Relationships among blending conditions,size of dispersed phase,and oil resistance in natural rubber and nitrile rubber blends

The rheological properties, morphology, and oil resistance in natural rubber and nitrile‐butadiene rubber (NR/NBR) blends are investigated as functions of the blending conditions. It is found that the Mooney viscosity of the blends depends more strongly on the blending time than the rotor speed. The size of the NR dispersed phase is approximately independent of the rotor speed, but it decreases with increasing blending time up to 25 min. With a further increase in the blending time the NR dispersed phase size decreases. The results for the relative tensile strength, which is an indicator of oil resistance, are in agreement with those of the blend morphology, indicating that the oil resistance in a 20/80 NR/NBR blend strongly depends on the phase morphology of the blend. The smaller the size of NR dispersed phase, the higher the blend resistance to oil. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1232–1237, 2001     

Oil and thermal aging resistance in compatibilized and thermally stabilized chlorinated polyethylene/natural rubber blends

Influences of EPDM-g-MA as a compatibilizer and a phenolic antioxidant on oil and thermal aging resistance in 50/50 CPE/NR blends were investigated. It has been found that EPDM-g-MA could decrease phase size of the blend system, indicating compatibilizing effect. The optimal concentration of EPDM-g-MA is 1 phr. Beyond this concentration, phase size starts to increase. The addition of phenolic antioxidant apparently decreases the phase size in blends. This is probably due to the improvement in a thermal stabilization of NR phase in blends provided by the antioxidant, which leads to a reduction in phase coalescence during blending. In addition, the results of oil and thermal aging resistance are in good agreement with the morphological results, indicating that the oil resistance and thermal aging properties based on relative tensile strength in the 50/50 CPE/NR blends are strongly controlled by the size of the NR dispersed phase in CPE matrix. The smaller the dispersed phase size, the higher the resistance to oil and thermal aging.     

Peroxide cured natural rubber/fluoroelastomer/high‐density polyethylene via dynamic vulcanization

In this work, blends of fluoroelastomer (FKM), natural rubber (NR) along with high‐density polyethylene (HDPE) by dynamic vulcanization using peroxide (DBPH, DCP) as a curing agent were prepared. HDPE was melt‐mixed with NR and FKM at different compositions (HDPE/FKM/NR i.e. 30/60/10, 30/55/15, 30/50/20, and 30/35/35%wt) using an internal mixer at 150°C and 50 rpm rotor speed. The mechanical properties and oil swelling resistances of these blends were analyzed according to ISO 37 (Type 1) and ASTM D471, respectively. The results suggest that DBPH works better as a curing agent for the dynamic vulcanization system than DCP. The optimum mechanical properties and oil resistance were revealed in 30/50/20 and 30/60/10 HDPE/FKM/NR, being dynamic vulcanized with DBPH, respectively. In addition, was found that a dispersed HDPE phase shows the percent crystallinity in the range of 53% to 55% upon increasing the NR content. The SEM micrographs reveal the NR phase is well dispersed in FKM as small particles. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers .     

Effects of fillers,maleated ethylene propylene diene diene rubber,and maleated ethylene octene copolymer on phase morphology and oil resistance in natural rubber/nitrile rubber blends

The phase morphology and oil resistance of 20/80 NR/NBR blends filled with different types of fillers and copolymers were investigated. In the case of filler effect, N220, N330, and N660 carbon blacks with different particle sizes were used. Additionally, the blends filled with nonblack‐reinforcing fillers, that is, precipitated and silane‐treated silica, were investigated. To study the compatibilization effect, maleated ethylene propylene diene rubber (EPDM‐g‐MA) and maleated ethylene octene copolymer (EOR‐g‐MA) were added to the blends. The results revealed that the addition of filler, either carbon black or silica, to the blend caused a drastic decrease in NR dispersed phase size. Carbon blacks with different particle sizes did not produce any significant difference in NR dispersed phase size under the optical microscope. Silica‐filled blends showed lower resistance to oil than did the carbon black–filled blends. In addition, it was determined that neither EOR‐g‐MA nor EPDM‐g‐MA could act as a compatibilizer for the blend system studied. The oil resistance of the blends with EPDM‐g‐MA is strongly affected by the overall polarity of the blend. In the case of EOR‐g‐MA, the oil resistance of the blends is significantly governed by both overall polarity of the blend and phase morphology. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1156–1162, 2003     

Mechanical properties,oil resistance,and thermal aging properties in chlorinated polyethylene/natural rubber blends

