Rheological behavior of gel‐filled raw natural rubber and styrene‐butadiene rubber with reference to gel‐matrix intermixing

Natural rubber (NR) and styrene‐butadiene rubber (SBR) latex gels were prepared by sulfur prevulcanization technique with varying amounts of curing agent and accelerator systems to generate gradient in crosslink density. These gels were characterized by solvent swelling, dynamic light scattering, atomic force microscopy, and mechanical properties. Crosslinked NR gels were intermixed with neat SBR matrix and vice versa. Rheological behavior of chemically crosslinked gel‐filled NR and SBR was studied by capillary rheometry. Intermixing of crosslinked gels in the rubber matrices resulted in a considerable reduction in apparent shear viscosity and die swell values. This behavior was found to be dependent on several factors like gel concentration in the matrix, crosslink density of the gels, their size, and distribution. The effect of temperature on viscosity was studied extensively following the Arrhenious‐Eyring model. A shear rate‐temperature superposition mastercurve was constructed to predict the melt viscosities of the systems as a function of temperature. The change in die swell values was related to the change in first normal stress difference. The scanning electron photomicrographs of the extrudates revealed that presence of gels markedly improved the surface roughness of the raw rubbers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Studies of reinforcement behavior of unique elastomer‐based nanocomposite gels

Unique nanocomposite (NC) gels were prepared by blending water swollen unmodified montmorillonite clay suspension with natural rubber (NR) and styrene‐butadiene rubber (SBR) latices followed by prevulcanization. These were extensively characterized by dynamic light scattering, solvent swelling, tensile, and dynamic mechanical measurements. Reinforcement behavior of NC gels was investigated by adding NC gels into virgin NR and SBR matrices at various loadings. The distribution and morphology of NC gels in the elastomer matrices was studied by X‐ray dot mapping and high‐resolution transmission electron microscopy. Experimental results indicated tremendous improvement of tensile strength (TS) and modulus of the NC gel‐filled matrices along with noticeable changes in dynamic mechanical and rheological properties. Compared with virgin NR, the TS of 16 phr NC gel‐filled NR system increased by 117%. Similar level of enhancement of TS was also registered for the NC gel‐filled SBR systems. NC gel‐filled systems showed higher shear viscosities and lower die‐swell values compared with their virgin counterparts. Contemporary particulate composite and nanofiller reinforcement models were used to understand the reinforcing behavior of these NC gels. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers

BACKGROUND: Tack and green strength of filled and gum (unfilled) natural rubber (NR), poly(styrene‐co‐butadiene) rubber (SBR), polybutadiene rubber (BR) and (SBR‐BR) blend with different loadings of reinforcement agent, silanized silica nanofiller (Coupsil 8113), were studied and the results compared and discussed. RESULTS: It was found that silica was fully dispersed in rubber matrix after 13 min of mixing. In addition, with some exceptions for NR and (SBR‐BR) blend, filler loading decreased the tack strength of the studied filled rubbers. Green strength and Mooney viscosity increased with filler loading for all studied filled rubbers but with different rates and amounts. The optimum filler loadings for NR and (SBR‐BR) filled blend were 30 and 10 phr, respectively. Tacks of NR filled rubbers were much higher than those of synthetic filled rubbers. CONCLUSION: It was concluded that filler loading alters substantially the tack and green strength of the rubbers under investigation. Copyright © 2009 Society of Chemical Industry     

New approach for preparation of dry natural rubber nanocomposites through acid‐free co‐coagulation: Effect of organoclay content

Natural rubber (NR) vulcanizates exhibit good mechanical properties compared to vulcanizates of synthetic rubbers. Incorporation of a conventional filler at higher loadings to NR enhances its modulus, while reduction in tensile strength and elongation. This paper presents a new strategy for development of a NR‐clay nanocomposite with enhanced mechanical properties by incorporation of lower loadings (2–8 phr) of cetyl trimethyl ammonium bromide modified montmorillonite clay (OMMT‐C) under acid‐free environment. The effect of OMMT‐C loading on cure characteristics, rubber‐filler interactions, crosslink density, dynamic mechanical thermal properties, and mechanical properties were evaluated. Incorporation of OMMT‐C accelerated the vulcanization process and enhanced mechanical properties. X‐ray diffraction analysis and scanning electron microscopy images revealed that the formation of intercalated clay structures at lower OMMT‐C loadings, and clay aggregates at higher loadings. A nanocomposite at OMMT‐C loading of 2 phr exhibited the best balanced mechanical properties, and was associated with highest crosslink density and rubber–filler interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46502.     

