Organomodified kaolin as a reinforcing filler for natural rubber

China clay (kaolin) has been modified with sodium salt of rubber seed oil (SRSO). SRSO was characterized using X‐ray diffraction (XRD), infrared spectroscopy (FTIR), and differential thermal analysis (DTA). XRD of the unmodified and SRSO‐modified kaolins showed an increase in the d‐(001) spacing of kaolin platelets from 7.15 to 14 Å. FTIR spectroscopy indicated possible grafting of the organic moiety of rubber seed oil (RSO) onto the clay surface. DTA of the SRSO‐modified kaolin indicated that the SRSO is more strongly bound in a constraint environment within the lamellae of kaolin. Natural rubber (NR) mix containing 10 phr of SRSO‐modified kaolin was found to cure faster than that of a similar mix containing unmodified kaolin. NR vulcanizates containing SRSO‐modified kaolin showed considerable increase in tensile modulus, tensile strength, and elongation at break indicating its potential as an organomodified nanofiller. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nano ZnO as cure activator and reinforcing filler in natural rubber

Zinc oxide (ZnO) nanoparticles of size 20–90 nm and surface area 9.56 m²/g were synthesized from ZnCl₂ and Chitosan and characterized by X‐ray diffraction, high resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM). Natural rubber (NR) vulcanizates containing nano ZnO was prepared by mill mixing and characterized by SEM, energy dispersive X‐ray analysis (EDAX), and HRTEM. Cure characteristics, free volume studies, bound rubber, crosslink density, and dynamic mechanical properties were evaluated and compared with that of NR vulcanizate containing conventional micro ZnO. Considering the cure characteristics, it was found that NR vulcanizate with 0.5 phr (parts per 100 g rubber) of nano ZnO showed low values of optimum cure time (t₉₀) and very high cure rate index compared with 5 phr of conventional micro ZnO. The study shows that micro ZnO can be successfully replaced with nano ZnO for accelerated sulfur vulcanization process in NR, and preparation of vulcanizate containing nano ZnO with better properties as that of micro ZnO. The optimum dosage of nano ZnO as a cure activator in NR vulcanization was found to be 0.5 phr compared with conventional grade micro ZnO. This will lead to substantial cost reduction in the manufacture of rubber products and alleviate environmental pollution due to excess ZnO in rubber compounds. POLYM. ENG. SCI., 2013 © 2013 Society of Plastics Engineers     

Kaolin modified with sodium salt of rubber seed oil as a reinforcing filler for blends of natural rubber,polybutadiene rubber and acrylonitrile–butadiene rubber

Blends of natural rubber (NR) and synthetic rubbers are widely used in the rubber industry to meet specific performance requirements. Further, the emerging field of organomodified clay/rubber nanocomposites could provide a host of novel materials having a unique combination of properties to meet various stringent service conditions. Previous studies have shown that at very low dosages, china clay (kaolin) modified with sodium salt of rubber seed oil (SRSO) improved the cure characteristics and physico‐mechanical properties of NR. Results of the present study show improved cure characteristics and physico‐mechanical properties for blends of NR with butadiene rubber and nitrile rubber containing 4 phr of SRSO‐modified kaolin as indicated by reduction in optimum cure time along with higher tensile strength, tensile modulus and elongation at break for their vulcanizates as compared to those containing unmodified kaolin. The SRSO‐modified kaolin/rubber nanocomposites showed improved flex resistance, reduced heat build‐up, tan delta and loss modulus and higher chemical crosslink density index, indicating a reinforcing effect of the SRSO‐modified kaolin, enabling the nanocomposites to have potential industrial applications. © 2015 Society of Chemical Industry     

Novel CNC/silica hybrid as potential reinforcing filler for natural rubber compounds

This work describes the development of a low-density, renewable, and high reinforcing filler for natural rubber (NR) compounds. The cellulose nanocrystal (CNC)-based hybrid filler was synthesized by decorating the surface of CNCs with silica using a simple and efficient coprecipitation method. The properties of the prepared hybrid were investigated by field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, nitrogen physisorption measurements, and Thermogravimetric analysis. Then, the prepared hybrid was incorporated in NR using two different approaches, namely, dry mixing and coprecipitation. The dynamic and tensile mechanical properties of the hybrid/NR compounds were evaluated indicating that: the coprecipitation method was found much more effective for homogeneous dispersion and the CNC/silica hybrid provided quite higher reinforcement to NR than reference silica; however, much lower density of the final compounds was obtained. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48332.     

