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At least 19 records

Sustainable Use of Chloroprene Rubber Waste as Blend Component with Natural Rubber, Epoxidized Natural Rubber and Styrene Butadiene Rubber

Recycling of rubber waste and finding the effective methods to extend its use are one of major challenges nowadays. The potential approach to reduce rubber waste is to blend it with virgin rubber, perhaps with synergistic advantages. In this study, chloroprene rubber waste (CRw) is used as blend component in binary blends with natural rubber (NR), epoxidized natural rubber with 50 mol% epoxidation level (ENR50), and styrene butadiene rubber (SBR). The effects of blend ratio [95/5, 85/15, 75/25, 65/35 and 50/50 (phr/phr)] on the properties were studied. The results indicate that CRw prolongs scorch and curing times, due to the differences in unsaturation contents and cure incompatibility. The maximum torque (M{sub H}), minimum torque (M{sub L}), and torque difference (M{sub H}–M{sub L}) in all cases increased with CRw content in the blend. Because CRw has a crosslink precursor, crosslink density also increased with CRw content. This is clearly confirmed by the combination of swelling resistance, crosslink density and dynamic mechanical properties observed. SEM micrographs showed mostly rough surface and tearing areas for low CRw contents in the blends. The blends also showed less crack paths with increasing CRw content over 50 phr. Further increase in CRw content obviously enhanced the thermal stability of the blends, with elevated decomposition temperatures in TGA results.

36 MATERIALS SCIENCE↗

Alkali-activated slag (AAS) and OPC-based composites containing crumb rubber aggregate: Physico-mechanical properties, durability and oxidation of rubber upon NaOH treatment

Value-added utilization of waste tires in cementitious materials has been studied for decades, whereas the synergy between rubber and alkali-activated cements deserves more investigations. To this end, we compared physico-mechanical and durability properties of alkali-activated slag (AAS) and OPC-based composites containing NaOH-pretreated/as-received crumb rubber (CR). It was found that the incorporation of CR had both positive and negative effects on specimens due to its special attributes. CR reduced electrical conductivity which was associated with the ion transport ability, since it worked as an electrical insulator and increased hydrophobicity of pore walls. The sulfate expansion decreased with CR content because the flow of sulfate ions was demobilized, and the flexibility of CR relieved the internal stress. CR also improved the freeze-thaw durability of composites if the total CR content was less than 30% in specimens. However, the low Young's modulus of CR impaired the compressive strength and failed to effectively control the total shrinkage upon drying. The composites with CR must avoid high temperature exposure which resulted in the pyrolysis of rubber. In addition, the NaOH pretreatment enhanced adhesion between CR and hydrated cement and improved overall performances of composites. The FTIR spectra confirmed the NaOH-induced accelerated oxidation of CR surface and the generation of polar functional groups including carbonyl and carboxyl groups, increasing the total surface energy of rubber. More importantly, the alkali-activation process for AAS could treat the CR aggregate in the meantime, which means the use of CR in alkali-activated cements does not require the pretreatment of CR before blending.

36 MATERIALS SCIENCE↗

In situ friction and wear behavior of rubber materials incorporating various fillers and/or a plasticizer in high-pressure hydrogen

Polymers are used routinely for equipment and infrastructure in hydrogen vehicle refueling stations, but significant gaps remain in understanding their hydrogen compatibility. The tribological properties of these materials in a high-pressure hydrogen environment is important in preventing component failure and the need for frequent replacement. We present in situ tribological studies on model rubbers, which include common fillers and plasticizer, using an in situ tribometer developed previously. Results suggest a clear, yet complicated, combined effect of the high-pressure hydrogen and the additives on the tribological performance of the chosen materials, as compared to matching experiments performed in ambient air. We find that the additives improved wear resistance in EPDM but deteriorated that in NBR due to disparate additive-polymer interactions.

Kuang, Wenbin↗

Microscopic Origins of the Nonlinear Behavior of Particle-Filled Rubber Probed with Dynamic Strain XPCS

