氧化亚铁硫杆菌脱硫天然橡胶粉及其填充胶的性能

从铁矿土壤中分离出1株氧化亚铁硫杆菌,比较了其在不同Fe2+质量浓度的改进9 K培养基中的生长情况,确定最佳的天然橡胶胶粉加入时间为培养开始后的第30 h。利用氧化亚铁硫杆菌在较低Fe2+质量浓度的改进9 K培养基中进行脱硫实验,脱硫橡胶表面的傅里叶变换红外光谱、X射线光电子能谱分析和培养液中SO42-的浓度变化都表明氧化亚铁硫杆菌是通过氧化硫黄的代谢途径来断裂橡胶中的硫黄交联键。用该脱硫胶粉填充天然橡胶硫化胶的力学性能有一定程度的提高;通过扫描电子显微镜可以看出脱硫胶粉与天然橡胶基质的界面结合较好,应力集中点较少,脆断面的断裂线均匀。     

Physicomechanical properties of filled natural rubber vulcanizates modified with phosphorylated cashew nut shell liquid

Effect of fillers like carbon black, silica, and china clay on the cure characteristics and physicomechanical properties of natural rubber (NR) modified with phosphorylated cashew nut shell liquid (PCNSL) in various proportions has been studied. Prominent cure retardation has been observed with progressive increase in concentration of PCNSL from 0 to 20 phr. The softening effect of PCNSL on the vulcanizate has been displayed by the linear decrease in hardness and tensile modulus and the increase in elongation at break with the increase in concentration of PCNSL. The results on the tensile and tear strengths of the vulcanizates showed that the reinforcing effect of the fillers were maximized at concentrations of PCNSL ranging from 5 to 10 phr. Also, the PCNSL-modified NR vulcanizates showed improved resistance to thermo-oxidative ageing and decomposition, especially at the higher concentration of 20 phr. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1303–1311, 1998     

Stress softening in natural rubber vulcanizates. Part V. The anomalous tensile behavior of natural rubber

Stress-strain cycling of natural rubber to high strains produces greater softening than amorphous rubbers, but only if the force on the sample is relaxed below a certain value during the cycle. This phenomenon, attributed to crystallization shows why nonrelaxing tests give a longer fatigue life than relaxing tests.     

酵母菌生物脱硫胎面胶粉及其填充天然橡胶的力学性能

用酵母菌对胎面胶粉(GTR)进行了生物脱硫实验,考察了酵母菌与GTR共培养脱硫过程中酵母菌的生长情况,对比了GTR和脱硫GTR(DGTR)填充天然橡胶(NR)硫化胶的交联密度、表面元素含量和力学性能.结果表明,在共培养脱硫过程中酵母菌依然可以保持较高的生物量,脱硫6 d后可获得生物脱硫的GTR.随着胶粉用量的增加,填充NR硫化胶的交联密度和力学性能逐渐降低.相比较GTR/NR硫化胶,DGTR/NR硫化胶的表面硫元素含量和交联密度更低,力学性能明显提高.     

Crack growth and abrasion resistance of carbon black‐filled purified natural rubber vulcanizates

The influence of parameters contributing to rubber stiffness, including, crosslink density, hardness, and modulus, on the crack growth and abrasion resistance of carbon black‐filled purified natural rubber (PNR) vulcanizates as well as a whole natural rubber (WNR) vulcanizate counterpart or a control were elucidated. In addition, the tensile properties of PNR and WNR were also determined. PNR containing the same curative level as that of the control had lower stiffness and exhibited superior crack growth resistance. The results revealed that the improved crack growth resistance of PNR, compared to the control, was due to its lower crosslink density, hardness, and modulus. In addition, the tensile strength and abrasion resistance of PNR vulcanizates were not as sensitive as the crack growth resistance to the changes of their stiffness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1793–1796, 2003     

Fracture behavior of NR and SBR vulcanizates filled with ground rubber having uniform particle size