An investigation on the reinforcing potential of red earth as filler for natural rubber compounds

Locally sourced red earth (RE) was air‐dried, pulverized, and screened with a sieve of mesh size 75 nm. It was characterized in terms of its moisture content, loss on ignition, silica content, iodine adsorption number, oil absorption, pH, and metal oxide compositions. Natural rubber, standard Nigerian rubber used for this work was first characterized in terms of its dirt, ash and nitrogen contents, volatile matter, plasticity retention index, and Mooney viscosity. The RE was applied as filler wholly and in blends with standard carbon black, CB (N330) filler in the natural rubber compounding using efficient vulcanization system. The cure and the physicomechanical properties of the compounds and vulcanizates were, respectively, measured as function of filler loading. The results were compared with those of the standard carbon black (N330)‐filled natural rubber. It was found, that the RE‐filled natural rubber showed substantial reinforcement of the rubber, though inferior to carbon black (N330) filled vulcanizates, the tensile strength of the carbon black‐filled vulcanizates is about one half times that of the RE‐filled vulcanizates. The tensile properties of the RE‐filled vulcanizates improved markedly by blending the RE‐filler with the carbon black (N330). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Grape stalk fibers as reinforcing filler for polymer composites with a polystyrene matrix

Lignocellulosic fibers have been one of the most used reinforcements for different types of composites. In this context, grape stalks—often discarded in landfills—can be a potential reinforcement for composites. The present study aimed to incorporate in natura and alkali treated grape stalks into the polystyrene (PS) matrix. Initially, the grape stalks were treated with NaOH and 10, 20, and 30 wt % of stalks were added into the PS matrix. The alkaline treatment of the grape stalk fibers promoted the removal of hemicellulose and the partial removal of lignin, thus increasing the surface roughness and crystallinity index of the fibers. An improvement in the mechanical and dynamic-mechanical properties and an increase in the maximum degradation temperature of the composites were observed. In conclusion, the use of grape stalks is a promising alternative for reinforcing composites, and, in addition, a more proper destination can be given to this type of residue. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47427.     

Novel method for toughening of polystyrene based on natural rubber latex

γ‐Radiation vulcanized natural rubber latex/phase transfer/bulk polymerization is a novel process for the preparation of toughened polystyrene based on natural rubber latex. The negatively charged γ‐radiation vulcanized natural rubber latex was first titrated with benzyldimethylhexadecylammonium chloride in the presence of a styrene monomer. At a critical transfer concentration, the crosslinked rubber particles transferred from the aqueous phase into the styrene phase in which they swelled, depending on the irradiation dose used. By bulk polymerization of the styrene phase containing transferred particles, the polymer blends exhibited two‐phase morphology similar to that of commercial high‐impact polystyrene that was microscopically obtained. The final product showed an increase in the unnotched Izod impact energy over the unmodified polystyrene. The effect of irradiation dose, rubber content, and initiator concentration on the impact property and morphology of toughened polystyrene prepared was investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1333–1345, 1999     

Structured latex particles based on natural rubber for high-impact polymer blends

Natural latex (NR) particles, modified with a hard shell of poly(methyl methacrylate) (PMMA) and with a substructure of PMMA (type "NR-M") or polystyrene (type "NR-SM"), were tested as compatibilizers in blends of polycarbonate (of bisphenol A, PC) and PMMA or PS. During melt blending, the modified NR particles were torn apart, from an original size of >0.5 μm down to ≅0.1 μm in diameter. Two different types of particle distribution were observed in the blends: in PC/PMMA/NR-M blends, the NR-M particles were dispersed in the PMMA phase, whereas, in PC/PS/NR-SM blends, the NR-SM particles formed interface layers between PC and PS phase domains. The latter blend morphology, distinguished by continuous rubbery interface layers of NR-SM, turned out to be mechanically excellent in injection-moulded parts. The poor impact strength of PC/PS was raised by an order of magnitude. The effect depends on the orientation in the injection-moulded test bars.     

Stress‐relaxation behavior of natural rubber/polystyrene and natural rubber/polystyrene/natural rubber‐graft‐polystyrene blends

We studied the stress‐relaxation behavior of natural rubber (NR)/polystyrene (PS) blends in tension. The effects of strain level, composition, compatibilizer loading, and aging on the stress‐relaxation behavior were investigated in detail. The dispersed/matrix phase morphology always showed a two‐stage mechanism. On the other hand, the cocontinuos morphology showed a single‐stage mechanism. The addition of a compatibilizer (NR‐g‐PS) into 50/50 blends changed the blend morphology to a matrix/dispersed phase structure. As a result, a two‐step relaxation mechanism was found in the compatibilized blends. A three‐stage mechanism was observed at very high loadings of the compatibilizer (above the critical micelle concentration), where the compatibilizer formed micelles in the continuous phase. The aged samples showed a two‐stage relaxation mechanism. The rate of relaxation increased with strain levels. The aging produced interesting effects on the relaxation pattern. The rate of relaxation increased with temperature due to the degradation of the samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