The underlying microscopic response of filler networks in reinforced rubber to dynamic strain is not well understood due to the experimental difficulty of directly measuring filler network behavior in samples undergoing dynamic strain. This difficulty can be overcome with in situ X-ray photon correlation spectroscopy (XPCS) measurements. The contrast between the silica filler and the rubber matrix for X-ray scattering allows us to isolate the filler network behavior from the overall response of the rubber. This in situ XPCS technique probes the microscopic breakdown and reforming of the filler network structure, which are responsible for the nonlinear dependence of modulus on strain, known in the rubber science community as the Payne effect. These microscopic changes in the filler network structure have consequences for the macroscopic material performance, especially for the fuel efficiency of tire tread compounds. In this work, we elucidate the behavior with in situ dynamic strain XPCS experiments on industrially relevant, vulcanized rubbers filled (13 vol %) with novel air-milled silica of ultrahigh-surface area (UHSA) (250 m 2 /g). The addition of a silane coupling agent to rubber containing this silica causes an unexpected and counterintuitive increase in the Payne effect and decrease in energy dissipation. For this rubber, we observe a nearly two-fold enhancement of the storage modulus and virtually equivalent loss tangent compared to a rubber containing a coupling agent and conventional silica. Interpretation of our in situ XPCS results simultaneously with interpretation of traditional dynamic mechanical analysis (DMA) strain sweep experiments reveals that the debonding or yielding of bridged bound rubber layers is key to understanding the behavior of rubber formulations containing the silane coupling agent and high-surface area silica. These results demonstrate that the combination of XPCS and DMA is a powerful method for unraveling the microscale filler response to strain which dictates the dynamic mechanical properties of reinforced soft matter composites. With this combination of techniques, we have elucidated the great promise of UHSA silica when used in concert with a silane coupling agent in filled rubber. Such composites simultaneously exhibit large moduli and low hysteresis under dynamic strain.

36 MATERIALS SCIENCE↗

Evapotranspiration of rubber ( Hevea brasiliensis ) cultivated at two plantation sites in Southeast Asia

The expansion of rubber (Hevea brasiliensis) cultivation to higher latitudes and higher elevations in southeast Asia is part of a dramatic shift in the direction of rural land cover change in the region toward more tree covered landscapes. To investigate the possible effects of increasing rubber cultivation in the region on ecosystem services including water cycling, eddy covariance towers were established to measure ecosystem fluxes within two rubber plantations, one each in Bueng Kan, northeastern Thailand, and Kampong Cham, central Cambodia. The results show that evapotranspiration (ET) at both sites is strongly related to variations in available energy and leaf area, and moderately controlled by soil moisture. Measured mean annual ET was 1128 and 1272 mm for the Thailand and Cambodia sites, respectively. After adjustment for energy closure, mean annual was estimated to be 1211 and 1459 mm yr at the Thailand and Cambodia sites, respectively. Based on these estimates and that of another site in Xishuangbanna, southwestern China, it appears that of rubber is higher than that of other tree dominated land covers in the region, including forest. While measurements by others in non rubber tropical ecosystems indicate that at high net radiation sites is at most only slightly higher than for sites with lower net radiation, mean annual rubber increases strongl with increasing net radiation across the three available rubber plantation observation sites. With the continued expansion of tree dominated land covers, including rubber cultivation, in southeast Asia, the possible association between commercially viable, fast growing tree crop species Giambelluca et al. Evapotranspiration of rubber (Havea brasiliensis) cultivated at two sites in southeast Asia and their relatively high water use raises concerns about potential effects on water and food security.

54 ENVIRONMENTAL SCIENCES↗

Structural evolution of recycled tire rubber in asphalt

ABSTRACT The performance of recycled‐tire‐rubber‐modified asphalt mainly depends on the structure of rubber in the asphalt. The effects of the curing temperature, mixing time, and shearing on the evolution of the chemical structure and morphological structure of crumb rubber in asphalt were investigated. The crosslink density, compositions, and morphological evolution of the residual crumb rubber were characterized. The results show that the structure evolution of tire rubber in asphalt was greatly affected by the curing temperature. At a low curing temperature (180°C), the crosslinking network of the tire rubber was broken down, and this led to the partial dissolution of natural rubber (NR). However, at high curing temperature (240°C), the dissolution of NR, synthetic rubber, carbon black, and inorganic filler was observed. The released carbon black covered with a thin layer of bound rubber dispersed at a microstructured or nanostructured size in the asphalt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 42954.

