Analysis of unbound materials in carbon‐black‐filled NR vulcanizates

Extraction of unbound materials from carbon‐black‐filled natural rubber (NR) vulcanizates with different cure systems was studied using various solvents with different dielectric constants of n‐hexane, toluene, THF, acetone, and acetonitrile. The extraction was performed at room temperature and 40°C for 2 days and in the boiling solvent for 8 h. Amounts of extracted materials from the NR vulcanizates increase by increasing the temperature. Amounts of extracted materials from the NR vulcanizates with n‐hexane, toluene, and THF are more than those with acetone and acetonitrile. Amounts of extracted materials from the NR vulcanizate with a high crosslink density are less than those from the NR vulcanizate with a low one. Thermogravimetric analysis of the NR vulcanizates before and after the extraction were carried out to investigate components of the extracted materials. It was found that there were polymer components and metal complexes, as well as organic matters with a low molecular weight in the extracted materials. Abilities of the solvents to extract unbound materials from the NR vulcanizates were discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1995–2005, 1999     

Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging

Variation of the crosslink density of a rubber vulcanizate depending on the rubber composition after the thermal aging was studied with single rubber, biblend, and triblend vulcanizates of natural rubber (NR), butadiene rubber (BR), and styrene‐butadiene rubber (SBR). The efficient vulcanization (EV) system was employed to minimize the influence of free sulfur in the vulcanizate on the change of the crosslink density. Thermal aging was performed at 40, 60, and 80°C for 20 days with 5‐day intervals. The crosslink densities of the vulcanizates after the thermal aging increase. For the single rubber vulcanizates, variation of the crosslink density by the thermal aging has the order: SBR > BR > NR. For the biblend vulcanizates, variations of the crosslink densities of the NR/SBR and SBR/BR blends are larger than that of NR/BR blend. Variation of the crosslink density of the vulcanizate increases by increasing the SBR content in the vulcanizate. Variation of the crosslink density of the rubber vulcanizate depending on the rubber composition was explained by miscibility of the blends, combination reaction of the pendent groups, and mobility of the pendent group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1378–1384, 2000     

Effect of crosslink structures on dynamic mechanical properties of natural rubber vulcanizates under different aging conditions

The effects of crosslink structures on the dynamic mechanical properties (DMPs) of unfilled and carbon black N330‐filled natural rubber (NR) vulcanizates cured with conventional (CV), semiefficient (SEV), and efficient (EV) cure systems and having about the same total crosslink densities were investigated before and after aerobic and anaerobic aging at 100°C. The three unfilled NR vulcanizates cured with the CV, SEV, and EV systems had about the same mechanical loss factor (tan δ) values at about 0°C but showed some apparent differences in the tan δ values in the order EV > SEV > CV at relatively high temperatures of 40–80°C before aging. However, N330‐filled NR vulcanizates gave higher tan δ values than the unfilled vulcanizates and showed little effect of the crosslink types on the tan δ at different temperatures over the glass‐transition temperature (T_g) before aging. Aerobic heat aging increased the T_g and tan δ values of the vulcanizates over a wide range of temperatures from ?80 to 90°C that was mainly due to the changes in the total density and types of crosslinks. The unfilled vulcanizates cured with the CV system showed the greatest change in DMP because of their poor resistance to heat aging. Aerobic heat aging of NR vulcanizates caused a more significant change in the DMP than anaerobic heat aging because of the dominant effect of the oxidative degradation during aerobic heat aging on the main‐chain structure, crosslink structures, and DMPs of the vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 710–718, 2001     

Compatibilization of SBR/NBR blends using chemically modified styrene‐co‐butadiene rubber Part 2. Effect of compatibilizer loading

The present work focuses on the compatibization of styrene‐co‐butadiene rubber (SBR)/acrylonitrile‐co‐butadiene rubber (NBR) blends with dichlorocarbene modified styrene‐co‐butadiene rubber (DCSBR) as a function of concentration of compatibilizer and composition of the blend. FTIR studies, differential scanning calorimetry and dynamic mechanical analysis reveal molecular level miscibility in the blends in the presence of compatibilizer. The formation of interfacial bonding is assessed by analysis of swelling behaviour, cure characteristics, stress–strain data and mechanical properties. These studies show that the compatibilizing action of DCSBR becomes more prominent as the proportion of NBR in the blend increases. The resistance of the vulcanizate towards thermal and oil ageing improved with compatibilization. The change in technological properties is correlated with the crosslink density of the blends assessed from swelling and stress–strain data. © 2001 Society of Chemical Industry     

