Biodegradation of Natural Rubber and Natural Rubber Products by <Emphasis Type="Italic">Streptomyces</Emphasis> sp. Strain CFMR 7

The rubber degrading activity of Streptomyces sp. CFMR 7 whose whole genome sequence was recently determined was tested with non-vulcanized fresh latex and common vulcanized rubber products such as latex glove, latex condom and latex car tyre. The degradation activity was unequivocally demonstrated by scanning electron microscopy with respect to microbial colonization efficiency, disintegration of rubber material and biofilm formation after 3, 6 and 9 months of inoculation. Fourier transform infrared spectroscopy comprising the attenuated total reflectance analysis on these inoculated products revealed insights into the biodegradation mechanism of this strain whereby, a decrease in the number of cis -1,4 double bonds in the polyisoprene chain, the appearance of ketone and aldehyde groups formation indicating an oxidative attack at the double bond of rubber hydrocarbon. In the presence of strain Streptomyces sp. CFMR 7, gel permeation chromatography analysis revealed a significant shift of the molecular weight distribution to lower values. Clear decrease in the molecular weight was observed over 3, 6 and 9 months of cultivation on fresh latex samples compared to other vulcanized products. No shift in the molecular weight distribution was observed for non-inoculated control. These results clearly showed that Streptomyces sp. CFMR 7 was able to cleave the carbon backbone of poly (cis -1,4-isoprene). Although this strain was able to degrade both non-vulcanized and vulcanized rubber products, faster degradation was obtained with natural rubber and rubber products with low complexity.     

Two-Step Cultivation Method for Microbial Disintegration of Tire Rubber Particles

A rubber-degrading strain of Nocardia was cultured on tread rubber particles from a truck tire by a two-step cultivation method. At the first step, the culture medium was either not agitated or stirred at very slow rate of 40 rpm for one or 2 weeks. At the second step, the culture medium was stirred at relatively higher stirring rate of 150 or 300 rpm for seven or six weeks. It was found that the rate of disintegration was greatly increased and the weight losses of the particles with diameters of about 2.3 mm were as high as 40% in the two-step method and only 20–30% in a one-step method in which the stirring rate was kept constant throughout the culture period. With this method, microbial colonization and disintegration were depressed particularly at the corners of the cubic particles and characteristic protuberant structures were observed at the corners after the removal of microbial cells by washing.     

The Potential of Chicken Eggshell Waste as a Bio-filler Filled Epoxidized Natural Rubber (ENR) Composite and its Properties

Eggshell calcium carbonate (ECC) and eggshell calcium carbonate treated with high temperature (ECC-600) were prepared from chicken eggshell waste. ECC was obtained by crushing eggshell waste, eliminating membranes and followed by sieving. In the case of ECC-600, ECC powder was additionally heated at 600 °C for 2 h. Both were used to promote as fillers compared to that of commercial light-precipitated calcium carbonate (commercial CaCO₃) with various loading levels (i.e., 0, 25, 50 and 75 phr) in epoxidized natural rubber containing 25 mol% of epoxide group (ENR-25). Among the three types of fillers (i.e., ECC, ECC-600 and commercial CaCO₃), ECC filled materials showed superior vulcanization characteristics by the increasing of maximum torque (M_H) and cure rate index (CRI) with the reducing of cure time (t_c90) and scorch time (t_s2). The highest tensile properties as well as the lowest tension set value were also observed. Morphological property revealed that ECC was greater interfacial adhesion than those of others. In addition, dynamic mechanical properties of vulcanizates containing ECC, storage modulus (E′) was the highest and glass transition temperature (T _g ) shifted toward high temperature. Increasing of loading levels of any fillers affected the increase of M_H and CRI with reducing of t_c90 and t_s2. However, tensile properties decreased with increasing filler content but it did not affect T _g shifting except for a series of vulcanizates containing ECC.     

