环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

Properties of silica/clay filled heavy‐duty truck tire thread formulation

A tire thread formulation for heavy‐duty trucks containing SBR/BR rubber blend and varying proportions of silica/clay fillers including a silane‐coupling agent have been investigated. The various mixes were compounded in a Banbury ‘O’ mixer and vulcanized using the EV‐system. Silica/clay (80/0) served as the control mix. The oscillating disc rheometer (ODR) was used in determination of cure characteristics. Substitution of silica (80 phr) with china clay up to 40 phr increased the cure rate of the rubber blend mixes as well as their maximum torque level (T_max). T_max was observed to be highest at a filler blend ratio of 40/40 phr. Synergism between silica and clay at this filler blend mixture is suggested to be responsible for the observation. The heat buildup was reduced from 43 to 20°C as the clay content increased. Results also showed that the rubber blend compound containing silica/clay (60/20) filler blend in the stated ratio exhibited the best balance of properties in the critical parameters such as the absolute torque level (69.5 dNm), heat buildup (39°C), and abrasion resistance (0.574 mg.loss/1,000 rev). The rate of depreciation of abrasion resistance of rubber blend compound as the clay content increased was found to be 0.035 mg loss/1,000 rev as silica is substituted with one part of china clay phr. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1024–1028, 2004     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

Effect of carbon black loading on curing characteristics and mechanical properties of waste tyre dust/carbon black hybrid filler filled natural rubber compounds

Curing characteristics, tensile properties, fatigue life, swelling behavior, and morphology of waste tire dust (WTD)/carbon black (CB) hybrid filler filled natural rubber (NR) compounds were studied. The WTD/CB hybrid filler filled NR compounds were compounded at 30 phr hybrid filler loading with increasing partial replacement of CB at 0, 10, 15, 20, and 30 phr. The curing characteristics such as scorch time, t₂ and cure time, t₉₀ decreased and increased with increment of CB loading in hybrid filler (30 phr content), respectively. Whereas maximum torque (M_HR) and minimum torque (M_L) increased with increasing CB loading. The tensile properties such as tensile strength, elongation at break, and tensile modulus of WTD/CB hybrid filler filled NR compounds showed steady increment as CB loading increased. The fatigue test showed that fatigue life increased with increment of CB loading. Rubber–filler interaction, Q_f/Q_g indicated that the NR compounds with the highest CB loading exhibited the highest rubber–filler interactions. Scanning electron microscopy (SEM) micrographs of tensile and fatigue fractured surfaces and rubber–filler interaction study supported the observed result on tensile properties and fatigue life. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

炭黑/煤矸石/碳纳米管复合填料体系对天然橡胶性能的影响研究*

利用硝酸氧化法对碳纳米管(CNTs)进行纯化,并用环氧天然橡胶(ENR)进行改性处理。结合胶质量分数测定结果表明, ENR用量15%(质量)时效果最佳。采用胶乳凝聚法制备CNTs/天然橡胶(NR)母料。煤矸石粉(CG)经高温煅烧和表面改性处理。 将CNTs/天然橡胶(NR)母料、CG和炭黑(CB)通过机械混炼法与天然橡胶及配合剂混合,制备CB/CG/CNTs/NR复合材料,并对复合材料进行硫化特性及物理机械性能。结果表明： CNTs延迟硫化效应明显;相比炭黑,CG对硫化具有促进作用。硫化特性和甲苯溶胀法测定结果表明,在填料份数相同的条件下,单独由CB填充的NR有最大的交联密度,CNTs对交联密度影响不明显。物理机械性能测试结果表明,当CG：CB：CNTs=17.5:16.5:1(Phr)时,NR硫化胶的300%定伸应力和扯断伸长率明显高于单独由CB填充NR,而拉伸强度与之接近,复合填料样填充NR具有较好的综合性能。扫描电镜测试结果表明,复合填料在NR基体中分布均匀。     

Hybridized reinforcement of natural rubber with silane‐modified short cellulose fibers and silica