Effect of crosslinking on the conductivity of conductive silicone rubber

We investigated the effect of polyvinylsilicone oil (C gum) as a crosslinker and 2,5‐bis(tert‐butyl peroxy)‐2,5‐dimethyl hexane (DBPMH) as a curing agent on the conductivity of conductive silicone rubber with two different kinds of conducting mechanisms. The experimental results show that the volume resistivity of conductive silicone rubber changed with its degree of crosslinking. When the carbon black loading was 25 parts per hundred rubber (phr) and a completely continuous conducting network had not formed, the volume resistivity of the vulcanizates decreased with increasing crosslink density. The volume resistivity of the vulcanizate with a suitable amount of C gum decreased to 53%, and the tensile strength increased by 0.8 MPa compared to the vulcanizate without C gum. When the carbon black loading was 40 phr and a completely continuous conducting network had formed, the crosslink density of vulcanizates changed as the amount of DBPMH changed. The volume resistivity of vulcanizates first decreased and then increased with increasing crosslink density. There was a valley value in the resistivity–crosslink density curve. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3471–3475, 2003     

Effect of norbornyl modified soybean oil on CB‐filled chloroprene rubber

Carbon black (CB)‐filled chloroprene rubber (CR) compounds and vulcanizates containing naphthenic oil (NO), soybean oil (SO), and two different levels of norbornyl modified soybean oil (MSO) were prepared and investigated. The MSO was prepared through the reaction of SO and dicyclopentadiene (DCPD) at different ratios. Various properties including gel fraction, crosslink density, bound rubber fraction, curing behavior, thermal, mechanical, and aging properties of CB‐filled CR containing different oils were compared. It was observed that the addition of SO and MSO could benefit the dispersion of the filler, lower the glass transition temperature, and increase the thermal stability of the CB‐filled CR/MSO compounds and vulcanizates, and also slightly decrease the crosslink density of the CB‐filled CR/MSO vulcanizates compared to that of the CR/NO vulcanizate. With the increase of the modification level of the MSO, the curing time of the CB‐filled CR/MSO compounds was found to be decreased, the tensile property, tear strength, abrasion resistance, and aging resistance of the CB‐filled CR/MSO vulcanizates were improved compared with those of the CB‐filled CR/NO vulcanizate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43809.     

Swelling of crosslinked polyacrylates in isotropic and anisotropic solvents

The purpose of this study was to examine the swelling and deswelling of photochemically crosslinked poly(n‐butylacrylate) networks in isotropic and anisotropic solvents. The phase diagrams were established in terms of composition and temperature for five isotropic solvents, acetone, cyclohexane, methanol, tetrahydrofuran, and toluene, and two low‐molecular‐weight nematic liquid crystals, 4‐cyano‐4′‐n‐pentyl‐biphenyl and an eutectic mixture of cyanoparaphenylenes. Networks were formed by ultraviolet curing in the presence of 0.5 wt % difunctional monomer (hexane diol‐di‐acrylate) and 0.5 wt % photoinitiator (Darocur 1173). Immersion in excess solvent allowed us to measure the solvent uptake by weight and to determine the size increase by optical microscopy in terms of temperature. We calculated weight and diameter ratios considering the swollen‐to‐dry network states of the samples. Phase diagrams were analyzed with the phantom network model according to the Flory–Rehner theory of rubber elasticity, and for the anisotropic solvents, modeling was supplemented with the Maier–Saupe theory of nematic order for free energy. The polymer–solvent interaction parameter was deduced as a function of temperature, but the values were in discrepancy with Fedors's model of solubility parameters, which overestimated the interaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1–9, 2004     

Investigation of the degradation properties of low molecular weight natural rubber blends in oven,oxygen, ozone,water, and some organic solvents