The use of natural rubber (NR) for partly substituting elastomeric chlorinated polyethylene (CPE) was determined. Mechanical and thermal aging properties as well as oil resistance of the blends were also investigated. The amount of NR in blends significantly affected the properties of the blends. The blends with NR content up to 50 wt % possessed similar tensile strength to that of pure CPE even after oil immersion or thermal aging. Modulus and hardness of the blends appeared to decrease progressively with increasing NR content. These properties also decreased in blends after thermal aging. After oil immersion, hardness decreased significantly for the blends with high NR content, whereas no change in modulus was observed. The dynamic mechanical properties were determined by dynamic mechanical thermal analysis. NR and CPE showed damping peaks at about ?40 and 4 °c, respectively; these values correlate with the glass‐transition temperatures (T_g) of NR and CPE, respectively. The shift in the T_g values was observed after blending, suggesting an interfacial interaction between the two phases probably caused by the co‐vulcanization in CPE/NR blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 22–28, 2002; DOI 10.1002/app.10171     

Phase morphology development and melt rheological behavior in nylon 6/polystyrene blends

Phase morphology development in immiscible blends of polystyrene (PS)/nylon 6 was investigated. The blends were prepared by melt blending in a twin‐screw extruder. The influence of the blend ratio, rotation speed of the rotors, and time of mixing on the phase morphology of the blends was carefully analyzed. The morphology of the samples was examined under a scanning electron microscope (SEM) and the SEM micrographs were quantitatively analyzed for domain‐size measurements. From the morphology studies, it is evident that the minor component, whether PS or nylon, forms the dispersed phase, whereas the major component forms the continuous phase. The 50/50 PS/nylon blend exhibits cocontinuous morphology. The continuity of the dispersed phase was estimated quantitatively based on the preferential solvent‐extraction technique, which suggested that both phases are almost continuous at a 50/50 blend composition. The effect of the rotor speed on the blend morphology was investigated. It was observed that the most significant breakdown occurred at an increasing rotor speed from 9 to 20 rpm and, thereafter, the domain size remained almost the same even when the rotor speed was increased. The studies on the influence of the mixing time on the blend morphology indicated that the major breakdown of the dispersed phase occurred at the early stages of mixing. The melt rheological behavior of the blend system was studied using a capillary rheometer. The effect of the blend ratio and the shear stress on the melt viscosity of the system was investigated. Melt viscosity decreased with increase in the shear stress, indicating pseudoplastic behavior. With increase of the weight fraction of PS, the melt viscosity of the system decreased. The negative deviation of the measured viscosity from the additivity rule indicated the immiscibility of the blends. The domain size versus the viscosity ratio showed a minimum value when the viscosities of the two phases were matched, in agreement with Wu's prediction. The morphology of the extrudates was analyzed by SEM. From these observations, it was noted that as the shear rate increased the particle size decreased considerably. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3537–3555, 2002     

白炭黑用量对氯丁橡胶/天然橡胶共混物性能的影响

研究了不同用量的沉淀法白炭黑填充质量比75/25的氯丁橡胶/天然橡胶共混物的物理机械性能、耐热老化性能和耐油性能,并用扫描电镜研究了共混物的结构。结果显示,白炭黑的加入改善了共混硫化物的拉伸强度、100%定伸应力和邵尔A硬度。压缩永久变形减小,黏度增大,从而导致在形变的过程中天然橡胶分散相占有率相对减少。相关性能也证明随着白炭黑用量的增加,硫化胶的耐热和耐油性能显著提高。     

Influence of precipitated silica on dynamic mechanical properties and resistance to oil and thermal aging in CPE/NR blends

Blends of 80/20 CPE/NR filled with various silica loadings were prepared, and their properties were determined. It was found that cure properties are influenced significantly by the addition of precipitated silica. Scorch time and cure time decrease with increasing silica loading, which could be explained by the thermal history attributed to the shear heating in the blending stage. An increase in crosslink density as a function of silica loading is believed to be caused by a migration of curatives to the NR phase. In terms of phase morphology, with increasing silica loading, the NR dispersed phase size decreases due to the increase in compound viscosity and, thus, the shear stress available for efficient blending. An increase in silica loading also enhances resistance to oil due to the decrease in the NR dispersed phase size associated with the dilution effect, but gives no significant impact on thermal aging resistance. According to the change in damping peak height associated with the shift in T_g of the CPE phase, silica appears to preferentially migrate to the CPE phase due to the strong interaction between CPE and silanol groups of the silica surfaces. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2218–2224, 2005     

Influence of silica loading on the mechanical properties and resistance to oil and thermal aging of CR/NR blends

