Rice‐husk‐ash‐filled natural rubber. II. Partial replacement of commercial fillers and the effect on the vulcanization process

In a previous investigation, we observed that in the presence of a conventional vulcanization system, the addition of white rice husk ash (WRHA) to natural rubber (NR) compounds increased the rate of crosslinking and lowered the apparent activation energy (E_a) of the vulcanization reaction more strongly than the other fillers used. In this work, commercial fillers, such as precipitated silica (Zeosil‐175) and carbon black (N762), were partially replaced by black rice husk ash and WRHA. Cure studies were carried out on a TI‐100 curometer at 150, 160, 170, and 180°C, and the overall rates and the E_a's for the vulcanization process were calculated for each compound, with the assumption that vulcanization followed first‐order kinetics. Again, WRHA showed some catalytic effect on the NR vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1405–1413, 2003     

Rice husk ash filled natural rubber. III. Role of metal oxides in kinetics of sulfur vulcanization

In preceding investigations the overall rate and apparent activation energy for the vulcanization process were calculated for natural rubber compounds, assuming that vulcanization follows first‐order kinetics. It was observed that the addition of white rice husk ash (WRHA) increased the rate of crosslinking and lowered the apparent activation energy more profoundly than commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N762), with a conventional vulcanization system. In this work, a specific model for the vulcanization process accelerated by N‐cyclohexylbenzothiazole sulfenamide was used to investigate the real role of WRHA in crosslink formation. Cure studies were carried out at 150°C, and the kinetics constants were evaluated. In relation to the other fillers, WRHA seems to develop catalytic activity, resulting in a positive effect on the specific rate of crosslink formation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1519–1531, 2003     

Design and analysis of single-factor experiments: Analysis of variance of the effect of rice husk ash and commercial fillers in NR compounds

Summary White rice husk ash (WRHA) and black rice husk ash (BRHA) were incorporated into natural rubber (NR) using a laboratory-sized two-roll mill. A conventional vulcanization system was used for curing and physical tests of the NR vulcanized involved determining of tensile and tear resistances. For comparison purposes, precipitated silica (Zeosil-175) and carbon black (N774) were used too. Using the analysis of variance of single-factor experiments, it can be concluded that: BRHA is non-reinforcing filler and its use is limited to 20 phr; WRHA is semi-reinforcing filler and the variation of filler loading (0 up to 50 phr) causes the maximum variation upon tensile strength of NR compounds; and, that although carbon black and silica are reinforcing fillers, a real reinforcement is reached up to 20 phr for tensile strength.     

RICE HUSK ASH FILLED NATURAL RUBBER COMPOUNDS – THE USE OF RHEOMETRIC DATA TO QUALITATIVELY ESTIMATE OPTIMUM FILLER LOADING

White rice husk ash (WRHA) and black rice husk ash (BRHA) were incorporated as filler in natural rubber (NR) compounds. A conventional vulcanization system (CV) was chosen and cure studies were carried out on a TI-100 Curometer at 150, 160, 170 and 180°C. From the rheometric data obtained at 150°C, a specific constant related to the filler structure was evaluated that allowed predictions on how the presence of filler would affect mechanical properties such as tensile and tear resistances, and hardness. Swelling behavior and examination of the fracture surface, which was carried out on a Scanning Electron Microscope (SEM), were used to get some idea on the interaction between the rubber matrix and the filler. WRHA showed a good reinforcing potential for NR compounds and catalytic effect upon vulcanization.     

Mechanical and dynamic mechanical properties of rice husk ash–filled natural rubber compounds

A laboratory‐sized two‐roll mill was used to incorporate rice husk ash into natural rubber (NR). A conventional vulcanization system was used for curing and cure studies were carried out on a Monsanto rheometer. Physical testing of the NR vulcanizates involved determining tensile and tear resistances and hardness. Swelling behavior of NR compounds and scanning electron microscopy were used to investigate the interaction between rice husk ash and natural rubber. Also, dynamical mechanical thermal analysis was used to assess filler–rubber interactions in terms of storage modulus (E′) and loss tangent (tan δ). For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N774), were also used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2331–2346, 2002     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry     

The effect of coupling agent and chemical treatment on rice husk ash‐ filled natural rubber composites