Studies into how heat, oxygen, ozone, water, and some organic solvents affect the physico‐mechanical properties of vulcanizates prepared from blends of natural rubber (NR) and low molecular weight natural rubber (LMWNR) were investigated. Various ratios of NR and LMWNR (100:0, 95:5, 90:10, 80:20, 50:50, 25:75 10:90, 5:95, and 0:100 w/w) were mixed and labeled as mixes A to I. The physico‐mechanical properties of all the vulcanizates before and after ageing in oven, oxygen, ozone, and water were measured and compared while the resistance of the vulcanizate in toluene, carbon tetrachloride, acetone, ethanol, cyclohexane, mineral oil, and brake fluid were determined in terms of swelling and solubility measurements. From the unaged results, mix A with 100% NR has the best physico‐mechanical properties. After degradation, mix C with 10% LMWNR showed the best ageing resistant. Similarly, mix D with 20% LMWNR showed more resistance in most of the solvents used, and this was closely followed by mix C. The results generally have proven that LMWNR is capable of improving the ageing properties and solvent resistance of NR. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

三种微生物脱硫废乳胶及其填充天然橡胶的力学性能比较

利用三种微生物鞘氨醇单胞菌、脂环酸芽孢杆菌和酵母菌对废乳胶(WLR)进行了脱硫再生,考察了脱硫过程中微生物的生长情况以及脱硫前后WLR溶胀和交联密度的变化,并将WLR和脱硫WLR(DWLR)以不同份数填充到天然橡胶(NR)中,对比了DWLR/NR硫化胶和WLR/NR硫化胶的力学性能和交联密度。结果表明,利用鞘氨醇单胞菌脱硫的WLR溶胀值较高,交联密度较低。随着乳胶用量的增加,填充NR硫化胶的拉伸强度和交联密度逐渐降低,扯断生长率逐渐增加。DWLR/NR硫化胶的力学性能明显优于WLR/NR硫化胶,且鞘氨醇单胞菌脱硫的DWLR/NR的力学性能明显优于其它两种微生物脱硫的DWLR/NR硫化胶。     

Influences of the grafting percentage of natural rubber‐graft‐poly(2‐hydroxyethyl acrylate) on properties of its vulcanizates

The graft copolymerization of 2‐hydroxyethyl acrylate (HEA) monomer onto natural rubber (NR) latex was successful using cumene hydroperoxide and tetraethylene pentamine as redox initiators. The grafting of poly(2‐hydroxyethyl acrylate) (PHEA) on the NR particles was confirmed by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy and TEM. The NR‐g‐PHEA with various grafting percentages (0%, 8.7%, 14.3% and 18.7%) was compounded on a two‐roll mill with a sulfur vulcanization system. The effects of grafting percentage on the cure characteristics, dielectric properties, thermal properties and physical properties of NR‐g‐PHEA vulcanizates were investigated. It was found that increased grafting caused NR‐g‐PHEA vulcanizates to have reduced water contact angle, scorch time and cure time, while the dielectric constant and dissipation factor increased. The NR‐g‐PHEA vulcanizate with 8.7% grafting exhibited the highest delta torque (M_H ? M_L), crosslink density, tensile strength, moduli at 100%, 200% and 300% strains, and hardness, with insignificant loss of elongation at break in comparison to the other cases. © 2018 Society of Chemical Industry     

Characterization of ethylene–propylene rubber and ethylene–propylene–diene rubber networks

The stress–strain (S/S) and the swelling equilibrium behavior in a series of ethylene propylene rubber (EPR) and ethylene propylene diene monomer (EPDM) networks were investigated and the results were employed to evaluate the effects of varying the cure conditions on the crosslinking efficiency in these networks. The S/S curve of completely swollen vulcanizates is in agreement with the predictions of rubber elasticity theory, while that of dry or partially swollen vulcanizates is fully described by the Mooney-Rivlin equation. ? values determined in benzene were found to vary linearly with v_r (v_r = equilibrium volume fraction of rubber in swollen sample). Crosslinking efficiency, moles of crosslinks produced per moles of crosslinking agent used, ranges from 3.7 in peroxide-cured EPDM (55% wt ethylene and 2.6% unsaturation) to 0.15 in similarly cured EPR (43% ethylene). Efficiency in the latter system improves to 0.6 by addition of a coagent (sulfur) to the cure formula. Crosslinking efficiency in EPDM (55% ethylene) was found to increase in the order: peroxide- > resin- > sulfur-cured. In the EPDM sulfur vulcanizates, changing the terpolymer in the cure formula resulted in significant changes in the crosslinking efficiency.     