Naturally occurring halloysite nanotubes for enhanced durability of natural rubber/ethylene propylene diene monomer rubber vulcanizate

A facile approach of using halloysite nanotubes (HNTs) was proposed to address the durability performance demands of natural rubber (NR)/ethylene propylene diene monomer rubber (EPDM) blends and to protect them from the deleterious effects of the service environment including ozone, chemicals, abrasion, and cyclic loading. The introduction of HNTs substantially improved the stability of NR/EPDM when exposed to ozone (over fourfold enhancement with the addition of 5 phr HNTs). Moreover, the HNT-filled NR/EPDM vulcanizates offered approximately 66% reduction in the solvent-mediated swelling in comparison to the unfilled sample. Fatigue life studies showed that the HNT-reinforced NR/EPDM composite could withstand 30% more cycles to failure than the un-reinforced NR/EPDM blend. The effect of various HNT loading on the morphological, mechanical, physical, and rheological properties of nanocomposite vulcanizates based on NR/EPDM was also investigated. The morphological investigations revealed that the introduction of HNT into the NR/EPDM rubber matrix caused a rough morphology in fracture surface and a well-dispersed structure was obtained with the addition of up to 5 phr of HNTs. These findings were further supported by rheological, mechanical, and thermodynamical results.     

Studies on blends of natural rubber and ethylene propylene diene rubber modified with phosphorylated cardanol prepolymer: Processability,physico‐mechanical properties,and morphology

The melt processability and physico‐mechanical properties of blends of natural rubber (NR) and ethylene propylene diene rubber (EPDM) containing different dosages (0–10 phr) of phosphorylated cardanol prepolymer (PCP) were studied in unfilled and china‐clay‐filled mixes. The plasticizing effect of PCP in the blends was evidenced by progressive reduction in power consumption of the mixing and activation energy for melt flow with an increase in the dosage of PCP. The PCP‐modified blend vulcanizates showed higher tensile properties and tear strength despite a decrease in the chemical crosslink density (CLD) index. This is presumably due to the formation of a crosslinked network structure of PCP with the rubbers and improved dispersion of the filler particles in the rubber matrix, as evidenced by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Thermogravimetric analysis showed an increase in thermal stability of the blend vulcanizate in presence of 5 phr of PCP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5123–5130, 2006     

Role of lignin filler in stabilization of natural rubber–based composites

The stabilizing effect of a natural filler, sulfur‐free lignin, on the thermal degradation of natural rubber (NR) was examined. Lignin was incorporated into NR in amounts of 10–30 phr (parts per hundred parts of rubber). It was shown that the lignin preparation used improved the physicomechanical properties of the rubber vulcanizates. Thermogravimetric analysis and differential scanning calorimetry were used to study the thermal degradation of unfilled and lignin‐filled vulcanized natural rubber. Measurements were carried out under atmospheric conditions. It was revealed that lignin used as filler increased the resistance of NR vulcanizates to thermooxidative degradation in air. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1226–1231, 2007     

Influence of Nanogels on Mechanical, Dynamic Mechanical, and Thermal Properties of Elastomers