Visualization of the Malleability of the Rubber Core of Rubber Particles from Parthenium argentatum Gray and Other Rubber-Producing Species Under Extremely Cold Temperatures

Rubber particles from Parthenium argentatum Gray (guayule) were frozen in liquid nitrogen (–196°C), fractured, and visualized using cryo-scanning electron microscopy. We observed that the rubber polymer core of the rubber particles was still malleable at this extremely cold temperature, and the core stretched substantially during separation of the fracture planes. This malleability was observed in situ in tissue sections, as well as in purified rubber particles, and was found to be independent of purification procedure, guayule line, tissue age, or season. The malleability or stretching phenomenon suggests that P. argentatum rubber has some unique properties because rubber particles from Hevea brasiliensis Müll. Arg. and Ficus elastica Roxb. were brittle at this temperature, fractured cleanly, or showed only tiny threads of material pulling out of the core.     

Water Absorption Kinetics and Hygrothermal Aging of Poly(lactic acid) Containing Halloysite Nanoclay and Maleated Rubber

Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E _a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T _g ), cold-crystallization temperature (T _cc ) and melting temperature (T _m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.     

Microbial Degradation of the Natural Rubber in Tire Tread Compound by a Strain of Nocardia

Tread compound of truck tires is based primarily on natural rubber or blends of natural rubber (NR) and synthetic polymers in combination with high grade carbon black. When the tread compound is attacked by a strain of Nocardia capable of degrading NR, part of the NR in the compound is mineralized, and part is disintegrated to very small black particles. The small black particles consist of the residual rubber and inorganic fillers. At higher NR content, large and deep cavities are formed on the surface of the pieces of the tread compound after microbial disintegration. At lower content of NR, large but very shallow cavities or very small pits can be seen on the tread surface. During microbial growth on the tread compound, isoprene oligomers with molecular weight of about two thousand are produced. Not only the isoprene oligomers, but also butadiene oligomers are produced during microbial disintegration of the tread compound of NR/synthetic rubber blend.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Devulcanization of Ground Tires by Different Strains of Bacteria: Optimization of Culture Condition by Taguchi Method

Biological devulcanization of ground tires (GTs) was evaluated by eleven different bacteria belonging to the genera Thiobacillus, Gordonia, Nocardia, Amycolaptopsis and Pseudomonas. The GTs were treated by each bacterium in a mineral medium and devulcanization was measured by increasing the sulfate of the medium and decreasing the sulfur of the GTs. The effects of incubation time (10 and 20 days) and the percent of ground tire in the medium (0.5 and 5 w/v %) on desulfurization were investigated. No significant changes were observed after 10 days of incubation. The total sulfur contents of all bio-treated GTs were decreased by 6–21% in 0.5% GTs after 20 days of incubation. While in 5% GTs, the total sulfur contents were mainly decreased using Thiobacillus ferroxidans DSMZ 583 and PTCC 1647 up to 27 and 15%, respectively. SEM photograph further indicated a good coherency interface between the bacteria and the GTs. Subsequently, Taguchi method was applied for the optimization of the culture condition of DSMZ 583. An L12 orthogonal array was performed by which the effects of eleven factors in two levels were evaluated. It was found that the amount and mesh size of GTs are the most important factors in biological devulcanization of ground tires.     

Preparation of Natural Rubber/Condensed Tannin Semi-interpenetrating Polymer Network Composites by Hematin-Catalyzed Cross-Linking

