elastomer) were used as the rubber component, the oil-free elastomer and the elastomer extended with paraffin oil during its synthesis. The blends were vulcanized in the presence of a sulfur accelerating system. It was shown that blends with crumb rubber having a particle size of less than 0.1 mm exhibited the best mechanical and rheological characteristics. The introduction of crumb rubber into thermoplastic elastomers that contain the oil-free ethylene-propylene-diene terpolymer leads, at a certain ratio of the components, to a rise in the melt flow index, regardless of the crumb-rubber particle size and of whether the rubber component was vulcanized.     

Effect of P(MMA-co-MAA) compatibilizer on the miscibility of nylon 6/PVDF blends

With the ultimate objective of enhancing the impact strength and weatherability of nylon 6 engineering plastic, blending with poly(vinylidene fluoride) (PVDF) was studied. In the absence of a compatibilizer the two polymers phase separate, resulting in a deterioration of the properties. Since poly(methyl methacrylate) is known to be miscible with PVDF, we evaluated poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) of low methacrylic acid content as the compatibilizer. The carboxylic acid groups in the MAA units were expected to react with the end amino groups of nylon 6 forming block or graft copolymers, P(MMA-co-MAA)-g-nylon 6, in situ, which will function as the actual compatibilizer. The amount of P(MMA-co-MAA) added, the MMA/MAA composition and heat treatment time were varied to study their effects on the miscibility, morphology, and mechanical properties of nylon 6/PVDF blends. The enhancement of the compatibility of nylon 6 and PVDF by addition of P(MMA-co-MAA) and the partial miscibility of nylon 6 and PVDF has been confirmed through DSC, dynamic mechanical testing, SEM of fracture surfaces, and tensile testing. The decrease in the crystallization temperatures on addition of compatibilizer in DSC experiments suggests that the compatibilizer enhances the interaction between the two components and retards the crystallization. The dynamic mechanical thermal analysis experiments suggest that the compatibility in the amorphous regions of nylon 6 and PVDF in particular has been enhanced. The increase in the heat treatment time in the molten state resulted in further enhancement of the miscibility. The enhancement of compatibility by addition of a reactive compatibilizer and heat treatment resulted in a significant increase in the energy of rupture in tensile testing.     

Thermal stability and ageing properties of sulphur and gamma radiation vulcanized natural rubber (NR) and carboxylated styrene butadiene rubber (XSBR) latices and their blends

The thermal stability of natural rubber (NR) and carboxylated styrene butadiene rubber (XSBR) latices and their blends was studied by thermogravimetric methods. Ageing characteristics of these latex blends were studied by applying hot air oven thermal ageing for seven days at 70 °C. The mechanical properties of the aged samples were studied. Thermal degradation and ageing properties of these individual latices and their blends were investigated with special reference to blend ratio and vulcanization techniques. As the XSBR content in the blends increased their thermal stability was also found to increase. Among sulphur and radiation-vulcanized samples, radiation cured possesses higher thermal stability due to the higher thermal stability of carbon-carbon crosslinks. DTG curves were used for the determination of different stages involved in the degradation. Activation energy for degradation was determined from Coats-Redfern plot. The properties of aged samples were found to decrease due to chain depletion. However, the moduli of XSBR and NR/XSBR blends were found to increase owing to the formation of crosslinks upon ageing.