补强填充剂TBC在橡胶中的应用

试验研究TBC作为补强填充剂在NR，SBR和NBR中的应用效果，并与轻质碳酸钙、白炭黑和炭黑进行对比。结果表明，TBC具有一定补强性，其补强效果优于轻质碳酸钙，不如白炭黑和炭黑，这种差别在NR中不明显，在SBR和NBR中较为明显TBC对NBR物理性能的改善效果较NR和SBR更为明显；TBC在NR，SBR和NBR中的适宜用量分别为40-50，60-70和70-80份。     

Organomodified montmorillonite as filler in natural and synthetic rubber

The filler action of dodecylamine (12C) intercalated montmorillonite (MNT) referred to as organomodified montmorillonite (12C‐MNT) up to 4 wt % on natural rubber (NR) and styrene butadiene rubber (SBR) was studied and findings were compared with respect to the unmodified Na‐MNT. X‐ray analysis was used to calculate the interchain separation (R and R′), degree of crystallinity (X_c), and distortion factor (k). It is noted that R and R′ showed the opposite trend, whereas X_c as well as k showed overall increasing trend with an increasing amount of 12C‐MNT on both NR and SBR. For Na‐MNT (1 wt %) filled NR and SBR, the corresponding magnitude of R and R ′ and X_c showed nearly no change, whereas k_c increased significantly. The crosslinking density (v_c) does not show any significant changes in NR, whereas for SBR, it increases with increasing 12C‐MNT as filler. Interestingly, in the case of 1 wt % pure Na‐MNT used as filler for both NR and SBR, v_c was lower compared to the virgin rubbers. Both swelling index (s_i) and sol fraction (Q) do not show any significant variation for NR composites, whereas these decrease for SBR composites with increasing concentration of 12C‐MNT filler. On the contrary, NR and SBR with 1 wt % of Na‐MNT filler show greater magnitude of s_i and Q corresponding to the pure ones. Measurements of mechanical properties showed a significant increase in tensile strength and elongation at break for NR‐12C‐MNT (4 wt %) when compared with either virgin NR. In addition, modulus at the elongation at 100 and 200% in general increases with increasing loading of 12C‐MNT filler in NR. Similar observations were also noted in the case of SBR. Interestingly, when only pure Na‐MNT is used as filler, the strength of NR and SBR decreases drastically. Scanning electron microscopic studies were also to used support the mechanical behavior of NR‐12MNT and SBR‐12CMNT composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3583–3592, 2004     

Polyester resin as a compatibilizing agent for some polymeric blends

Dielectric and viscosity techniques were used to determine the degree of the compatibility of poly(methyl methacrylate)/polycarbonate, poly(methyl methacrylate)/ polystyrene, and polycarbonate/polystyrene blends in different ratios (25/75, 50/50, and 75/25 w/w). The effect of the addition of 5, 10, and 20% concentrations of the prepared polyester resin [poly(butylene terephthalate adipate)] on the compatibility of these blends was studied. The dielectric properties were measured over a frequency range (from 100 Hz to 100 kHz) at various temperatures covering the glass‐transition temperatures of the polymers used (from 30 to 170°C). It was found from the dielectric and viscosity measurements that the addition of 10% polyester to poly(methyl methacrylate)/polycarbonate, 20% polyester to poly(methyl methacrylate)/polystyrene, and 5% polyester to polycarbonate/polystyrene blends enhanced the degree of compatibility of such blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of thermoplastic elastomeric blends of chitosan and natural rubber latex

Thermoplastic chitosan/natural rubber blends (Cs/NR) were prepared from natural rubber latex and chitosan by solution casting technique. The blends were characterized by mechanical analysis (stress–strain) and the mechanical properties were found to vary with chitosan/natural rubber ratios. Experimental values were compared with different theoretical models. Effect of thermal aging on mechanical properties was also investigated. Dicumyl peroxide was used as the crosslinking agent. The effect of crosslinking on mechanical properties of Cs/NR has also been studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of chemically modified waste rubber powder as a filler in natural rubber vulcanizates

Waste rubber powder (RP) was subjected to chemical modification by using different concentrations of oxidizing agents such as nitric acid and 30% hydrogen peroxide solution. This treatment leads to introducing some functional groups onto the surface of RP. The chemically modified RP was incorporated in natural rubber mixes either alone or in combination with carbon black (HAF). The physicomechanical properties of NR vulcanizates obtained were studied and compared to NR vulcanizates filled with untreated RP. It was found that the chemically modified RP improves tensile strength and aging resistance of NR vulcanizates compared with untreated RP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 30–36, 2004     