In this study, the preparation of semi-interpenetrating polymer network (semi-IPN) composites composed of natural rubber and condensed tannin was performed by means of the enzyme-mimetic cross-linking of condensed tannin catalyzed by hematin. Prior to the preparation of the composites, the hematin-catalyzed cross-linking behavior of condensed tannin was evaluated by the TGA measurement. The TGA results indicated that condensed tannin was sufficiently cross-linked by the hematin-catalyzed reaction in the presence of appropriate amounts of 30% (w/v) H₂O₂ aq. to give the relatively thermostable materials. For the preparation of the composites, a solution of condensed tannin and hematin, and subsequently 30% (w/v) H₂O₂ aq. were added to natural rubber latex and the mixture was stirred at room temperature for 10 min to perform the cross-linking of condensed tannin, followed by drying of the reaction mixture at 50 °C for 5 h, which was subsequently put into a heat device and hot-pressed at 100 °C and 20 MPa for 20 min to give the semi-IPN composite. The tensile stress?Cstrain measurement of the composites was conducted to evaluate the mechanical properties, which were changeable depending on the weight ratios of natural rubber to condensed tannin and the amounts of 30% (w/v) H₂O₂ aq. Moreover, the miscibility of the cross-linked tannin with natural rubber in the composite was evaluated by the SEM measurement.     

Production,Characterization and Bioemulsifying Activity of an Exopolysaccharide Produced by <Emphasis Type="Italic">Sphingomonas</Emphasis> sp. Isolated from Freshwater

This study aimed to evaluate the emulsion stability of solutions containing exopolysaccharide and culture medium of a Sphingomonas sp. strain with various hydrophobic compounds. The exopolysaccharide characterized belongs to a sphingan group, however, not being a gellan gum as produced by certain Sphingomonas strains. In general, the emulsifying indexes found in this study were above 70% for gasoline, hexane, kerosene and used frying oil. Nonetheless, the best results were achieved in kerosene solutions, which showed an index of 80% after 24 h, remaining stable for more than 168 h in combinations with various EPS concentrations. Interestingly, diesel oil best results were singly achieved in solution pH of 11, showing an index of around 65%. Furthermore, hexane obtained an index of 100% after 24 h when culture medium was used. Thus, these findings highlight the use of EPS as a potential bioemulsifier agent to enhance hydrocarbon degradation and emulsification effects in environmental biotechnology.     

Cetyltrimethyl Ammonium Bromide Modified Kaolin as a Reinforcing Filler for Natural Rubber

Cure characteristics, Mooney viscosity and physico-mechanical properties of natural rubber (NR) containing CTAB modified kaolin have been studied. NR mix containing 6 phr (parts per hundred part rubber) of CTAB modified kaolin showed significant increases in cure rate and state of cure as compared to gum NR compound and a mix containing the same amount of unmodified kaolin. Lower Mooney viscosity of the NR mix containing CTAB modified kaolin suggested improved processability. Reinforcing effect of CTAB modified kaolin in NR was evident from higher chemical crosslink density index, tensile modulus, hardness, tensile strength and tear strength. Besides, the NR vulcanizate containing 6 phr of CTAB modified kaolin showed lower abrasion loss and heat build-up which could be beneficial for applications such as tire treads.     

Experimental study of rubber tire aggregates effect on compressive and dynamic load-bearing properties of cylindrical concrete specimens

Sustainable development has become a major focus for engineers and planners as part of their collective efforts in finding, developing and integrating environmental-friendly solutions for material recycling and waste management into design and construction of civil engineering infrastructure. In the past three decades, there has been an increase in recycling and application of waste materials into the concrete to decrease costs and improve material properties of the concrete. Significant growth in automobile manufacturing industry and increased rubber tire supply for vehicles suggested the application of waste tire particles as concrete aggregates to minimize the ecological footprint of the rubber tire waste due to its recycling process difficulties. In this paper, the effect of rubber tire particles on compressive and dynamic strength of concrete specimens with different particle percentiles was tested on more than 55 cylindrical specimens. To achieve the optimal mix design properties of rubber tire concrete specimens, both fine and coarse aggregates got replaced by fine and coarse rubber particles. Introduction of rubber tire particles as coarse and fine aggregate reduces the brittleness of the concrete and provides more flexible aggregate bonding which ultimately improves the dynamic resistance of the concrete. It increases the concrete workability and provides environmental-friendly and cost-effective solutions in using recycled materials for concrete construction applications.     