Characterization of NBR networks from stress–strain and swelling equilibrium measurements

An improved stress–strain (S/S) method based on rubber elasticity theory and swelling equilibrium measurements was used to investigate the S/S behavior and the solvent swelling properties of nitrile–butadiene rubber (NBR) and also to study the effects of varying the cure agent and the curing conditions on the crosslinking efficiency in NBR vulcanizates. The S/S curve of completely swollen NBR vulcanizates is, as expected, in agreement with rubber elasticity theory, while that of dry or partially swollen vulcanizates is well described by the Mooney-Rivlin equation. Determined in benzene, χ was 0.494, compared to 1.338 in cyclohexane and 2.124 in n-heptane. The degree of crosslinking and the crosslinking efficiency in the NBR vulcanizates, moles of crosslinks produced per mole of crosslinking agent employed in the formula, are largely dependent on the nature of the crosslinking agent used and increase in the following order: peroxide, sulfur tetramethylthiuram disulfide, sulfur N-cyclohexyl-2-benzothiazolesulfenamide, sulfur benzothiazyl disulfide, and finally tetramethylthiuram disulfide.     

Influence of ZnO nanoparticles on the cure characteristics and mechanical properties of carboxylated nitrile rubber

Zinc oxide (ZnO) nanoparticles assembled in one dimension to give rod‐shaped morphology were synthesized. The effect of these ZnO nanoparticles (average particle size ～ 50 nm) as the curing agent for carboxylated nitrile rubber was studied with special attention to cure characteristics, mechanical properties, dynamic mechanical properties, and swelling. These results were compared with those of the conventional rubber grade ZnO. The study confirmed that the ZnO nanoparticles gave a better state of cure and higher maximum torque with a marginal decrease in optimum cure time and scorch time. The mechanical properties also showed an improvement. There was an increase in tensile strength by ～ 120%, elongation at break by ～ 20%, and modulus at 300% elongation by ～ 30% for the vulcanizate cured with ZnO nanoparticles, as compared with the one containing rubber grade ZnO. Dynamic mechanical analysis revealed that the vulcanizates exhibited two transitions—one occurring at lower temperature due to the T_g of the polymer, while the second at higher temperature corresponding to the hard phase arising due to the ionic structures. The second transition showed a peak broadening because of an increase in the points of interaction of ZnO nanoparticles with the matrix. The tan δ peak showed a shift towards higher T_g in the case of ZnO nanoparticle‐cured vulcanizate, indicating higher crosslinking density. This was further confirmed by volume fraction of rubber in the swollen gel and infrared spectroscopic studies. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Role of geopolymer as a cure activator in sulfur vulcanization of epoxidized natural rubber

Geopolymer (GP) was synthesized and used as activators in sulfur vulcanization of epoxidized natural rubber (ENR). Influences of GP on cure characteristics, crosslink density, mechanical, thermal, and morphological properties were investigated and compared to the conventional rubber formulation with ZnO activator. The ZnO is a hazardous chemical for the environment and has proclaimed that its application in rubber technology should be reduced and controlled. It was found that the GP-activated ENR compounds showed significantly higher vulcanization rate than cases with the conventional ZnO compound. This was indicated by the GP activated compounds having shorter scorch time, cure times, and lower activation energy but higher cure rate index (CRI). Also, the GP activated ENR compounded with stearic acid exhibited the highest conversion. This matches well the highest torque difference and crosslink density, observed by temperature scanning stress relaxation (TSSR) and swelling measurements. Furthermore, the GP-activated vulcanizate had better thermal stability than the ZnO-activated ENR material. In addition, the GP-activated ENR vulcanizate with stearic acid exhibited high 100% moduli, tensile strength, and hardness. This proves that GP has a high potential for use as activators in sulfur vulcanization of rubber compounds, as an alternative to the conventional ZnO. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48624.     