Rice husk ash was incorporated into natural rubber (NR) using a laboratory size two‐roll mill. Curing using a conventional vulcanization system (CV) was chosen, and cure studies were carried out on a Monsanto rheometer. Physical testing of the NR vulcanizates involved the determination of tensile, tear, and abrasion resistances, and hardness. Fourier transform infrared spectroscopy (FTIR) analysis was done to verify the presence of the characteristic functional groups of precipitated silica in MHA (milled husk ash) and THA (treated husk ash). The effect of the coupling agent, bis(3‐triethoxysilylpropyl)‐tetrasulfane (Si‐69), on the curing and physical properties of the vulcanizates was investigated. A chemical treatment on a rice husk ash was done, and the effects of this procedure are also reported. For comparison, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N774), were also used. Although the presence of the silane coupling agent had not brought the expected increase in properties, treated husk ash showed exceptional performance in terms of tensile strength and abrasion resistance of the filled vulcanizates. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1019–1027, 2000     

Effect of a silane coupling agent on the properties of white rice husk ash–polypropylene/natural rubber composites

White rice husk ash (WRHA)–polypropylene (PP)/natural rubber (NR) composites were prepared using a Brabender Plasticorder at 180 °C and a rotor speed of 50 rev min^?1. The mechanical and water‐absorption properties were studied. The incorporation of WRHA into the PP/NR matrix has resulted in the improvement of the tensile modulus; however, the tensile strength, elongation at break and stress at yield decreased with increasing WRHA loading. Poor filler matrix interactions are believed to be responsible for the decrease in the properties. Incorporation of a silane coupling agent, 3‐aminopropyl triethoxysilane (3‐APE), improved tensile modulus, tensile strength and stress at yield of the composites. Water‐absorption studies indicate that the use of the coupling agent reduced the amount of water absorbed by the composites. © 2001 Society of Chemical Industry     

Mechanical and morphological properties of white rice husk ash filled polypropylene/ethylene‐propylene‐diene terpolymer thermoplastic elastomer composites

The performance of white rice husk ash (WRHA) as filler for polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) thermoplastic elastomer (TPE) composites was investigated. The composites with different filler loadings were prepared in a Brabender plasticorder internal mixer. Both unvulcanized and dynamically vulcanized composites were prepared. Mixing and vulcanization processes of the composites were monitored through the typical Brabender torque‐time curves. The mechanical properties and morphology of the composites were also studied. The Brabender torque curves revealed that the dynamic vulcanization process employed was successful and incorporation of filler has no adverse effect on the processibility of the composites. Incorporation of WRHA improves the tensile modulus and flexural modulus and lowers tensile strength, elongation at break, tear strength, and toughness of both types of composites. Dynamic vulcanization significantly enhances the mechanical and TPE properties of the composites. Dynamic mechanical analysis (DMA) study revealed the existence of two phases in both types of composites. It further shows that neither dynamic vulcanization nor filler agglomeration has played a prominent role in the compatibility of the composites. Thermogravimetric investigation shows that dynamic vulcanization or WRHA loading has not adversely affected the thermal stability of the composites. The scanning electron micrographs provide evidence for the tendency to form filler agglomerates with increasing filler loading, better filler dispersion of dynamically vulcanized composites over unvulcanized composites, and effective vulcanization of elastomer phase of the composites in the presence of filler. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 438–453, 2002     

Effects of silane coupling agents on the vulcanization characteristics of natural rubber

The vulcanization characteristics of silica‐filled natural rubber (NR) were studied in the presence of silane coupling agents, 3‐octanoylthio‐1‐propyltriethoxysilane (NXT) and bis [(3‐triethoxysilylpropyl) tetra sulfide] (TESPT, or Si‐69). The scorch time, cure rate index, and the rate constant of NR were measured using an Oscillating Disk Rheometer in the temperature range of 140–170°C. The scorch time of NR decreases with increasing TESPT and NXT concentrations, and the scorch time of NR compound with NXT is longer than that with TESPT. The apparent activation energies of vulcanization for the compounds with NXT and TESPT both decrease with increasing silane concentration. The apparent activation energy of vulcanization of NR compound with NXT is lower than that with TESPT at various concentrations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1511–1518, 2004     

White Rice Husk Ash Filled Natural Rubber/Linear Low Density Polyethylene Blends

Abstract

Natural rubber (NR)/Linear low density polyethylene (LLDPE) blends were prepared using an internal mixer at 150°C and a rotor speed of 55 rpm. The tensile strength, tensile modulus and hardness increase with increasing LLDPE content whereas elongation at break and mass swell show decreasing trend. With 30/70 (W/W) NR/LLDPE blends, the increasing white rice husk ash (WRHA) loading also increases the tensile modulus and hardness but reduced the tensile strength, elongation at break, and mass swell.     

