Effect of Mixing Schemes on Physico-Mechanical,Aging Properties,and Permeability of Aldehydes through Blends of Natural Rubber and Low Molecular Weight Natural Rubber

This article reports on the physico-mechanical properties, chemical resistance, aging properties, sorption, diffusion, and permeability of aldehydes (acetaldehyde and formaldehyde) through vulcanizates from blends of natural rubber (NR) and low molecular weight natural rubber (LMWNR) compounded by three different mixing schemes. The compounding ingredients were mixed with the two mentioned rubbers using three different mixing schemes by adopting the semi-efficient sulphur vulcanization compounding formulation. In scheme 1, the natural rubber and LMWNR were first mixed before adding the compounding ingredients. In scheme 2, the compounding ingredients were first mixed with the NR before adding the LWMNR and in scheme 3, the compounding ingredients were first mixed with the LMWNR before adding the NR. The physico-mechanical results of the vulcanizates showed that changes in the mixing schemes significantly influence the tensile properties of the vulcanizates. The tensile strengths of the vulcanizates prepared with mixing scheme 2 were 3.5 MPa lower than vulcanizates from scheme 1, whereas scheme 3 was lower than scheme 1 by 7.8 MPa. The aging result of the vulcanizates from all the mixing schemes were found to be similar. The activation energy and free energy change were highest with scheme 1 whereas the extent of acetaldehyde and formaldehyde penetrations were lowest with scheme 1, signifying a well crosslinked and aldehyde-resistant vulcanizate.     

甲基丙烯酸固态原位接枝改性炭黑对天然橡胶和顺丁橡胶性能的影响

考察了固态原位接枝改性制备的甲基丙烯酸接枝改性炭黑对天然橡胶(NR)和顺丁橡胶。(BR)静态力学性能、动态力学性能的影响。结果表明。甲基丙烯酸改性炭黑比普通商品炭黑填充的NR硫化胶具有更好的静态力学性能;甲基丙烯酸改性炭黑曼有利于降低NR和BR硫化胶的滚动阻力。同时,有利于提高NR硫化胶的抗湿滑性。     

THERMAL AGING PROPERTIES AND MOLECULAR TRANSPORT OF SOLVENTS THROUGH VULCANIZATES PREPARED FROM THIOGLYCOLLIC ACID MODIFIED EPOXIDIZED LOW MOLECULAR WEIGHT NATURAL RUBBER BLENDS FILLED WITH ADMIXTURES OF CARBON BLACK AND CARBONIZED RUBBER SEED SHELL

Physico-mechanical, aging, swelling, solubility, and permeability properties of blends of natural rubber (NR) and thioglycollic acid modified epoxidized low molecular weight natural rubber (TGA-ELMWNR) filled with admixtures of carbon black (CB) and carbonized rubber seed shell (CRSS) in ketones, alcohols, aldehydes, and petroleum fuels (petrol, kerosene, and diesel) were investigated as a function of different filler compositions. The physico-mechanical properties were found decreasing as the level of CRSS increases, but were within the accepted level for natural rubber compounds, showing that CRSS can find uses as fillers in materials of low tensile strength. The aging results of all the mixes were nearly of the same magnitude. The swelling and solubility results showed that ketones swell the vulcanizates more and faster than alcohols and aldehydes. The sorption, diffusion, and permeability of the blends as determined from the gravimetric method confirm the better resistance of blends with higher ratio of carbon black. Petrol was found diffusing through the vulcanizates faster than kerosene and faster than diesel. Above all, replacement of carbon black with 15% carbonized rubber seed shell has not shown any serious deleterious effects on the vulcanizates.     