Utilization of waste tire rubber in manufacture of oriented strandboard

Some physical and mechanical properties of oriented strandboards (OSBs) containing waste tire rubber at various addition levels based on the oven-dry strand weight, using the same method as that used in the manufacture of OSB. Two resin types, phenol–formaldehyde (PF) and polyisocyanate, were used in the experiments. The manufacturing parameters were: a specific gravity of 0.65 and waste tire rubber content (10/90, 20/80 and 30/70 by wt.% of waste tire rubber/wood strand). Average internal bond values of PF-bonded OSB panels with rubber chips were between 17.6% and 48.5% lower than the average of the control samples while polyisocyanate bonded OSBs were 16.5–50.6%. However, water resistance and mechanical properties of OSBs made using polyisocyanate resin were found to comply with general-purpose OSB minimum property requirements of EN 300 Type 1 (1997) values for use in dry conditions at the lowest tire rubber loading level (10%) based on the oven-dry panel weight. The tire rubber improved water resistance of the OSB panel due to its almost hydrophobic property. Based on the findings obtained from this study, we concluded that waste tire rubber could be used for general-purpose OSB manufacturing up to 10% ratio based on the oven-dry panel weight.     

Environmental impact of highway construction and repair materials on surface and ground waters. Case study: crumb rubber asphalt concrete

The practice of incorporating certain waste products into highway construction and repair materials (CRMs) has become more popular. These practices have prompted the National Academy of Science, National Cooperative Highway Research Program (NCHRP) to research the possible impacts of these CRMs on the quality of surface and ground waters. State department of transportations (DOTs) are currently experimenting with use of ground tire rubber ( crumb rubber) in bituminous construction and as a crack sealer. Crumb rubber asphalt concrete (CR-AC) leachates contain a mixture of organic and metallic contaminants. Benzothiazole and 2(3H)-benzothiazolone (organic compounds used in tire rubber manufacturing) and the metals mercury and aluminum were leached in potentially harmful concentrations (exceeding toxic concentrations for aquatic toxicity tests). CR-AC leachate exhibited moderate to high toxicity for algae ( Selenastrum capriconutum) and moderate toxicity for water fleas ( Daphnia magna). Benzothiazole was readily removed from CR-AC leachate by the environmental processes of soil sorption, volatilization, and biodegradation. Metals, which do not volatilize or photochemically or biologically degrade, were removed from the leachate by soil sorption. Contaminants from CR-AC leachates are thus degraded or retarded in their transport through nearby soils and ground waters.     

A Study on Functionalization of Waste Tire Rubber Powder Through Ozonization

In this study, ozone treatment was used to improve the surface wettability of waste tire rubber (WTR) powders. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) were performed in order to characterize the surface composition of the treated samples. The progress of surface modification was also monitored by contact angle measurements of different test liquids (water and liquid paraffin). The surface energy values were evaluated in terms of the Owens’ method and the contact angle data were compared with the results obtained by the surface analytical methods (i.e. FTIR and XPS measurements). These results showed that ozone treatment lead to a remarkable decrease in water contact angle owing to the implantation of oxygen-containing functional groups. Using XPS and FTIR, the oxygen-containing groups can be identified as C–O, O–C=O and C=O. With prolongation of ozone treatment time, WTR exhibited increasing oxygen-containing groups, surface energy and wettability.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Processing and Characterization of Recycled Polypropylene and Acrylonitrile Butadiene Rubber Blends

