Synthesis of nano zinc oxide and its effect on the cure characteristic and properties of natural rubber vulcanizates

In this work, nano ZnO was synthesized by a simple method using a polymeric substance as a dispersing agent. Characterization of the synthesized ZnO by XRD and SEM confirmed the ZnO was nanometric in size and had a wurtzite structure. The synthesized nano ZnO was used as an activator for natural rubber vulcanization. Different amount of ZnO, 1, 2 and 3 phr, was investigated in the rubber formulation and compared to convention ZnO at a typical amount (6 phr). The sample with 3 phr nano ZnO showed the lowest curing induction time with the highest (ML-MH) at all studied temperatures. Furthermore, the rubber sample with 3 phr ZnO achieved the best properties, i.e., crosslink density, rebound resilience, and hardness compared to the rubber sample with 6 phr conventional ZnO. Interestingly, the properties of rubber sample with 2 phr nano ZnO were probably equivalent and comparable to that of 6 phr conventional ZnO. Thus, it suggested that the synthesized nano ZnO could replace the convention ZnO as an activator for rubber vulcanization even at a lower amount.

Mullins Effect and Crack Growth in Natural Rubber Vulcanizates during Heat Aging and Cyclic Loading

The effect of thermal aging and cyclic loading on mechanical properties and development of cracks in natural rubber vulcanizates was studied. After aging at 70oC and 110oC vulcanizates were subjected to cyclic loading. At a certain number of loading cycles, the samples were conducted in a tension test. At the aging condition of 70oC, the static tensile properties of material stay almost unchanged even after 88 aged hours and 8000 loading cycles. On the contrary, the dynamic fatigue resistance of vulcanizates decreases with increasing aging time. These results are attributed to the post-curing and the development of microcracks that might be caused by Mullins effect: in the case of static loading, the strain-induced crystallization may prevent cracks growth, but in the case of cyclic loading the strain-induced crystallization does not occur, so cracks develop without hindrance. However, at 110oC both static properties and dynamic fatigue resistance of material reduced dramatically because at high temperature the heat degradation exceeds both post-curing and strain-induced crystallization. Crack formation and propagation were examined by a digital optical microscope in the progress of cyclic loading. Results showed that natural rubber vulcanizate filled with carbon black has the best crack growth resistance (CGR) while the addition of modified and unmodified silica reduces CGR of materials. Moreover, the vulcanizate with unmodified silica has the lowest CGR.

Thermal Degradation of Natural Rubber Vulcanizates Reinforced with Organomodified Kaolin Intercalates

In this study, Natural Rubber Vulcanizates (NRV) reinforced with organomodified kaolin was developed. The NRV were subjected to thermal degradation to ascertain its suitability for high-temperature automotive applications. Kaolin intercalation was achieved using derivatives of Rubber seed oil (Hevea brasiliensis) and Tea seed oil (Camellia sinensis) in the presence of hydrazine hydrate as co-intercalate. The developed Natural Rubber Vulcanizates were characterised using Thermogravimetric Analysis (TGA), Fourier Transform Infrared (FTIR) Spectroscopy and Scanning Electron Microscopy (SEM). FTIR spectra obtained for the organomodified natural rubber vulcanizates revealed the presence of carbonyl groups at bands 1564cm-1 and 1553cm-1 which is an indication of organomodified kaolin intercalation within the Natural Rubber matrix for kaolin intercalates of Rubber seed oil and Tea seed oil respectively while no value was reported for the Natural Rubber vulcanizates obtained from the pristine kaolin filler. TGA results indicated that NRV developed from kaolin intercalates of Rubber seed oil (RSO) with onset degradation and final degradation temperatures of 354.2°C and 601.3°C were found to be the most thermally stable of the Natural Rubber Vulcanizates investigated. The SEM micrograph revealed that the kaolin nanofillers in Rubber Seed Oil modified Natural Rubber Vulcanizates were well dispersed as compared to that of Tea Seed Oil modified Natural Rubber Vulcanizates.

Effects of chemically treated and carbonized spear grass fibre on the curing and mechanical properties of natural rubber vulcanizates

Effects of chemically treated and carbonized spear grass fibre on the curing and mechanical properties of natural rubber vulcanizates were carried out. Natural rubber (NR) was filled with carbonized (at carbonization temperatures of 400°C, 600°C and 800°C respectively) and chemically treated (treatment with HCl and NaOH of 5% concentration) spear grass fillers respectively, at a filler loading of 30phr. The rubber compounding was carried out in a bambury mixer. The effect of carbonization temperature and chemical treatment of the filler on the mechanical properties (tensile strength, % elongation, hardness strength, abrasion resistance and compression set) and rheological properties (cure time, scorch time, maximum and minimum torque) were carried out on the samples. The results of the mechanical properties of carbonized spear grass fibre (C-SGF) filled vulcanizates show that the optimum carbonization temperature for an improved tensile strength, % elongation, hardness, abrasion and compression set was obtained at 400°C. NaOH treated fibre filled vulcanizates showed better mechanical properties; with the highest abrasion resistance of 67.65%, while untreated and acidified fibre filled vulcanizates showed poor mechanical properties. Acidified (HCl) uncarbonized spear grass fibre (U-SGF) filled vulcanizate had the highest compression set of 48% against C-SGF filled vulcanzates and carbon black filled vulcanizate, with carbon black filled vulcanizate having 47% as its compression set value. This reveals that at a carbonization temperature of 400°C, C-SGF appears to be a potential substitute filler for carbon black (CB). Keywords: Spear Grass Fibre, Natural Rubber, Chemical Treatments, Cure Characteristics, Mechanical Properties, Carbonization

Alleviating Molecular-Scale Damages in Silica-Reinforced Natural Rubber Compounds by a Self-Healing Modifier

The property retentions of silica-reinforced natural rubber vulcanizates with various contents of a self-healing modifier called EMZ, which is based on epoxidized natural rubber (ENR) modified with hydrolyzed maleic anhydride (HMA) as an ester crosslinking agent plus zinc acetate dihydrate (ZAD) as a transesterification catalyst, were investigated. To validate its self-healing efficiency, the molecular-scale damages were introduced to vulcanizates using a tensile stress–strain cyclic test following the Mullins effect concept. The processing characteristics, reinforcing indicators, and physicomechanical and viscoelastic properties of the compounds were evaluated to identify the influences of plausible interactions in the system. Overall results demonstrate that the property retentions are significantly enhanced with increasing EMZ content at elevated treatment temperatures, because the EMZ modifier potentially contributes to reversible linkages leading to the intermolecular reparation of rubber network. Furthermore, a thermally annealing treatment of the damaged vulcanizates at a high temperature, e.g., 120 °C, substantially enhances the property recovery degree, most likely due to an impact of the transesterification reaction of the ester crosslinks adjacent to the molecular damages. This reaction can enable bond interchanges of the ester crosslinks, resulting in the feasibly exchanged positions of the ester crosslinks between the broken rubber molecules and, thus, achievable self-reparation of the damages.