铁系乙烯基丁二烯橡胶/天然橡胶共混物的性能

研究了铁系乙烯基丁二烯橡胶(FVBR)与天然橡胶(NR)以50/50(质量比)共混硫化胶的物理机械性能和黏弹特性,并与溶聚丁苯橡胶(SSBR)与NR共混胶进行了对比。结果表明,FVBR与NR有良好的相容性,共混胶只存在1个玻璃化转变温度。FVBR/NR的混炼行为良好,但必需添加操作油,否则难以获得理想的硫化胶性能。FVBR/NR与SSBR/NR相似,不仅具有良好的拉伸和撕裂性能,而且具有高抗湿滑性;其生热和滚动阻力以及热老化性能优于后者,但耐磨性略逊于SSBR/NR。     

Effects of antimicrobial agents on the processing and performance properties of rubber material formulations with no cytotoxicity

The present work aims to develop antimicrobial rubber for safe industrial toys. For this purpose, natural rubber (NR) and synthetic rubber as styrene butadiene rubber (SBR) and ethylene propylene diene monomer (EPDM) were examined. Rubber and their ingredients as well as antimicrobial agents (doxycycline and cephalexin) were mixed in a rubber mixer. The rheological properties of compounded rubber were studied, and the curing time was determined. Mechanical properties and cytotoxicity were evaluated at optimally cured rubber compounds. Scanning electron micrographs of vulcanizates showed good dispersion of ingredients throughout the investigated matrices. Rheology study for the investigated vulcanizates in presence of tested antimicrobial species exhibited no significant change in their flow behaviors. It is significant to remember that the desired physical characteristics of rubber products, including their chemical and mechanical characteristics (elongation at break and tensile strength) enhanced when doxycycline and cephalexin are present, depending on their nature and concentration. Similar results were obtained for both the SBR and EPDM rubber vulcanizates. The cytotoxicity of the prepared vulcanizates towards human normal retina cell line (RPI-1) indicated good safety of these rubber products. Furthermore, developed rubber vulcanizates showed good antimicrobial efficacy towards the test bacteria and fungi strains.”     

Effect of triblock copolymers on homogeneity,mechanical properties and swelling behavior of IIR/SBR rubber blends

The present research concerns with the preparation and characterization of isobutylene isoprene/butadiene–styrene rubber (IIR/SBR) blends with different blend ratios, in the presence and absence of styrene–isoprene–styrene (SIS) and styrene–isobutylene–styrene (SiBS) triblock copolymers to be tested as compatibilizers. Effect of the triblock copolymers on the blend homogeneity was investigated with the aid of scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) measurements. Characterization of the rubber blends was conducted by measuring the physico-mechanical properties after and before thermal aging, in presence and absence of the triblock copolymers. In addition, weight swell % in toluene, motor oil and brake fluid of the rubber blend vulcanizates was assessed. The incorporation of SIS and SiBS triblock copolymers improved the homogeneity of IIR/SBR blends as well as increased both tensile strength and elongation at break of the rubber blend vulcanizates. Of the entire blend ratios examined, IIR/SBR (25/75) blend containing SIS compatibilizer possessed the best physico-mechanical properties (12.6 MPa tensile strength and 425 % elongation at break) and (14 MPa tensile strength and 555 % elongation at break) after and before thermal aging, respectively. Utilization of SIS and SiBS triblock copolymers enhanced the thermal stability of IIR/SBR blend vulcanizates. Moreover, IIR/SBR blends of different blend ratios showed superior swelling resistance in the brake fluid. IIR/SBR (25/75) blend containing SIS compatibilizer and cured with CBS/ZDEC/S vulcanizing system possessed the best physico-mechanical properties (14.4 MPa tensile strength and 440 % elongation at break) and (16.5 MPa tensile strength and 610 % elongation at break) after and before thermal aging, respectively.     

加料顺序对炭黑/NR相互作用及性能的影响

研究了加料顺序对炭黑/NR间相互作用及胶料性能的影响。结果表明,配方相同时,采用先加小料后加炭黑的加料顺序可使混炼过程能耗最低,混炼胶加工性能较好,综合物理机械性能较好;加料顺序对交联密度基本没有影响;在混炼过程中,加入小料会迅速降低胶料扭矩值,起到增塑作用,有利于分散;提前加入炭黑会增强炭黑/NR间相互作用,生成较多结合橡胶。     

Blending of NR/BR/EPDM by reactive processing for tire sidewall applications. I. Preparation,cure characteristics and mechanical properties