In this paper investigation on thermoplastic elastomers (TPE) and thermoplastic vulcanizates (TPV) derived from waste polypropylene (WPP) of Municipal Solid Waste (MSW) and acrylonitrile-butadiene rubber (NBR) are reported. The WPP was segregated, cleaned, dried and melt processed with NBR at 180 °C in a Brabender Plasticorder at different blend ratios. TPV was prepared by dynamic vulcanization of the TPE with conventional sulfur accelerator curing system. The mechanical properties measured were found to decrease with increase in NBR proportion in the blend; however the dynamic vulcanization of the nitrile rubber phase enhanced the strength properties of the corresponding TPE. The crystallinity of the WPP reduced with increase in NBR ratio. The dynamic modulus decreased with nitrile rubber content in the TPE. Interestingly, the storage modulus of the TPV at higher rubber content enhanced significantly and damping characteristics increased sharply. The rheology studies reveal that the damping of the blend has been reduced with the addition of high storage modulus rubber at melt processing conditions and hence increased viscosity. The amorphous rubber content with higher storage modulus imparts higher viscosity for the polypropylene (PP) matrix at the processing temperature. The SEM study reveals that the dynamic vulcanization of the rubber phase in the blend caused a smoother and finer surface morphology.     

Recovery of glass fibers from glass fiber reinforced plastics by pyrolysis

Fiber-reinforced plastic sheets containing unsaturated polyester cross-linked with styrene, CaCO₃ and glass fibers as fillers were pyrolyzed in a helium and steam atmosphere in order to recover glass fibers and valuable organic pyrolysis products. Glass fibers were separated from CaCO₃ and CaO by dissolving calcium salts in hydrochloric acid. Residual organic material was burnt afterwards. Best results were obtained at a pyrolysis temperature of 600 and 700 °C, resulting in a large liquid fraction high in styrene, leaving little residual organic material on the surface of the glass fibers. At a pyrolysis temperature of 500 °C, the degradation of the polymer matrix was incomplete, and at 900 °C, glass fibers were destroyed in the presence of CaO, leaving CaSiO₃ as a product.     

Fouling and Degradation of Polycarbonate in Seawater: Field and Lab Studies

Biofouling and ensuing microbial mediated degradation of Bisphenol A polycarbonate was studied by immersing the samples in sea water of Bay of Bengal (Chennai, India) for 3 months and also under controlled laboratory conditions with marine mixed microbial consortia for 12 months. A 9% weight loss in the sample was observed after 1 year of incubation under in vitro laboratory conditions. A 5% reduction in number average molecular weight and an additional oligomer with a molecular weight of 930 was observed in the same sample. Contact angle decreased by 11% indicating an increase in the surface hydrophilicity. The specific heat decreased by 44% and glass transition temperature decreased by 3 °C with respect to the control indicating chain scission. Formation of new hydroxyl groups and cleavage of carbonate bonds in polycarbonate suggested biodegradation. About 9 μg mL⁻¹ of Bisphenol A, a monomer of polycarbonate, as well as its oxidized products were detected in the supernatant. The nature of degradation in field and in vitro was different. It was predominantly oxidation in the former and hydrolysis in the later environment. A strain exhibiting hydrolase activity was isolated at the end of the 12 months from the in vitro mixed consortia and was identified, based on biochemical and 16S rDNA tests, as Pseudomonas sp. BP2 (GenBank accession no. EU920674).     

Effect of microsilica addition on compressive strength of rubberized concrete at elevated temperatures

An experimental investigation was carried out to study the effects of various percentages of fine/coarse tire waste and microsilica at various temperatures on the compressive strength of concrete. The compressive strength of concrete mixtures made with tire rubber was assessed statistically with those of concrete containing microsilica and conventional concretes in order to evaluate the usefulness of recycling rubber waste as a component of concrete. Results confirmed that the recipe and processing temperature of concrete cubes influence the compressive strength values. Generally, the use of microsilica or fine rubber mixed with microsilica as aggregate replacement of 5% by volume improved the compressive strength of concrete processed at a temperature of 150°C. The addition of coarse rubber did not achieve any increase in strength when used as an aggregate replacement at any percentage. Moreover, the reductions in the compressive strength of concrete mixes at higher temperatures were much smaller for the fine rubber with 5 vol% microsilica than those for control and coarse rubber mixes. The specimens made with fine rubber and 5 vol% microsilica at elevated temperatures above 400°C appeared to show very similar compressive strength values. The use of fine rubber in building construction could help save energy and reduce costs and solve the solid waste disposal problem posed by this type of waste.