Synthesis and characterization of soybean‐oil‐based polyurethane composites containing industrial and agricultural residual wastes as fillers

Thermosetting composites were prepared from soybean‐oil‐based polyols (hydroxyl number = 190 mg of KOH/g, [OH]/[NCO] for 2,4‐toluene diisocyanate = 0.9) and fillers (10 wt %) from industrial and agricultural residual wastes. Different types of inexpensive residual wastes were used: black rice husk ash, coconut husk ash, calcined retorted oil shale, and retorted oil shale. The fillers were characterized by thermogravimetric analysis and measurements of particle size distribution, specific surface area, and pore size distribution. The fillers were microporous materials with different chemical compositions, with average particle diameters varying from 5.6 to 76.6 μm, specific surface areas varying between 6 and 165 m²/g, and thermal stability at the polyurethane cure temperature (65°C). All composites were characterized by dynamic mechanical analysis, flexural tests, Shore A hardness tests, thermogravimetric analysis, and scanning electron microscopy analysis. Coconut husk ash, rice husk ash, and retorted oil shale presented better mechanical properties; nevertheless, coconut husk ash and rice husk ash had higher particle sizes, which caused bad dispersion of the filler in the matrix and resulted in nonhomogeneous composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Use of rice husk ash as filler in natural rubber vulcanizates: In comparison with other commercial fillers

Rice husk ash is mainly composed of silica and carbon black remaining from incomplete combustion. Both silica and carbon black have long been recognized as the main reinforcing fillers used in the rubber industry to enhance certain properties of rubber vulcanizates, such as modulus and tensile strength. In this study, two grades of rice husk ash (low‐ and high‐carbon contents) were used as filler in natural rubber. Comparison was made of the reinforcing effect between rice husk ashes and other commercial fillers such as talcum, china clay, calcium carbonate, silica, and carbon black. Fourier transform infrared spectroscopy (FTIR) analysis was employed to study the presence of functional groups on the ash surface. The effect of silane coupling agent, bis(3‐triethoxysilylpropyl)tetrasulfane (Si‐69), on the properties of ash‐filled vulcanizates was also investigated. It was found that both grades of rice husk ash provide inferior mechanical properties (tensile strength, modulus, hardness, abrasion resistance, and tear strength) in comparison with reinforcing fillers such as silica and carbon black. However, the mechanical properties of the vulcanizates filled with rice husk ash are comparable to those filled with inert fillers. The addition of silane‐coupling agent has little effect on the properties of the ash‐filled vulcanizates. This is simply due to the lack of silanol groups on the ash surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2485–2493, 2002     

A comparison of the properties of rice husk ash,silica, and calcium carbonate filled 75 : 25 NR/EPDM blends

The effects of incorporation of three different fillers, i.e., rice husk ash (RHA), silica, and calcium carbonate (CaCO₃), over a loading range of 0–60 phr on the curing characteristics, processability, mechanical properties, and morphology of 75 : 25 natural rubber (NR)/ethylene‐propylene‐diene monomer (EPDM) blends were studied using a conventional vulcanization system. Filler loading and type influence the processability of the blends in which RHA and CaCO₃ offer better processing advantage over silica. The best improvement in the tensile and tear strength and abrasion resistance of the 75 : 25 NR/EPDM blends with additional fillers was achieved when filled with silica. However, RHA and CaCO₃ were better in resilience property compared to that of silica. The RHA filled blends showed higher failure properties and abrasion resistance but lower ozone resistance than that containing CaCO₃. Scanning electron micrographs revealed that the morphology of the blend filled with silica is finer and more homogenous compared to the blend filled with RHA and CaCO₃. According to these observations, RHA can be used as a cheaper filler to replace CaCO₃ in rubber blends where improved mechanical properties are not so critical. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparison of Water Absorption and Mechanical Behaviors of Polypropene Composites Filled with Rice Husks Ash

Composite materials were obtained by filling polypropene with raw and thermally treated rice husks at filler contents from 1 to 20%. The physicochemical properties were determined. A slight increase was observed in the tensile strength of the composites based on white rice husk ash (WRHA) and aerosil (AR) at degree of filling up to 3%. Young's modulus increased and the elongation at break and energy to break point showed a tendency to decrease for all the composites studied. The thermodynamics and kinetics of water absorption at immersion were studied in the temperature interval 25–90°C. The values of the changes in standard free energy, ΔG°, enthalpy, ΔH°, and entropy, ΔS° of adsorption were calculated. Water absorption was found to be thermodynamically difficult due to the diffusion mechanism of the process and it was accompanied by a decrease in the values of ΔH° and ΔS° with an increase in fillers contents. The effects of the amount of absorbed water, temperature, and treatment time on the composites tensile properties were estimated.     