Yao, Hongru↗

Chemical Recycling of Polybutadiene Rubber with Tailored Depolymerization Enabled by Microencapsulated Metathesis Catalysts

The effective management of plastic waste streams to prevent plastic land and water pollution is a growing problem that is also one of the most important challenges in polymer science today. Polymer materials that are stable over their lifetime and can also be cheaply recycled or repurposed as desired could more easily be diverted from waste streams. However, this is difficult for most commodity plastics. It is especially difficult to conceive this with intractable, cross-linked polymers such as rubbers. In this work, we explore the utility of microencapsulated Grubbs’ catalysts for the in-situ depolymerization and reprocessing of polybutadiene (PB) rubber. Second-generation Hoveyda-Grubbs catalyst (HG2) contained within glassy thermoplastic microspheres can be dispersed in PB rubber below the microsphere’s glass transition temperature (T g ) without adverse depolymerization, evidenced by rubber with and without these microspheres obtaining similar shear storage moduli of ≈16 and ≈28 kPa, respectively. The thermoplastic’s T g can be used to tune the depolymerization temperature, via release of HG2 into the rubber matrix. For example, using poly(lactic acid) (PLA) vs polysulfone results in an 85 and 162 °C depolymerization temperature, respectively. Liquefaction of rubber to a mixture of small molecules and oligomers is demonstrated using a 0.01 mol % catalyst loading using PLA as the encapsulant. Furthermore, at that same catalyst loading, depolymerization occurs to a greater extent in comparison to two ex-situ approaches, including a conventional solvent-assisted method, where it occurs at roughly twice the extent at each given catalyst loading. In addition, depolymerization of the microsphere-loaded rubbers was demonstrated for samples stored under nitrogen for 23 days. Lastly, we show that the depolymerized products can be reprocessed back into solid rubber with a shear storage modulus of ≈32 kPa. Thus, we envision that this approach could be used to recycle and reuse cross-linked rubbers at the end of their product lifetime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application

The availability of concentrated epoxidised natural rubber (ENR-LC) has provided a better opportunity for using epoxidised natural rubber (ENR) with silica to reinforce natural rubber for tyre application. ENR-LC mixed directly with silica to rubber by high speed stirrer without using any coupling agent. Some rubber compounds were prepared by mixing a large amount of precipitated amorphous white silica with natural rubber. The silica was prepared in aqueous dispersion and the filler was perfectly dispersed in the ENR-LC. The performance of the composites was evaluated in this work for the viability of ENR-LC/Si in tyre compounding. Compounding was carried out on a two roll mill, where the additives and curing agents was later mixed. Characterization of these composites was performed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) for dispersion as well as mechanical testing. C-ENR/Si showed efficient as primary reinforcing filler in ENR with regard to modulus and tensile strength, resulting on an increase in the stiffness of the rubbers compared to ENR latex. Overall improvement in the mechanical properties for the ENR-LC over the control crosslinked rubber sample was probably due to synergisms of silica reinforcement and crosslinking of the polymeric matrix phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process

Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.

30 DIRECT ENERGY CONVERSION↗

Rubber friction on road surfaces: Experiment and theory for low sliding speeds

We study rubber friction for tire tread compounds on asphalt road surfaces. The road surface topographies are measured using a stylus instrument and atomic force microscopy, and the surface roughness power spectra are calculated. The rubber viscoelastic modulus mastercurves are obtained from dynamic mechanical analysis measurements and the large-strain effective modulus is obtained from strain sweep data. The rubber friction is measured at different temperatures and sliding velocities, and is compared to the calculated data obtained using the Persson contact mechanics theory. We conclude that in addition to the viscoelastic deformations of the rubber surface by the road asperities, there is an important contribution to the rubber friction from shear processes in the area of contact. The analysis shows that the latter contribution may arise from rubber molecules (or patches of rubber) undergoing bonding-stretching-debonding cycles as discussed in a classic paper by Schallamach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of vinyl acetate grafted natural rubber by irradiation method

Improvement in properties of natural rubber could be done by several methods. In this research, gamma radiation technique, which is simple, accurate, easy to control and clean, was applied to enhance the properties of natural rubber (NR) in latex state. The purpose of this research is to study the appropriate condition for preparing grafted natural rubber latex by using irradiation method. Vinyl acetate monomers (VAc) were grafted onto natural rubber latex (NR-g-PVAc) at 0-10 kGys by gamma radiation from Cobalt-60 source at room temperature. Physical properties of grafted natural rubber such as chloroform number, swelling ratio and gel content were measured. The VAc content of NR-g-PVAc was investigated by titration and visualized by FTIR spectroscopy. The FTIR spectra of NR-g-PVAc prepared at 0-10 kGys showed characteristic peaks of the vinyl acetate confirming that VAc could be grafted onto natural rubber molecular chains effectively under appropriate irradiation conditions. From the result, radiation grafting was found to be a useful technique for grafting of vinyl acetate onto natural rubber.