The use of recycled rubber including ground scrap vulcanizates in rubber compounds was studied. When ground rubber was incorporated into rubber compounds, the physical properties, especially the tensile strength, were deteriorated compared to the virgin rubber compound. Also, incorporating ground rubber caused a change of the cure behavior via migration of sulfur or an accelerator between the virgin rubber matrix and the ground rubber vulcanizate. In this study, the fracture behavior and abrasion property of carbon black‐filled SBR and NR compounds containing ground rubber vulcanizate were investigated. Also, the effect of the particle size or loading volume of ground rubber powder on those properties was studied. Four different sizes, 420–600, 177–250, 125–150, and 75–88 μm, of ambient ground rubber powder recycled from waste tire were selected and used in the compounding. The loading amounts of ground rubber powder were 10, 30, and 50 phr. The flex crack growth of SBR‐ and NR‐based compounds was altered by the addition of ground rubber particles. More delayed crack growth was observed with an increasing loading volume and decreasing particle size of the ground rubber powders, and this behavior was more prominent in SBR than in NR compounds. Tangent delta, a direct measure of internal energy dissipation, increased with an increasing loading volume of the ground rubber particles. The abrasion rate of ground rubber‐filled compounds was more dependent on the size of the abrasion pattern than on the loading level or particle size of the ground rubber powders. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2491–2500, 2002     

Stress softening in natural rubber vulcanizates. Part IV. Unfilled vulcanizates

Stress softening (Mullins effect) is observed in gum natural rubber vulcanizates. The magnitude of this softening is similar to that in carbon black-filled vulcanizates. The amount of stress softening is slightly greater in vulcanizates cured to produce predominantly polysulfide crosslinks than in those containing monosulfide or carbon–carbon crosslinks. The total recovery of stress softening in the vulcanizates containing monosulfide or carbon–carbon crosslinks suggests that the phenomenon is attributable to a quasi-irreversible rearrangement of molecular networks due to localized nonaffine deformation resulting from short chains reaching the limit of their extensibility. This non-affine deformation results in a displacement of the network junctions from their initial random state.     

Properties of natural rubber vulcanizates containing mechanochemically devulcanized ground tire rubber

The devulcanization of ground tire rubber (GTR) was carried out with a self-designed pan-mill type mechanochemical reactor. Gel fraction and crosslink density measurements confirmed the occurrence of stress induced mechanochemical devulcanization of GTR. The partially devulcanized GTR (dGTR) was blended with virgin natural rubber (NR) at different ratios. The curing characteristics and mechanical properties of these composites were investigated and compared with those composites of raw ground tire rubber (rGTR) and NR. The results showed that the tensile properties of the dGTR/NR vulcanizates were much better than those of the rGTR/NR vulcanizates, which are comparable to or even better than the virgin vulcanizate, indicating the significant benefit of mechanochemical devulcanization. At the GTR content of 10%, the tensile strength of the dGTR/NR blends increased to 23.2 MPa from 13.7 MPa of the rGTR/NR blends, enhanced by 69% through partial devulcanization of GTR, and the elongation at break increased by 47%.     

A study of sulfur bridges in filled natural rubber vulcanizates by pyrolysis gas chromatography with flame-photometric detection

Natural rubber vulcanizates of two formulations, with sulfur/N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and tetramethylthiuram disulfide (TMTD), respectively, were analyzed by pyrolysis gas chromatography. A sulfur-selective flame-photometric detector was utilized. The main pyrolysis products were identified as CS₂ and some thiophenes. The yields of the pyrolysis products from the two types of rubber were very different. The yields also varied with the curing time of the rubbers.     