Recycling of roofing membrane rubber by ultrasonic devulcanization

The recycling of vulcanizates based on EPDM roofing membrane rubber using a new ultrasonic devulcanization reactor with a grooved barrel was carried out. This reactor provided continuous devulcanization at an output as high as 2.52 g/s. Die pressure and ultrasonic power consumption were measured as a function of processing conditions. The mechanical properties of virgin vulcanized and revulcanized roofing membranes were measured. Tensile strength of the revulcanized rubber was found to be similar to that of the virgin vulcanizate. Gel fraction, crosslink density, and dynamic properties of the virgin vulcanizate, the ultrasonically devulcanized rubber, and the revulcanized rubber were determined. Also, dynamic properties and the cure behavior of the virgin compound and of the devulcanized roofing membrane were investigated. All these properties were found to be dependent on processing conditions during devulcanization. The thermal stability of the virgin compound, virgin vulcanizate, and devulcanized and revulcanized rubbers were studied by means of TGA. It was found that the thermal stability of all the vulcanizates in air and nitrogen environments remained practically intact, while that of devulcanized rubber in air environment was a function of processing conditions.     

Vulcanization of butyl rubber by p-quinone dioxime dibenzoate

The maximum crosslink density for the dioxime-butyl vulcanizate was obtained at equimolar quantity of the dioxime and red lead. The formation of each quinoid crosslink required about 1.25 molecule of p-quinone dioxime dibenzoate. The vulcanizates consisted mainly of the anil-type crosslink. It was estimated that about 20% of the combined dinitro compounds was wasted in the form of the pendent groups. The vulcanization mechanisms are also discussed.     

Reinforcement of EPDM by in situ prepared zinc dimethacrylate

The mechanical properties and crosslink density of peroxide‐cured ethylene‐propylene‐diene rubber (EPDM) reinforced with zinc dimethacrylate (ZDMA) were studied. ZDMA was in situ prepared in EPDM matrix through the neutralization reaction of zinc oxide (ZnO) and methacrylate acid (MAA). The effect of ZnO/MAA amount and molar ratio of ZnO/MAA on the properties of the EPDM vulcanizate were investigated in detail. The experimental results showed that EPDM can be greatly reinforced by ZDMA. The excess amount of ZnO considerably increases the tensile strength of the EPDM vulcanizate to reach as high as 37 MPa, whereas its elongation at break keeps over 350%. The process of in situ formation of ZDMA in the EPDM compound was verified by WAXD. Such vulcanizate contains both covalent crosslinks and ionic crosslinks. Crosslink density was determined by an equilibrium swelling method. Dependence of crosslink density on the amount and molar ratio of ZnO/MAA was studied and the extraordinary high tensile strength of the EPDM/ZDMA vulcanizate was related to ionic crosslink density. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1339–1345, 2002; DOI 10.1002/app.10112     

RPA分析硫黄用量对天然橡胶动态性能的影响

用橡胶加工分析仪(RPA)分析硫黄用量对NR动态性能的影响。结果表明:不同硫黄用量的混炼胶的动态模量随频率的升高和温度的降低而增加,损耗因子降低;应变超过28%,混炼胶的储能模量下降。不同硫黄用量的硫化胶随交联密度的提高,动态性能对频率的依赖性变小,对应变的依赖性变强;而温度越高,硫化胶的"橡胶弹性"越明显。     

Preparation of lignin-based filling antioxidant and its application in styrene-butadiene rubber

A novel filling antioxidant (Lig-g-RT) to improve the mechanical properties and antiaging performance of styrene-butadiene rubber (SBR) composites was prepared by grafting antioxidant intermediate p-aminodiphenylamine (RT) on the surface of lignin via the linkage of silane coupling agent. Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) measurements confirmed that RT was successfully grafted on the surface of lignin to produce the functionalized Lig-g-RT which shows a better thermal stability than lignin. Compared with SBR/lignin composite, the SBR/Lig-g-RT composite using latex co-precipitation method exhibits a much better filler dispersion, which contributes to the maintain of the physical mechanical properties of SBR vulcanizates. Moreover, the SBR/Lig-g-RT vulcanizate exhibits less chemical crosslink concentration and higher entanglement density than SBR/lignin vulcanizate according to the Mooney–Rivlin model analysis. In addition, the stabilizing effect of lignin/Lig-g-RT on the carbon-black filled SBR vulcanizates is comparable with that of commercial antioxidant N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020), especially the SBR vulcanizate filled with 10 phr Lig-g-RT obtains the optimum thermo-oxidative aging properties. This functionalized Lig-g-RT not only provides an intramolecular synergistic antiaging effect for SBR vulcanizates and an improvement of filler dispersion, but greatly extends the comprehensive utilization of industrial lignin.