36 MATERIALS SCIENCE↗

Bio-Based Polyisoprene Can Mitigate Climate Change and Deforestation in Expanding Rubber Production

Biomass is a promising renewable feedstock to produce polyisoprene for the rubber industry. Through metabolic engineering, sugars derived from pretreated and hydrolyzed cellulose and hemicellulose can be directly fermented to isoprene to produce rubber. Here we investigate the life cycle environmental impact of isoprene fermentation to produce bio-polyisoprene from agricultural residues (of Zea mays L.). Results show that the greenhouse gas (GHG) intensity of bio-polyisoprene (−4.59 kg CO2e kg−1) is significantly lower than that of natural rubber (Hevea brasiliensis) and synthetic rubber (−0.79 and 2.41 kg CO2e kg−1, respectively), while supporting a circular biogenic carbon economy. We found the land use intensity of bio-polyisoprene to be 0.25 ha metric ton−1, which is 84% lower than that from rubber tree plantations. We compare the direct fermentation to isoprene results with indirect fermentation to isoprene through the intermediate, methyl butyl ether, where dehydration to isoprene is required. The direct fermentation of isoprene reduces reaction steps and unit operations, an expected outcome when employing process intensification, but our results show additional energy conservation and reduced contribution to climate change. Among the ReCiPe life cycle environmental impact metrics evaluated, air emission related impacts are high for bio-polyisoprene compared to those for natural and synthetic rubber. Those impacts can be reduced with air emission controls during production. All other metrics showed an improvement for bio-polyisoprene compared to natural and synthetic rubber.

Batten, Rahamim↗

Experimental Validation of the Horikx Theory to be Used in the Rubber Devulcanization Analysis

The waste rubber and end-of-life tires management has become a serious environmental problem. It is well known that the best way to carry out the disposal of these wastes is through recycling by devulcanization. Therefore, in the last decades, many methods have been developed to perform this treatment. Nevertheless, the degree and quality of the achieved devulcanization is still difficult to evaluate. The Horikx theory is an approach often used for this purpose. Hence, in this work, the validity of this theory was experimentally checked. The theoretical curve that represents crosslink scission was experimentally built for sulfur-cured natural rubber, sulfur-cured natural rubber reinforced with carbon black, sulfur-cured ethylene propylene diene monomer rubber and peroxide-cured ethylene propylene diene monomer rubber. Several samples with vulcanization (or devulcanization) degree ranging from 0 to 100% were processed, and the corresponding soluble fractions and crosslink densities were measured by the swelling test. The experimental results were in good agreement with the theoretical predictions, independently of the studied material, fact that confirms the validity of the Horikx approach. This finding will contribute to improve the waste rubber devulcanization, and therefore to progress in the environmental protection.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Catalytic conversion of rubber wastes to produce aromatic hydrocarbons over USY zeolites: Effect of SiO 2 /Al 2 O 3 mole ratio

Catalytic conversion of rubber wastes to produce an alternative fuel resource is a promising approach to dispose of solid wastes and address environmental issues. In this study, catalytic fast pyrolysis (CFP) of rubber wastes over acidic zeolites was conducted, and the effect of SiO 2 /Al 2 O 3 mole ratio of USY zeolites on the formation of aromatic hydrocarbons was explored. Experimental results indicated that alkenes and aromatic hydrocarbons were the main pyrolytic products obtained from fast pyrolysis of rubber wastes, and the pyrolysis temperature played a vital role in the formation of aromatics with the highest concentration achieved at 750 °C. Furthermore, catalyst types also affected the catalytic degradation of rubber wastes since limonene was completely decomposed in the presence of zeolites. Compared to SAPO-34, zeolites with higher external surface area, stronger Brønsted acid sites, and larger pore size, including USY, HY, and Hβ, were more effective in the production of aromatic hydrocarbons with the highest content obtained from USY catalyzed run. Given the observed effect of SiO 2 /Al 2 O 3 mole ratio of USY zeolites on the formation of aromatic hydrocarbons during the CFP of rubber wastes, USY with low SiO 2 /Al 2 O 3 ratio of 5.3 was more beneficial to the generation of aromatic hydrocarbons, while that with higher SiO 2 /Al 2 O 3 mole ratio (11.5) facilitated the formation of alkenes. Simultaneously, the product distribution of aromatic hydrocarbons obtained from CFP of rubber wastes over USY zeolites was dominated by xylenes, alkylbenzenes, and toluene, and USY with SiO 2 /Al 2 O 3 mole ratio of 5.3 was more active in the production of toluene and xylenes.

30 DIRECT ENERGY CONVERSION↗