The use of cryogenically ground rubber tires as a filler in polyolefin blends

The effects of cryogenically ground rubber tires (CGT) on some of the mechanical properties of blends with linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) are presented. Precoating the CGT particles with an ethylene-acrylic acid copolymer is shown to overcome most of the deleterious effects of adding CGT to LLDPE, while still retaining composite processability. A blend of 40 wt% EAA coated CGT particles with LLDPE is shown to have impact and tensile strengths that are 90% of those for the pure LLDPE, representing increases of 60 and 20%, respectively, over blends with uncoated particles. Blends of LLDPE with ground tire bladders demonstrate that even better mechanical properties can be obtained with similar large rubber particle size but somewhat better adhesion. For HDPE, however, it is shown that with large rubber particles, moderate adhesion is not sufficient to produce useful composites.     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.     

Dichlorocarbene modification of natural rubber and its role as a modifier in blends of natural rubber and hydrogenated nitrile rubber

Dichlorocarbene modification of natural rubber (NR) carried out by alkaline hydrolysis of chloroform in presence of cetyl trimethyl ammonium bromide as phase‐transfer catalyst was investigated. Extent of chemical reaction was characterized by estimation of chlorine content and FTIR studies. Rate of dichlorocarbene addition depends on the time and temperature of reaction. Reaction carried out at 60°C for 2 h yielded a material with a chlorine content of 15%. Chemical modification of NR was accompanied by introduction of chlorine through cyclopropyl ring to the main chain of NR as revealed from FTIR studies. As level of chlorination increased, the physical nature of NR changed from a soft flexible state to a hard nontacky form. Blends of NR with hydrogenated nitrile rubber (HNBR) containing three to seven parts of dichlorocarbene‐modified NR (DCNR) of chlorine content 15% could be prepared by conventional mill mixing. Incorporation of DCNR into blends of NR and HNBR promoted polar interaction between the chlorine segments and acrylonitrile segments of the blend as shown from the shift in characteristic IR absorption peaks and shift in T_g from DSC studies. As a consequence, DCNR acted as an interface modifier in blends of NR and HNBR. Blends of NR and HNBR containing DCNR showed a considerable improvement in cure behavior, physical properties, and ageing characteristics in oil, ozone, and high temperature compared to pure blends of NR and HNBR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4401–4409, 2006     

Mechanical and viscoelastic behavior of natural rubber and carboxylated styrene‐butadiene rubber latex blends

The morphology, mechanical and viscoelastic behavior of latex blends of unvulcanized natural rubber (NR) with carboxylated styrene‐butadiene rubber (XSBR) were investigated, with special reference to the effect of the blend ratio, temperature, and frequency. Mechanical properties like tensile strength, modulus, and elongation at break were also studied. As the XSBR content increased, the tensile strength increased up to a 50:50 NR/XSBR ratio and then decreased as a result of the self‐curing nature of XSBR. The dynamic mechanical properties of these latex blends were analyzed for loss tangent, storage modulus, and loss modulus. The entire blend yielded two glass‐transition temperatures, which corresponded to the transitions of individual components, indicating that the system was immiscible. To determine the change in modulus with time, a master curve of 50:50 NR/XSBR blends was plotted. Time–temperature superposition and Cole–Cole analysis were done to understand the phase behavior of the latex blends. The experimental and theoretical values of storage modulus of blends were compared using the Kerner and Halpin–Tsai models. With the help of optical micrographs, attempts were made to correlate the morphology and viscoelastic behavior of these blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2639–2648, 2003     

Utilization of bowstring hemp fiber as a filler in natural rubber compounds

The cure characteristics and physicomechanical properties of natural rubber (standard Nigerian rubber) vulcanizates filled with the fiber of bowstring hemp (Sansevieria liberica) and carbon black were investigated. The results showed that the scorch and cure times decreased, whereas the maximum torques increased, with increasing filler loadings for both bowstring hemp fiber and carbon black filled vulcanizates. The tensile strength of both bowstring hemp fiber and carbon black filled vulcanizates increased to a maximum at a 40 phr filler concentration before decreasing. The elongation at break and rebound resilience decreased, whereas the modulus, specific gravity, abrasion resistance, and hardness increased, with increasing filler contents. The carbon black/natural rubber vulcanizates had higher tensile strength, which was about 1.5 times that of bowstring hemp fiber/natural rubber vulcanizates. This superiority in the tensile strength was probably due to the higher moisture content and larger particle size of the bowstring hemp fiber. However, the bowstring hemp fiber/natural rubber vulcanizates showed superior hardness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008