Blends of 75/25 chloroprene rubber(CR)/natural rubber (NR) filled with various loadings of precipitated silica were prepared and their processability and mechanical properties as well as their resistance to thermal aging and oil were determined. The blend morphology was also studied using the atomic force microscopy technique. The results reveal that the mixing energy and the Mooney viscosity of the compound are increased continuously with increasing silica loading. It is also found that both scorch and optimum curing times are shortened while the total crosslink density is increased with increasing silica loading. The positive effect on cure could be explained by the chemical reaction between the allylic chlorine atom of CR and the silanol group on silica surface. The tensile strength, modulus, and hardness of the blend vulcanizate are noticeably improved while the compression set at elevated temperature is impaired with increasing silica loading. The results also reveal that both thermal aging resistance and oil resistance of the blend vulcanizates, as represented by the relative properties, are enhanced with the addition of silica. The resistance enhancement is believed to arise from the combination of the dilution effect, the increased crosslink density and also the reduction of NR dispersed phase size. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Rheological properties,oil, and thermal resistance in sulfur‐cured CPE/NR blends

The use of natural rubber (NR) for partly substituting elastomeric chlorinated polyethylene (CPE) was carried out. Sulfur curing was used to vulcanize NR phase in the blends. Mechanical, rheological, and thermal aging properties as well as oil resistance of the blends were investigated. The amount of NR in blends significantly affects properties of the blends. With NR content in blends up to 20 wt %, tensile properties are similar to those of the pure CPE, even after either oil immersion or thermal aging. Rheological properties of CPE/NR blends determined from the rubber process analyzer (RPA 2000) and parallel‐plate rheometer are controlled strongly by the blend composition. The viscoelastic behavior of pure CPE and the blends with CPE as a major component is governed by the viscous response, which could be seen from the high damping factor, particularly at high strain, the short linear viscoelastic range, and the high degree of pseudoplasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1129–1135, 2004     

Nylon 6/ethylene propylene rubber (EPM) blends: Phase morphology development during processing and comparison with literature data

The morphology of immiscible blends of nylon 6 and ethylene propylene rubber blends (EPM) was studied. The blends were prepared by melt blending in a twin‐screw miniextruder and a Haake Rheocord mixer. The influence of the blend ratio, time of mixing, rotation speed of the rotors, mixing temperature, and quenching of the extruded melt at low temperature on the phase morphology of the blends was quantitatively analyzed. The morphology was examined by scanning electron microscopy (SEM) after preferential extraction of the minor phase. The SEM micrographs were quantitatively analyzed for domain‐size measurements. The morphology of the blends indicated that the EPM phase was preferentially dispersed as domains in the continuous nylon matrix up to 40 wt % of its concentration. A cocontinuous morphology was observed at 50 and 60 wt % EPM content followed by a phase inversion beyond 60 wt % of EPM where the nylon phase was dispersed as domains in the continuous EPM phase. The size, shape, and distribution of the domains were evaluated by image analysis as a function of the blend composition. The effect of the time of mixing on the phase morphology was studied up to 20 min for the 30/70 EPM/nylon blend. The most significant domain breakup was observed within the first 3 min of mixing followed by a leveling off up to 15 min. This may be associated with the equilibrium between the domain breakup and coalescence. The influence of rotor speed on the morphology was insignificant at a high rotor speed although a significant effect was observed by changing the rotor speed from 9 to 20 rpm. The influence of high‐temperature annealing, repeated cycles of extrusion, the molecular weight of the nylon matrix, and the nature of the mixer type (twin‐screw miniextruder versus Haake Rheocord mixer) on the morphology was also investigated in detail. The experimental results were compared with literature data. Finally, the extent of interface adhesion in these blends was analyzed by examination of the fracture‐surface morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1405–1429, 1999     

Development of dispersed phase size and its dependence on processing parameters

Through measurement of phase dimension via laser scattering, phase morphology development in immiscible blends of polyamide 12/poly(ethylene glycol) (PEG) with an extremely high viscosity ratio was investigated. The blends were prepared by melt blending in a batch mixer. The objective was to examine the influence of mixing time, rotor speed, as well as blending temperature on the size distribution of the minor phase. It is of interest that the breakup process of the dispersed PA 12 phase was observed for the blend systems even for extremely high viscosity ratios of ≤ 10²–10³. Mixing time had a significant effect on the development of dispersed phase size distribution. It was found that the bulk of particle size reduction took place very early in the mixing process, and very small droplets with a diameter of 0.1–10 μm were produced. The number of small particles then decreased, resulting in a larger average particle size. With further prolonged mixing, the particle size levels off. The particle size and its distribution were also found to be sensitive to the rotor speed. The average particle size decreased with increased rotor speed. The effect of blending temperature on size and size distribution, which has seldom been studied, was also examined in this work. When the blending temperature altered from 190°C to 220°C, the size and its distribution of the dispersed phase varied considerably, and the change of viscosity ratio was found to be the key factor affecting the dispersed phase size. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3201–3211, 2006     