EPDM incorporated into blends of natural rubber/butadiene rubber (NR/BR) improves ozone resistance. In this work, the inferior mechanical properties of NR/BR/EPDM blends generally obtained by conventional straight mixing are overcome by utilizing a reactive processing technique. The entire amount of curatives, based on a commonly employed accelerator N‐cyclohexyl‐2‐benzothiazole sulfenamide (CBS) and sulfur, is first added into the EPDM phase. After a thermal pretreatment step tuned to the scorch time of the EPDM phase, the modified EPDM is mixed with premasticated NR/BR. The reactive blend vulcanizates show a significant improvement in tensile properties: tensile strength and elongation at break, as compared to those prepared by straight mixing, in both gum and carbon black‐filled blends. The increase of tensile properties in gum and filled reactive blend vulcanizates does suggest that the reactive processing technique leads to more homogeneous blends due to, either a better crosslink distribution, or more homogeneous filler distribution, or both. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:2538–2546, 2007     

Thermal Aging Properties and Molecular Transport of Solvents through Vulcanizates Prepared from Thioglycollic Acid Modified Epoxidized Low Molecular Weight Natural Rubber Blends Filled with Admixtures of Carbon Black and Carbonized Rubber Seed Shell

Physico-mechanical, aging, swelling, solubility, and permeability properties of blends of natural rubber and thioglycollic acid modified epoxidized low molecular weight natural rubber (TGA-ELMWNR) filled with admixtures of carbon black and carbonized rubber seed shell (CRSS) in ketones, alcohols, aldehydes, and petroleum fuels (petrol, kerosene, and diesel) were investigated as a function of different filler composition. The physico-mechanical properties were found reducing as the level of CRSS increases, but were within the accepted level for natural rubber compounds, showing that CRSS can find uses as fillers in materials of low tensile strength. The aging results of all the mixes were nearly of the same magnitude. The swelling and solubility results showed that ketones swell the vulcanizates more and faster than alcohols and than aldehydes. The sorption, diffusion, and permeability of the blends as determined by the gravimetric method confirm the better resistance of blends with higher ratio of carbon black. Petrol was found diffusing through the vulcanizates faster than kerosene and faster than diesel. Above all, replacement of carbon black with 15% carbonized rubber seed shell has not shown any serious deleterious effects on the vulcanizates.     

THERMAL AGING PROPERTIES AND MOLECULAR TRANSPORT OF SOLVENTS THROUGH VULCANIZATES PREPARED FROM THIOGLYCOLLIC ACID MODIFIED EPOXIDIZED LOW MOLECULAR WEIGHT NATURAL RUBBER BLENDS FILLED WITH ADMIXTURES OF CARBON BLACK AND CARBONIZED RUBBER SEED SHELL

Physico-mechanical, aging, swelling, solubility, and permeability properties of blends of natural rubber (NR) and thioglycollic acid modified epoxidized low molecular weight natural rubber (TGA-ELMWNR) filled with admixtures of carbon black (CB) and carbonized rubber seed shell (CRSS) in ketones, alcohols, aldehydes, and petroleum fuels (petrol, kerosene, and diesel) were investigated as a function of different filler compositions. The physico-mechanical properties were found decreasing as the level of CRSS increases, but were within the accepted level for natural rubber compounds, showing that CRSS can find uses as fillers in materials of low tensile strength. The aging results of all the mixes were nearly of the same magnitude. The swelling and solubility results showed that ketones swell the vulcanizates more and faster than alcohols and aldehydes. The sorption, diffusion, and permeability of the blends as determined from the gravimetric method confirm the better resistance of blends with higher ratio of carbon black. Petrol was found diffusing through the vulcanizates faster than kerosene and faster than diesel. Above all, replacement of carbon black with 15% carbonized rubber seed shell has not shown any serious deleterious effects on the vulcanizates.     

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     

Evaluation of Some Diphenylamine Derivatives as Thermal Stabilizers and Antifatigue Agents in Natural Rubber Vulcanizates

ABSTRACT

Four compounds of diphenylamine derivatives were prepared and evaluated as thermal stabilizers and antifatigue agents in natural rubber (NR) mixes. The efficiencies of these compounds were compared with phenyl-B-naphthylamine, which is widely used in rubber industry. The rheological characteristics were determined using an oscillating disc rheometer. The physico-mechanical properties of the rubber vulcanizates were measured before and after exposure to accelerated thermooxidative ageing. The results revealed that the prepared compounds were good antioxidants and antifatigue agents for rubber vulcanizates. In addition, it was found that the chemical structure of the compounds has a great effect on their efficiency as stabilizers, that is, the presence of electron donating group increases their efficiency, whereas the presence of electron withdrawing group decreases it.     