Studies on double networks in natural rubber vulcanizates

The concept of double networks is a rather new idea, by which one imparts chain orientation in elastomers. Double networks were made in natural rubber vulcanizates cured with a single and a new binary accelerator system. Double networks with different extensions were prepared and their effects on tensile properties were analyzed. The influence of extent of initial cure on double‐network formation was examined. Thermal stability of the double network formed was analyzed by ageing of the double networks and was found to improve with residual extension. Crosslink density of the networks formed was determined by swelling methods and stress–strain analysis. It was found that crosslink density increased with double‐network formation and residual extension. The stress–strain behavior and moduli were analyzed to study the effect of these properties on double‐network formation. Double networks were hardly affected by the binary accelerator system. Based on the studies it was found that residual extension was the major factor determining the final properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1068–1076, 2004     

Stress softening in natural rubber vulcanizates. Part III. Carbon black-filled vulcanizates

Stress softening (Mullins effect) occurs in rubber vulcanizates during the first and subsequent deformations. This paper shows the similarity of the degree of stress softening in both unfilled and carbon black-filled vulcanizates of natural rubber when stressed almost to break. This confirms the earlier investigations which were confined to moderate stresses. A simple interpretation of the tensile stress–strain results for filled rubber is that the strain in the rubber is increased by the presence of the filler, so that the ratio of the average strain in the rubber to the measured overall strain is given by a strain amplification factor. The usefulness of this concept is confirmed by showing the similarity of the stress-softened curves after normalizing the strains, provided the vulcanizates of both gum and filled vulcanizates were subjected to the same initial stress.     

Dynamic properties of PBNA–natural rubber vulcanizates

Some crystalline organic compounds containing a β-naphthyl group stiffen rubbers considerably. This paper discusses the dynamic behavior of these systems when subjected to oscillatory strain of increasing amplitude. Modulus–strain amplitude plots similar to that in carbon black–natural rubber systems are obtained. The implication of these results to reinforcement theory is discussed.     

Application of computed X-ray tomography scanning in the study of thermo-oxidative degradation of thick-walled filled natural rubber vulcanizates

The aging of five thick-walled natural rubber compounds has been studied by computed X-ray tomography scanning and crosslink density measurements. The compounds were compouded as ordinary carbon-black-filled rubbers with sulfur and peroxide as curing agents. The rubber samples were aged in air at 70, 100, and 150°C for 1000h. The relatively new technique of computed X-ray tomography scanning proved to be a good method for studying the aging procedure, and especially for following the crack propagation in the surface. Antioxidants (TMQ and 6PPD) had a low effect on the resistance toward oxidative degradation and crosslinking under these conditions. Surprisingly, the efficient sulfur-vul-canized material had a poor resistance toward thermal degradation. When the crosslink density and the computed X-ray tomography scanning results were compared, it was assumed that the computed X-ray tomograph detected oxygen in the surface, both as elementary oxygen and as oxygen in degradation products, i.e., in carbonyls. The results agree well with the theory that oxidative aging is limited by the ability of the oxygen to diffuse into the material.     

Improving oxidation stability and mechanical properties of natural rubber vulcanizates filled with calcium carbonate modified by gallic acid

A novel technique to modify the surface of calcium carbonate (CaCO₃) nanoparticles, used as an antioxidant and reinforcing filler, by gallic acid is disclosed. The new properties of the modified CaCO₃ could make it more useful and practical for the rubber industry. Thermal gravimetric (TGA), Fourier transform infrared spectroscopy, and transmission electron microscopy analyses showed that the gallic acid was bound onto the surface of CaCO₃. The gallic acid modified CaCO₃ exhibited a significant antioxidation property, as revealed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) analysis. The mechanical properties of natural rubber vulcanizates filled with the gallic acid modified CaCO₃ showed an enhanced reinforcement with increasing loading levels, and increased resistance to ozonolysis over that seen with the unmodified CaCO₃ mixed with Irganox 1010 as the commercial antioxidant.     

Temperature dependence of birefringence for strained natural rubber vulcanizates

The birefringence for uniaxially extended DCP-cured natural rubber was measured in the temperature range of 213K–353K. The variation of birefringence reflected the changes of the network structure, i.e. the development and disappearence of strain-induced crystals, and the degree of the orientation of amorphous network chains. It became clear from the variation of birefringence that the nucleation condition which is required to allow growth of an extended chain crystal occurred at extension ratio of 2.5–3.5.     