Comparison Properties of Natural Rubber (SMR L)/Ethylene Vinyl Acetate (EVA) Copolymer Blends and Epoxidized Natural Rubber (ENR-50)/Ethylene Vinyl Acetate (EVA) Copolymer Blends

Mixing torque, morphology, tensile properties and swelling studies of natural rubber/ethylene vinyl acetate copolymer blends were studied. Two series of unvulcanized blends, natural rubber/ethylene vinyl acetate (SMRL/EVA) copolymer blend and epoxidized natural rubber (50% epoxidation)/ethylene vinyl acetate (ENR-50/EVA) copolymer blend were prepared. Blends were prepared using a laboratory internal mixer, Haake Rheomix polydrive with rotor speed of 50 rpm at 120°C. Results indicated that mixing torque value and stabilization torque value in ENR-50 blends are lower than SMRL blends. The process efficiency of ENR-50/EVA blends is better due to less viscous nature of the blend compared to SMRL/EVA blends as indicated in stabilization torque graph. Tensile properties like tensile strength, M100 (modulus at 100% elongation) and E _b (elongation at break) increase with increasing EVA fraction in the blend. At the similar blend composition, ENR-50 blend shows better tensile properties than SMRL blends. In oil resistance test, swelling percentage increased with immersion time and rubber composition. At a similar immersion time, ENR-50 blends exhibit better oil resistance compared to SMRL blends. Scanning electron microscopy (SEM) of tensile fractured surface indicated that EVA/ENR-50 blends need higher energy to cause catastrophic failure compared to EVA/SMRL blends. In etched cryogenically fractured surface, size and distribution of holes due to extraction of rubber phase by methyl ethyl ketone (MEK) were studied and holes became bigger as rubber composition increased due to coalescence of rubber particle.     

Influences of the phenolic curative content and blend proportions on the properties of dynamically vulcanized natural rubber/acrylonitrile–butadiene–styrene blends

The vulcanization of natural rubber (NR)‐blended acrylonitrile–butadiene–styrene (ABS) was carried out with a phenolic curing agent by a melt‐mixing process. The NR compound was first prepared before blending with ABS. The effects of the phenolic curative contents (10, 15, and 20 phr) and blend proportions (NR/ABS ratio = 50 : 50, 60 : 40, and 70 : 30) on the mechanical, dynamic, thermal, and morphological properties of the vulcanized NR/ABS blends were investigated. The tensile strength and hardness of the blends increased with increasing ABS content, whereas the elongation at break decreased. The strength property resulting from the thermoplastic component and the vulcanized NR was an essential component for improving the elasticity of the blends. These blends showed a greater elastic response than the neat ABS. The thermal stability of the blends increased with increasing ABS component. Scanning electron micrographs of the blends showed a two‐phase morphology system. The vulcanized 60 : 40 NR/ABS blend with 15‐phr phenolic resin showed a uniform styrene‐co‐acrylonitrile phase dispersed in the vulcanized NR phase; it provided better dispersion between the NR and ABS phases, and this resulted in superior elastic properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42520.     

Mechanical properties and blend compatibility of natural rubber –chlorosulfonated polyethylene blends

Natural rubber (NR) was blended with chlorosulfonated polyethylene (CSM) with various formulation and blend ratios (NR/CSM: 80/20 –20/80, wt/wt). Rubber blends were prepared by using a two‐roll mill and vulcanized in a compression mold to obtain the 2 mm‐thick sheets. Tensile properties, tear resistance, thermal aging resistance, ozone resistance, and oil resistance were determined according to ASTM. Compatible NR/CSM blends are derived from certain blends containing 20–30% CSM without adding any compatibilizing agent. Tensile and tear strength of NR‐rich blends for certain formulations show positive deviation from the rule of mixture. Thermal aging resistance depends on formulation and blend ratio, while ozone and oil resistance of the blends increase with CSM content. Homogenizing agents used were Stuktol®60NS and Epoxyprene®25. Stuktol®60NS tends to decrease the mechanical properties of the blends and shows no significant effect on blend morphology. Addition of 5–10 phr of epoxidized natural rubber (ENR, Epoxyprene® 25) increases tensile strength, thermal aging resistance, and ozone resistance of the blends. It is found that ENR acts as a compatibilizer of the NR/CSM blends by decreasing both CSM particle size diameter and α transition temperature of CSM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 127–140, 2006     