Modified wheat flour–natural rubber blends. II

Effect of cyanoethylation of starch on the properties of starch xanthide–NR vulcanizates has been studied. Significant improvements in compounding, tensile modulus, tensile strength, and retention of wet strength of the vulcanizates have been recorded. Equilibrium swelling of vulcanizates by water is also greatly suppressed. The role of cyanoethylation of starch in imparting such specific effects has been analyzed in the light of the polarity of the cyanoethyl group and its effect in lowering the critical yield stress of the modified starch for efficient dispersive mixing in NR matrix.     

The mechanism of carbon–silica dual phase filler modified by ionic liquid and its reinforcing on natural rubber

The carbon–silica dual phase filler (CSDPF) was modified by ionic liquids (ILs): 1‐allyl‐3‐methyl‐imidazolium chloride (AMI) and 1‐butlyl‐3‐methyl‐imidazolium hexafluorophosphate (BMI). The modified CSDPF was then incorporated into natural rubber (NR) through mechanical mixing. The interactions between CSDPF and ILs were investigated using differential scanning calorimetry (DSC), Fourier‐transform infrared spectroscopy (FTIR), and Raman spectroscopy. The bound rubber of NR compounds, the mechanical properties, and dynamic properties of NR vulcanizates filled with ILs modified CSDPF (ILs‐CSDPF/NR) were measured. The results showed that the AMI interacted with CSDPF through both hydrogen bonds and van der Waals forces, while the interaction between BMI and CSDPF was merely weak van der Waals force. The modification of CSDPF by ILs could improve the tensile strength, tear resistance, and fatigue life of NR vulcanizates. The AMI‐CSDPF/NR gave the superior mechanical and dynamic properties among the NR vulcanizates with the highest bound rubber content and the most homogeneous filler dispersion, which was displayed in scanning electron microscope (SEM) images. POLYM. COMPOS., 36:1721–1730, 2015. © 2014 Society of Plastics Engineers     

Compatibility study in natural rubber and maize starch blends

Blends containing various ratios of natural rubber (NR) and maize starch (MS) were prepared on a two roll mill. The effect of starch contents on physico-mechanical properties and curing characteristics of the prepared blend vulcanizates was investigated. The data indicate poor mechanical properties, delayed cure rate index, and decreased maximum torque with increasing starch content in the blend formulation. This indicates that the interfacial interaction between the blend components was poor. Various contents of the compatibilizers, maleic acid anhydride (MAH) and glycidyl methacrylate (GMA), were mixed with the blend NR/MS (90/10). The effect of the compatibilizer contents on the physico-mechanical properties and curing characteristics of the binary blend was investigated. Compatibilized blends with GMA (1 phr) showed an improvement in the physico-mechanical properties in comparison with uncompatibilized blend samples. Blends with MAH exhibited higher modulus and hardness values with respect to GMA blends. The efficiency of the compatibilizers was also evaluated by studies of phase morphology (scanning electron microscope), Fourier transform infrared spectroscopy, and thermal stability (thermogravimetric analysis). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

蛋白质含量对天然橡胶性能的影响简

研究蛋白质含量为0.5%~2.7%的天然橡胶(NR)生胶的理化性能、硫化胶的物理性能、耐热老化性能、永久变形性能和压缩生热。结果表明:不同蛋白质含量的NR生胶的理化性能基本相同;随着蛋白质含量降低,NR硫化胶的定伸应力、拉伸强度和撕裂强度呈先升后降的趋势,压缩永久变形减小,压缩生热降低,蛋白质含量低于1%时耐热老化性能明显降低。蛋白质含量在1.0%左右NR硫化胶的综合性能最好。     

Effect of silica reinforcement on natural rubber and butadiene rubber vulcanizates by a sol–gel reaction with tetraethoxysilane