Use of sulfur crosslinked nanogels to improve various properties of virgin elastomers was investigated for the first time. Natural rubber (NR) and styrene butadiene rubber (SBR) nanogels were prepared by prevulcanization of the respective rubber lattices. These nanogels were characterized by dynamic light scattering, atomic force microscopy (AFM), solvent swelling, mechanical, and dynamic mechanical property measurements. Intermixing of gel and matrix at various ratios was carried out. Addition of NR gels greatly improved the green strength of SBR, whereas presence of SBR nanogels induced greater thermal stability in NR. For example, addition of 16 phr of NR gel increased the maximum tensile stress value of neat SBR by more than 48%. Noticeable increase in glass transition temperature of the gel filled systems was also observed. Morphology of these gel filled elastomers was studied by a combination of energy dispersive X-ray mapping, transmission electron microscopy, and AFM techniques. Particulate filler composite reinforcement models were used to understand the reinforcement mechanism of these nanogels. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

纳米二氧化钛填充橡胶复合材料的分散结构与性能

用粒径为20～40nm的纳米二氧化钛(B—TiO2)填充天然橡胶(NR)和丁腈橡胶(NBR)制备了橡胶复合材料,研究了B—TiO2在橡胶基体中的分散结构、复合材料的力学性能以及抗菌性能,并与德国Degussa公司的催化剂纳米TiO2(D—TiO2)进行了对比。结果表明,B—TiO2在NR和NBR中表现出良好的分散,绝大多数B—TiO2在橡胶中聚集体尺寸小于100nm,特别是在NR中B—TiO2分散颗粒大小与其原生颗粒大小相近,明显优于D—TiO2在NR中的分散;在B—TiO2用量小的情况下,橡胶复合材料的力学性能基本不受B—TiO2的影响。D—TiO2对橡胶复合材料的老化性能也没有影响。橡胶基体中填充B—TiO2后,其抗菌性能明显提高,当用量超过2份(质量)时,其抗菌性能已经达到较高的水平;D—TiO2／NR抗菌效果与B—TiO2／NR的抗菌效果相当,热氧老化不影响橡胶复合材料中TiO2发挥其抗菌特性。     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

Rheology,cure characteristics,physical and mechanical properties of tire tread reclaimed rubber/natural rubber compounds

This work aimed to examine the effect of addition of tire‐tread reclaimed rubber on the properties of two natural rubber (NR) compounds with respect to the reclaimed rubber concentration and mastication time, the properties of interest including rheological and cure characteristics, physical and mechanical properties. The results under the test conditions suggested that Mooney Plasticity and shear viscosity increased with reclaimed rubber content, but decreased with mastication time. The greater the molar mass of the natural rubber the higher the sensitivity to the change in compound viscosity due to mastication and reclaimed rubber content. The die swell was more dependent on the reclaimed rubber than the molar mass of the rubbers. The cure rate and scorch time were found to increase and decrease with reclaimed rubber content, respectively, whereas the cure time was independent of the reclaimed rubber content. For vulcanized rubbers, it was also observed that 100% modulus of the rubber increased with reclaimed rubber content, but this was not the case for tensile stress and elongation at break. The hardness and heat buildup properties of the vulcanizates increased with reclaimed rubber content whereas the tear strength became independent of the reclaimed rubber. The findings in this work suggested that the variations in the rheological and cure characteristics for the unvulcanized rubber were very much dependent on the molar mass of the rubber whereas the mechanical properties for the vulcanized rubber were influenced by crosslink density. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1723–1731, 2003     

Effect of nano zinc oxide on the cure characteristics and mechanical properties of the silica‐filled natural rubber/butadiene rubber compounds

With the increasing interest in environmental and health issues, legal restrictions, such as European Union (EU) End of Life Vehicle Directives, were strengthened. This led us to incorporate nano zinc oxide (nano‐ZnO), with particle sizes of 30–40 nm and specific surface areas of 25.0–50.0 m²/g, instead of conventional ZnO into natural rubber (NR)/butadiene rubber (BR) compounds to decrease the content of zinc in the formulation. In the unfilled system, only a 20 wt % nano‐ZnO content, compared to conventional zinc oxide content, showed the cure characteristics and mechanical properties of the same level. This was because the increase in the specific surface area of the nano‐ZnO led to an increase in the degree of crosslinking. The effect of nano‐ZnO on the cure characteristics and mechanical properties was more pronounced in the silica‐filled system than in the unfilled system. This was mainly because of the dispersing agent used in the silica‐filled system, which also improved the dispersion of nano‐ZnO. The silica‐filled NR/BR compounds containing 0.3–3.0 phr of nano‐ZnO showed improved curing characteristics and mechanical properties, such as optimum cure time, 100 and 300% modulus, tensile strength, and tear strength compared to the compound with 5 phr of conventional ZnO. The optimum amounts of nano‐ZnO and stearic acid were only 1.0 and 0.1 phr, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