Determination of filler content in thermoplastic composites by FTIR analysis

FTIR quantitative analytical method is described as an alternative technique for computation of the filler content in polypropylene composites. White rice husk ash (WRHA) was incorporated as a filler material into polypropylene homopolymer. Absorption peaks at 480, 621, and 790 cm^?1 chosen for the quantitative analysis work have been shown to give good linearity with increasing filler contents. © 1995 John Wiley & Sons, Inc.     

Water absorption behavior and its effect on tensile properties of ethylene–propylene–diene–terpolymer/polypropylene/filler ternary composites: a preliminary study

The water absorption behavior of white rice husk ash (WRHA) and silica filled ethylene-propylene-diene-terpolymer/polypropylene (EPDM/PP) ternary composites was studied with special reference to filler type, test specimen preparation (die cut or molded), and dynamic vulcanization of elastomer phase. The water uptake of composites was recorded as a function of them over 40 days of immersion period in distilled water. The influence of final water uptake on tensile properties of the composites was also studied. White rice husk ash filled composites and molded composites exhibit lower water uptake when compared to silica and die cut composites, respectively. All vulcanized composites showed lower water uptake than the unvulcanized composites. After the immersion period in water, tensile properties of unvulcanized composites were almost unaffected while vulcanized composites exhibit an increase in the tensile properties. None of the composites reached the equilibrium state within the immersion period. The results of this preliminary study suggest the importance of in-depth study of water absorption–tensile property correlation of this ternary system over a large span of time till the equilibrium state is reached. It is further revealed that the water absorption behavior depends on the characteristics of the test specimen used.     

The Fatigue Behaviour of Filled Epoxidized Natural Rubber Compounds

Abstract

The fatigue behaviour of white rice husk ash (WRHA) filled ENR-50 compounds was compared with those of silica (Vulcasil-S) and carbon black (N 330) filled compounds. The effect of WRHA loading on scorch time and Mooney viscosity was also studied. The incorporation of WRHA in ENR-50 compounds reduced the scorch time but increased the Mooney viscosity. The increment in filler loadings has resulted in the reduction of the fatigue fife. The fatigue behaviour of ENR-50 vulcanizates was observed to be strain dependent. At a similar filler loading, silica filled vulcanizates showed the highest fatigue life followed by those of WRHA and carbon black.     

White Rice Husk Ash-Filled Natural Rubber Compounds: The Effect of Bonding Agents

White rice husk ash (WRHA)-filled natural rubber compounds were prepared by using a laboratory-size two-roll mixing mill. Curing using a conventional vulcanization system was used and cure studies were carried out on a Monsanto rheometer. The mechanical testing of the vul-canizates involves the determination of tensile properties, tear strength, hardness, and resilience. Scanning electron microscopy (SEM) and swelling measurement were also done. The effects of bonding agents on the curing and mechanical properties have been investigated using re-sorsinol formaldehyde and hexamethylene tetramine as the bonding agents. Results show that the bonding agents prolonged the cure time t ₉₀ and scorch time t ₂ and, at the same time, improved the mechanical properties of the natural rubber vulcanizates. SEM and swelling studies indicate that the rubber-filler interaction is improved with the addition of bonding agents.     

Application of rice husk ash as fillers in the natural rubber industry

Rice husk ash (RHA) obtained from agricultural waste, by using rice husk as a power source, is mainly composed of silica and carbon black. A two‐stage conventional mixing procedure was used to incorporate rice husk ash into natural rubber. For comparison purposes, two commercial reinforcing fillers, silica and carbon black, were also used. The effect of these fillers on cure characteristics and mechanical properties of natural rubber materials at various loadings, ranging from 0 to 40 phr, was investigated. The results indicated that RHA filler resulted in lower Mooney viscosity and shorter cure time of the natural rubber materials. The incorporation of RHA into natural rubber improved hardness but decreased tensile strength and tear strength. Other properties, such as Young's modulus and abrasion loss, show no significant change. However, RHA is characterized by a better resilience property than that of silica and carbon black. Scanning electron micrographs revealed that the dispersion of RHA filler in the rubber matrix is discontinuous, which in turn generates a weak structure compared with that of carbon black and silica. Overall results indicate that RHA can be used as a cheaper filler for natural rubber materials where improved mechanical properties are not critical. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 34–41, 2005