The effect of silica reinforcement was studied for natural rubber (NR) and butadiene rubber (BR) vulcanizates by a sol–gel reaction with tetraethoxysilane at different temperatures. The formation of silica in the rubber vulcanizates was investigated analytically with Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis. The variations of the mechanical and dynamic properties were measured in the NR and BR vulcanizates with silica filling. The hardness of the rubber vulcanizates increased with silica filling in the rubber matrix. The tensile strength and elongation at break decreased with silica filling in the NR vulcanizates. The moduli at 50, 100, and 300% elongation increased with silica filling in the rubber matrix. The storage modulus of silica-filled rubber vulcanizates became higher than that of pure rubber vulcanizates. The temperature dependence of the loss modulus also increased with silica filling. The temperature dependence of the loss tangent was maintained, regardless of silica filling in the BR vulcanizates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

On the potential of organoclay with respect to conventional fillers (carbon black,silica) for epoxidized natural rubber compatibilized natural rubber vulcanizates

Onium modified montmorillonite (organoclay) was compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) in 10 parts per hundred rubber (phr) was used as a compatibilizer in this study. For comparison purposes, two commercial fillers: carbon black (grade N330) and silica (grade vulcasil‐S) were used. Cure characteristics were carried out on a Monsanto MDR2000 Rheometer. Organoclay filled vulcanizate showed the lowest values of torque maximum, torque minimum, scorch, and cure times. The kinetics of cure reaction showed organoclay could behave as a cocuring agent. The mechanical testing of the vulcanizates involved the determination of tensile and tear properties. The improvement of tensile strength, elongation at break, and tear properties in organoclay filled vulcanizate were significantly higher compared to silica and carbon black filled vulcanizates. In terms of reinforcing efficiency (RE), organoclay exhibited the highest stiffness followed by silica and carbon black filled vulcanizates. Scanning electron microscopy revealed that incorporation of various types of fillers has transformed the failure mechanism of the resulting NR vulcanizates compared to the gum vulcanizates. Dynamic mechanical thermal analysis (DMTA) revealed that the stiffness and molecular relaxation of NR vulcanizates are strongly affected by the filler–rubber interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2438–2445, 2004     

A comparative study of aging characteristics and thermal stability of oil palm ash,silica, and carbon black filled natural rubber vulcanizates

Filler‐filled natural rubber (NR) vulcanizates were prepared by conventional laboratory‐sized two roll mills and cured using sulfuric system. The effect of thermal aging on physical properties and thermogravimetric analysis (TGA) of oil palm ash (OPA) and commercial fillers (i.e., silica vulkasil C and carbon black N330)‐filled NR vulcanizates at respective optimum loading and equal loading were studied. Before aging, the OPA‐filled vulcanizates showed comparable optimum strength as carbon black‐filled vulcanizates. The hardening of aged filler‐filled NR vulcanizates happened after aging, thereby tensile strength and elongation at break reduced while the modulus increased. Fifty phr carbon black‐filled vulcanizates showed better retention in tensile properties as compared to silica (10 phr) and OPA (1 phr). This was attributed to the addition of different filler loading and this finding was further explained when equal loading of filler‐filled vulcanizates was studied. Fourier transform infra‐red analysis showed chemical structure had changed and tensile fractured surface exhibited smooth appearance due to the deterioration in tensile properties after aging. TGA also denoted the thermal stability was depending on the amount of filler loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4474–4481, 2013     

Comparative study on natural antioxidant as an aging retardant for natural rubber vulcanizates

The research aim is mainly to investigate the effectiveness of natural antioxidant (NA) obtained from oil palm leaves (Elaeis guineensis) as an aging retardant in natural rubber (NR) vulcanizates. Comparison of NA with other commercial antioxidants, trimethyl quinoline (TMQ) and butylated hydroxy toluene (BHT), is investigated. The effect of natural and commercial antioxidants on NR vulcanizates was explored before and after aging. Aging test was carried out at 70°C for three different periods, 4, 7, and 14 days to determine aging property by performing the tensile and tear tests. NA shows lower tensile properties, crosslink density, tack strength but high tear strength compared to the commercial antioxidants, BHT and TMQ. However, upon aging NR vulcanizates with NA retains its properties equivalent to that of commercial antioxidants, BHT and TMQ. Thus, NA can be used as an aging retardant for short‐term protection in application requiring moderate tensile properties and can be used as alternative source for commercial antioxidant. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012