Properties of vulcanizates from blends of natural rubber and thioglycolic acid modified,epoxidized, low‐molecular‐weight natural rubber filled with carbonized rubber seed shell

Vulcanizates from blends of natural rubber and thioglycolic acid modified, epoxidized, low‐molecular‐weight natural rubber filled with mixtures of carbon black and carbonized rubber seed shell, with semiefficient sulfur vulcanization recipes, were critically investigated and characterized. The investigated properties were the processing and rheological properties (the cure rate, cure time, scorch time, total oscillating disc rheometry torque, and Mooney viscosity), physicomechanical and chemical properties, solvent resistance, solubility, and swelling properties. On the basis of the investigated properties, it was observed that the carbonized rubber seed shell acted as a plasticizer and not as a reinforcing filler such as carbon black. The replacement of carbon black with up to 20% carbonized rubber seed shell produced vulcanizates having processing advantages in time gain and energy consumption, with their physical, chemical, and mechanical properties around the acceptable level for natural rubber compounds but lower than the properties obtained for a 100% carbon black filled vulcanizate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Oxidative aging of natural rubber vulcanizates. Part I. The scission of peroxide vulcanizates

A new method has been developed for measuring the number of molecules of oxygen required (?) to cause a main chain scission in peroxide vulcanizates of natural rubber. This method is based on experimentally derived relationships and is not dependent on statistical theories of rubber elasticity. The value ? is only slightly temperature dependent, ranging from 28 at 65°C. to 22 at 100°C. The effects of several types of antioxidant have been examined, in all cases ? was greatly reduced. The effect of antioxidant 2246 has been studied in more detail and the results indicate that there is a high probability of scission occurring at the termination step in the oxidation chain.     

Fracture properties of silica/carbon black-filled natural rubber vulcanizates

Crack growth property of natural rubber (NR) vulcanizate with varying silica/carbon black content was examined. Tensile specimen with edge cut was used for estimating fracture properties. All filled NR specimens showed critical cut-size (C _cr ), which is related to abrupt decrease in tensile strength. Carbon black-filled NR, S0 (Si/N330=0/50) has higher tensile strength than equivalently loaded silica-filled NR vulcanizates, S5 (Si/N330=50/0). When the precut size of specimen was less than critical cut-size, tensile strength of S1 (Si/N330=10/40) composition was the highest and that of S5 was the lowest. The critical cut-size passes through a maximum for S2 (Si/N330=20/30) and then decreases gradually with silica loading. An interesting result was that silica and carbon black-blended compounds gave higher critical cut size than the all-carbon black compounds, S0. The inherent flaw size decreased from 246 μm for S0 to 80 μm for S5 as the silica content increased.     

Mechanical properties of deproteinized natural rubber in comparison with synthetic cis‐1, 4 polyisoprene vulcanizates: Gum and black‐filled vulcanizates

Gum and black‐filled vulcanizates having various crosslink densities were prepared from 2 types of rubber, namely, deproteinized natural rubber (DPNR) and synthetic cis‐1, 4 polyisoprene vulcanizates (IR). Their mechanical properties, such as tensile strength, tear strength, abrasion loss, and heat buildup resistance, at various crosslink densities as well as at similar optimum crosslink density were compared. For both gum and black‐filled systems, IR possessed a higher crosslink density than that of DPNR at a fixed curative content. Tensile and tear strength of all vulcanizates passed through a maximum with increasing crosslink density. For gum vulcanizates, tensile and tear strengths of DPNR and IR below the maximum were not much different. However, IR had a narrower tear strength peak relative to DPNR. At a comparable optimum crosslink density, DPNR exhibited higher tensile strength and crack growth resistance than IR. For black‐filled vulcanizates, tensile and tear strengths, and heat buildup resistance of DPNR and IR at a given crosslink density were similar. The results revealed that the properties of gum samples were more dependent upon crosslink density than the black‐filled ones because the reinforcement by carbon black overshadowed the intrinsic properties of the rubbers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1139–1144, 2005