活性硅铝炭黑的性能及应用

将硅铝炭黑（ＳＡＣ）进行活化改性制成活性硅铝炭黑（ＡＳＡＣ）,并对ＳＡＣ和ＡＳＡＣ填充ＮＲ和ＳＢＲ胶料的硫化特性、物理性能及流变性能进行研究。结果表明,ＡＳＡＣ能明显改善ＳＡＣ的延迟硫化效应,提高填充胶料的力学性能;ＡＳＡＣ在ＮＲ中的填充补强效果接近半补强炭黑,在ＳＢＲ中的填充补强效果略优于优质陶土;ＡＳＡＣ填充ＮＲ胶料的流动性好,挤出胀大效应与填充半补强炭黑胶料相近     

Preparation and characterization of elastomer‐based nanocomposite gels using an unique latex blending technique

Nanocomposite (NC) gels based on natural rubber (NR) and styrene butadiene rubber (SBR) were prepared by using a unique latex blending technique. These NC gels were prepared by first blending the water swollen unmodified montmorillonite clay (Na⁺‐MMT) suspension into the respective latices followed by prevulcanization to generate crosslinked nanogels. Use of water assisted fully delaminated Na⁺‐MMT suspension resulted in predominantly exfoliated morphology in the NC gels, as revealed by X‐ray diffraction study and transmission electron microscopy. Addition of Na⁺‐MMT significantly improved various physical, mechanical and thermal properties of these NC gels. For example, 6 phr of Na⁺‐MMT loaded NR based NC gels registered 54% and 200% increase in tensile strength and Young's modulus, respectively, compared to the unfilled NR gels. SBR based NC gels also showed similar level of improvement in mechanical properties. Mechanical properties of NC gels prepared using this route were also compared with the NC gels prepared by co‐coagulation and conventional curing technique and found to be superior. In the case of dynamic mechanical properties, NC gels showed higher glass transition temperatures along with a concomitant increase in storage moduli, compared to the unfilled gels. These Na⁺‐MMT reinforced NC gels also exhibited markedly improved thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological behavior of a microcellular,oil-extended ethylene–propylene–diene rubber compound: Effects of the blowing agent curing agent,and conductive carbon black filler

The rheological behavior of microcellular, oil-extended ethylene–propylene–diene rubber (EPDM) compounds was studied in extrusions containing a blowing agent. The cell morphology development and rheological properties were studied for unfilled and conductive carbon black (Vulcan XC72, Cabot Corp., Ltd., Alpharetta, GA) filled compounds with variations of the blowing agent, extrusion temperature, and shear rate. The apparent shear stress, apparent viscosity, die swell (%), and total extrusion pressure of the Vulcan XC72 filled, oil-extended EPDM compounds were determined with a Monsanto processability tester (St. Louis, MO). The effects of the curing agent and blowing agent on the rheological properties of the compounds were also studied. A significant reduction in the stress and viscosity with the blowing agent was observed in the compound in the presence of the curing agent in comparison with those without the curing agent. The viscosity reduction factor was found to be dependent on the blowing agent loading, shear rate, and temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological behaviour of copoly(ethylene/octene) elastomer compunds: Effect of blowing agent and precipitated CaCO3 filler

Abstract

An experimental study of the rheological behaviour of ethylene/octene copolymer compounds in extrusion containing blowing agent has been carried out. The cell morphology development was studied using scanning electron microscopy. Rheological properties of unfilled and precipitated CaCO₃ filled systems with various blowing agents, extrusion temperatures, and shear rates were studied using a capillary rheometer. The total extrusion pressure, apparent shear stress, apparent viscosity, and die swell of the unfilled and CaCO₃ filled compounds were also determined and the effect of blowing agent on the rheological properties of the compounds studied. It was observed that there is reduction of stress and viscosity with blowing agent loading. Incorporation of blowing agent led to decreased shear thinning behaviour resulting in an increase in the power law index. The viscosity reduction factor of the unfilled compound was found to be dependent on the concentration of blowing agent, the shear rate, and the temperature.     

