Rice husk ash filled natural rubber. I. Overall rate constant determination for the vulcanization process from rheometric data

Black rice husk ash (BRHA) and white rice husk ash (WRHA) were incorporated into natural rubber (NR) using a laboratory‐size two‐roll mill. A conventional vulcanization system (CV) was chosen and cure studies were carried out on a TI‐100 Curometer. The torque curves were obtained at 150, 160, 170, and 180°C. The overall rate and the apparent activation energy for the vulcanization process were calculated for each compound assuming that vulcanization follows first‐order kinetics. For comparison purposes, two commercial fillers, precipitated silica (Zeosil‐175) and carbon black (N762), were also used. It was observed that addition of WRHA to NR compounds increased the cross‐linking rate and lowered the apparent activation energy more markedly than the other fillers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1194–1203, 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     

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     

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.     

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     

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     

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     

Electrical and thermal properties of γ‐irradiated nitrile rubber/rice husk ash composites

The effects of both the rice husk ash (RHA) loading and fumed silica (FS) loading on the structure, thermal stability, and electrical properties of acrylonitrile–butadiene rubber (NBR) composites were studied. The filler loading were chosen to be 5 and 20 phr for RHA and 5 and 30 phr for silica. Also, the effect of the γ‐irradiation dose (25 kGy) on these parameters was investigated. The structure and thermal stability were studied with X‐ray diffraction and thermogravimetric analysis techniques. Furthermore, some electrical parameters, such as the direct‐current electrical conductivity (σ_dc), activation energy (E_a), dielectric constant (?′), and dielectric loss (?″), were determined. The incorporation of both RHA and FS resulted in improved thermal stability after γ irradiation at 25 kGy. The loading of FS on NBR was shown to decrease σ_dc, ?′, and ?″ and increase E_a. On the other hand, the loading of RHA showed the opposite trend. Finally, γ irradiation of NBR composites filled with both fillers decreased the values of σ_dc, ?′, and ?″ for all the samples, which followed the trend for the unirradiated composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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     

Cure behavior and antimicrobial performance of sulfur‐cured natural rubber vulcanizates containing 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate or silver‐substituted zeolite

This work used 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate (HPQM) or silver‐substituted zeolite (SSZ) as antibacterial agents for natural rubber (NR) compounds vulcanized by conventional vulcanization (CV), semi‐efficient vulcanization, and efficient vulcanization (EV) systems. The cure behavior and antibacterial performance of the NR vulcanizates were studied by varying the loadings of HPQM or SSZ, contact times, and vulcanization systems. The antibacterial performance of the rubber compounds was examined by halo test and plate‐count‐agar methods against Escherichia coli (E. coli, ATCC 25922) and Staphylococcus aureus (S. aureus, ATCC 25923) as the testing bacteria. The cure time and crosslink density were dependent on the vulcanization recipe used but were not affected by the addition of HPQM or SSZ. Diphenylguanidine at the level of 1.0 phr (parts by weight per hundred parts of resin) in NR vulcanized by the EV system had the ability to kill the E. coli and S. aureus bacteria. The NR vulcanized by the CV system showed the most pronounced antibacterial performance, as compared with the other two vulcanization systems, via migration and diffusion of HPQM or SSZ onto the NR surfaces, this being identified by the relatively large reduction of contact angle values. The HPQM showed the most preference for NR compounds vulcanized with the CV system with a contact time of 120 min or longer to achieve a bacteria‐killing efficacy of 99.0–99.9%, the efficacy being more pronounced for E. coli bacteria. J. VINYL ADDIT. TECHNOL., 19:123–131, 2013. © 2013 Society of Plastics Engineers     

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     

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.     

Effect of non‐rubber substances on vulcanization kinetics of natural rubber

Effect of non‐rubber components on vulcanization kinetics of natural rubber was studied with the use of a Rheometer MDR‐2000. The results show that the rate constants of induction period and curing period of natural rubber (NR) are greater than that of natural rubber extracted with acetone (NR_E), and the activation energies of induction period and curing period of NR are lower than that of NR_E. The activation energy of induction period of NR is reduced by16.9% and the activation energy of curing period of NR is reduced by 3.2% compared to the activation energies of NR_E. The time t_dis of NR is shorter than that of NR_E at the same temperature. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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     

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.     

Degradation kinetics of vulcanized ethylene–propylene–diene terpolymer residues

In this study, ethylene–propylene–diene terpolymer residues (EPDM‐r) from the automotive industry were analyzed by thermogravimetric analysis (TGA) for determination of the activation energy (E_a) of decomposition by the Flynn‐Wall‐Ozawa (FWO) method. The degradation mechanism was determined by the method of Criado et al. Analysis of the nonvulcanized EPDM gum (EPDM‐g) and paraffinic oil used in the composition of the compound was also carried out. The E_a values for the decomposition of the EPDM‐g and paraffinic oil remained constant with the conversion, but for the EPDM‐r decomposition, they changed due to the initial oil elimination followed by decomposition of the EPDM fraction. It was observed that removal of the paraffinic oil occurred less easily in the tridimensional vulcanized network, and there were differences in the elimination mechanism. The EPDM degradation mechanism was also affected by vulcanization and the fillers present in the compound. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Vulcanization kinetics of low‐protein natural rubber with use of a vulcameter

Kinetics of vulcanization of low‐protein natural rubber (LPNR) was studied with the use of a vulcameter. In the induction period of vulcanization, the time t₀ of LPNR is longer than that of natural rubber (NR), and the temperature dependences of the time t_dis and the rate constant of LPNR are greater than that of NR. Both the curing periods of LPNR and NR (except 170°C for LPNR) consist of two stages. The first stage follows first‐order reaction. The rate constant k₂ of LPNR in the first stage is substantially the same as that of NR at the same temperature, and so is the activation energy E₂. The second stage (end stage of the curing period) does not follow first‐order reaction, and the calculated reaction order n is in the range of 0.67–0.73. Both rate constants of LPNR (except 170°C) and NR at the same temperature are approximately the same, and so is the activation energy E_3. The whole process of curing period for LPNR at 170°C follows n = 0.7 order reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007