Morphology evolution of immiscible LDPE/PVC blends in the presence of compatibilizer and phase dispersant

Phase dispersion and coalescence in low‐density polyethylene (LDPE)/polyvinyl chloride (PVC) (70/30) blends influenced by compatibilizer and phase dispersant was studied. It was found that the morphology evolution of blends is sensitive to not only processing conditions (shear strength and mixing time) but also the added compatibilizer or phase dispersant. In our conditions, the stable phase morphology of each blend is obtained after mixing 15–25 min. In addition, the dispersed PVC phase in blends is easy to aggregate when the mixing rotor speed changed from high to low for the binary blends. As a compatibilizer, chlorided polyethylene (CPE) or nitrile rubber (NBR) can stabilize the morphology and hinder the coalescence of the dispersed PVC phase when added to the blends. However, the phase dispersant butadiene rubber (BR) or styrene butadiene rubber (SBR) could not stabilize the phase structure, although it could accelerate phase dispersion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 763–772, 2004     

Changes in morphology and properties of NR–NBR blends. Effect of viscosity ratio modified by liquid natural rubber and epoxidised liquid natural rubber

Abstract

Changes in rheological properties, morphology, and oil resistance in NR–NBR blends by viscosity ratio have been investigated. In this study, the viscosity ratio was modified by mechanical mastication and addition of liquid natural rubber (LNR) and epoxidised liquid natural rubber (ELNR). The results reveal that as viscosity ratio increased from 0·5 to 1·0, Mooney viscosity of the blends increased, and then decreased sharply as the viscosity ratio further increased from 1·0 to 2·0. The addition of LNR and ELNR for plasticising NR and NBR, respectively, does not significantly affect cure properties of the blends. The phase size of the NR dispersed phase depends strongly on the viscosity ratio. The high viscosity of the matrix and/or the low viscosity of the dispersed phase promote breaking up of the dispersed phase. Unexpectedly, a decrease in size of the dispersed phase by the modification of viscosity ratio via the use of low molecular weight rubber (i.e. LNR and ELNR) did not result in an improvement in oil resistance.     

Properties of Polypropylene (PP)/Ethylene-Propylene Diene Terpolymer (EPDM)/Natural Rubber (NR) Vulcanized Blends: The Effect of N,N-m-Phenylenebismaleimide (HVA-2) Addition

This paper discusses process development, tensile properties, morphology, oil resistance, gel content, and thermal properties of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) vulcanized blends with the addition of N,N-m-phenylenebismaleimide (HVA-2) as a compatibilizer. Blends were prepared in several blend ratios in a Haake Polydrive with temperature and rotor speed of 180°C and 50 rpm, respectively. Results indicated that the combination of dicumyl peroxide (Dicup) with HVA-2 shows high torque development and stabilization torque as compared to the blend with Dicup vulcanization alone. In terms of tensile properties, the combination of Dicup with HVA-2 shows higher tensile strength, tensile modulus (M₁₀₀), elongation at break, oil resistance, and gel content in all blend ratios compared to similar vulcanized blends with Dicup without HVA-2 addition. Scanning electron microscope (SEM) micrographs of the blends support that the cross-linking and compatibilization occur during the process of the vulcanized blend containing HVA-2. In the case of crystallinity of the blends, the addition of HVA-2 in Dicup vulcanized blend revealed a tendency for the percentage of crystallinity (Xc) to decrease. The addition of HVA-2 in Dicup vulcanization also produced blends with good thermal stability dealing with the so-called coagent bridge formation.     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Phase morphology development of polypropylene/ethylene-octene copolymer blends: effects of blend composition and processing conditions

Summary Blends of polypropylene (PP)/ethylene-octene copolymer (EOC) was studied. The influences of blend composition and processing conditions on phase morphology development of the blends were investigated by scanning electron microscopy (SEM) in detail. The minor composition formed the dispersed phase and the major composition formed the continuous phase, and the blends formed interpenetrating co-continuous morphology just at the intermediate concentration. The effect of concentration on phase coarsening was explained by the increase of dispersed phase coalescence with dispersed phase concentration’s increase. Phase coarsening and phase fine dispersing were studied. The effect of mixing time on phase morphology development of the blends was investigated, the PP/EOC (80/20) blends has already formed a well-established droplet/matrix morphology after 1.5 min of mixing, and the similar blends phase morphology persisted until 11 min of mixing. The most prominent phenomenon is that the dispersed phase domain deformed from spherical droplet to elliptical droplet, even fibrillar or sheet morphology as the rotor speed increased. The increase of shear rate and elasticity ratio was applied to interpret this phenomenon.