Rheological behavior of ethylene–octene copolymer vulcanizates: Effect of blowing agent and precipitated silica filler

An experimental study of the rheological behavior of ethylene–octene copolymer vulcanizates in extrusion containing blowing agent has been carried out. The cell morphology development has been studied through a scanning electron microscope. Rheological properties of unfilled and precipitated silica‐filled systems with variations of blowing agent, extrusion temperature, and shear rate have been studied by using a Monsanto processibility tester (MPT). The total extrusion pressure (P_T), apparent shear stress (τ_wa), apparent viscosity (η_a), and die swell (%) of the unfilled and silica‐filled compounds have been determined by using MPT. The effect of blowing agent (ADC) on the rheological properties of the vulcanizates has also been investigated. There is a reduction of stress and viscosity with blowing agent loading. It was observed that the incorporation of a blowing agent led to decreased shear thinning behavior resulting in an increase in power law index. The viscosity reduction factor (VRF) of unfilled vulcanizates is found to be dependent on the concentration of the blowing agent, shear rate, and temperature, whereas VRF of silica‐filled vulcanizates is found to be dependent on shear rate, temperature, and blowing agent concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1132–1138, 2003     

用作载重子午线轮胎胎面胶的炭黑填充粉末NR结构与性能研究

以天然胶乳和炭黑N234为原料,采用凝聚共沉法制备炭黑填充型粉末NR[P(NR/CB)],研究炭黑用量和不同配方对胶料硫化特性、物理性能、交联密度、微观结构、Payne效应及动态力学性能的影响,并与采用传统机械混炼法制备的炭黑/NR(CB/NR)进行对比.结果表明,与CB/NR硫化胶相比,P(NR/CB)硫化胶具有较高的拉伸强度、撕裂强度、回弹值和抗湿滑性能以及较低的滚动阻力,耐屈挠性能和耐磨性能大致相当,而动态压缩生热和压缩永久变形则降低了近50%.     

Effects of the presence of water on ultrasonic devulcanization of polydimethylsiloxane

The effects of the presence of water on ultrasonic devulcanization of 30 phr silica‐filled polydimethylsiloxane (PMDS) were investigated at increasing feed rates and different die gap sizes. The results showed that the initial die entrance pressure without ultrasound for wet rubber was higher than in the case without water and then it decreased monotonously with applying ultrasound. The die pressure for wet rubber decreased significantly even at low ultrasonic amplitude, while that for dry rubber changed little at low amplitude. The power consumption at an amplitude of 10 μm, where devulcanization was most effectively achieved, was lower for wet rubber even though the pressure was lower. The crosslink density and gel fraction after the devulcanization of wet rubber were lower than those of dry rubber, indicating that the presence of water facilitates the devulcanization process under the same devulcanization conditions. The good mechanical properties of recycled silica‐filled PDMS were obtained at higher feed rates and at lower ultrasound amplitudes, which are directly related to the economics of a recycling process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2630–2638, 2003     

天然橡胶/再生胶共混胶的交联密度与力学性能

对不同天然橡胶(NR)/再生胶(RR)共混比、不同硫磺及轻质碳酸钙含量的NR/RR共混胶的交联密度和力学性能进行分析测试,并对RR的橡胶烃含量、炭黑含量和无机杂质含量进行热失重测试分析。结果表明,随着RR含量和硫磺含量的增加,硫化胶交联密度上升,轻质碳酸钙含量变化对于硫化胶交联密度没有产生规律性的影响。NR/RR共混比为70/30,硫磺用量为2.5份时NR/RR共混胶综合性能最佳。