Natural‐rubber‐based hybrid composites were prepared by the mixture of short cellulose fibers and silica of different relative contents with a 20‐phr filler loading with a laboratory two‐roll mill. The processability and tensile properties of the hybrid composites were analyzed. The tensile modulus improved, but the tensile strength and elongation at break decreased with increasing cellulose fiber content. The scorch safety improved with the addition of 5‐phr cellulose fiber in the composites. The Mooney viscosity significantly decreased with increasing cellulose fiber content. To modify the surface properties of the cellulose fiber and silica fillers, a silane coupling agent [bis(triethoxysilylpropyl)tetrasulfide, or Si69] was used. The effects of Si69 treatment on the processing and tensile properties of the hybrid composites were assessed. We found that the silane treatment of both fillers had significant benefits on the processability but little benefit on the rubber reinforcement. The strength of the treated hybrid composite was comparable to that of silica‐reinforced natural rubber. Furthermore, to investigate the filler surface modification and to determine the mixing effects, infrared spectroscopic and various microscopic techniques, respectively, were used. From these results, we concluded that the fillers were better dispersed in the composites, and the compatibility of the fillers and natural rubber increased with silane treatment. In conclusion, the hybridized use of short cellulose fibers from a renewable resource and silica with Si69 presented in this article offers practical benefits for the production of rubber‐based composites having greater processability and more environmental compatibility than conventional silica‐filler‐reinforced rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Epoxidized natural rubber as a reinforcement modifier for silica‐filled nitrile rubber

Hydrated silicas impart better physical properties to polar rubbers, compared to those of hydrocarbon rubbers. However, to achieve optimum properties silane coupling agents are crucial in such formulations. Epoxidized natural rubber (ENR) in small proportions is used as a reinforcement modifier for silica‐filled nitrile rubber (NBR). Two systems of cure were used: N‐cyclohexyl‐ 2‐benzthiazyl sulfenamide (CBS) alone and in combination with diphenyl guanidine (DPG). In the CBS accelerated system, incorporation of an optimum concentration of about 15% of ENR on total rubber was found to improve technological properties. Addition of a secondary accelerator further improves these properties. Comparable results are obtained with those containing coupling agent and NBR–ISAF. High bound rubber and volume fraction values indicate a high polymer–filler interaction and gel content resulting from the NBR–ENR interaction. Results of this study reveal that ENR could be used as a reinforcement modifier for the NBR–silica system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 292–306, 2002     

Dynamic Mechanical and ESCA Studies of Aluminium-Aluminium Bonding by an Epoxidised Natural Rubber-Polyacrylic Acid Blend

A polyacrylic acid (PAA)-epoxidised natural rubber (ENR) blend becomes crosslinked during high temperature moulding and such a blend was found to be a good adhesive for aluminium (Al)-aluminium (Al) bonding. The joint strength can be improved by the incorporation of silica filler into the adhesive up to a loading of 5 phr. However, higher filler loading causes deterioration of the joint strength. Electron Spectroscopy for Chemical Analysis (ESCA) studies of the peeled and then leached Al surface shows that the ENR phase of the blend is primarily responsible for the adhesion with the Al surface. With the increase in filler loading adhesion with Al increases at the cost of crosslinking between the component polymers. This is substantiated by dynamic mechanical analyses of the blends and joints (that is, Al/blend/Al composites). The changes in dynamic mechanical properties of the blends due to Al adhesion could be correlated with the peel strength of the Al/blend/Al joints.     

Curing Characteristics and Aging Properties of Natural Rubber/Epoxidized Natural Rubber and Cellulose II

In this work, natural rubber (NR) and regenerated cellulose (cel II) latexes were co-coagulated and to the mixture epoxidized natural rubber (ENR) was added on a two-roll mill. The cellulose content was fixed at 20 phr while ENR content varied from 0 to 75 phr. The influence of ENR was studied through the cure characteristics, aging and dynamic-mechanical properties. The aging provides nanocomposites with better solvent resistance and increased tensile strength at ENR content of 25 phr. The results suggest that a new type of light-colored nanocomposites were obtained, which presented high mechanical performance and resistance to solvents.     

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     

Reinforcement of maleated natural rubber by precipitated silica

Graft copolymers of maleic anhydride and natural rubber or so‐called maleated natural rubbers (MNRs) were prepared in a molten state with varying maleic anhydride contents from 4 to 10 phr. In this work, the filler–filler and filler–rubber interactions of the MNR and precipitated silica were investigated. The MNR compounds containing 40 phr of silica both with and without 9 wt % of silane coupling agent were prepared. By increasing the maleic anhydride contents, the Mooney viscosity and cure times were increased, but the torque differences and cure rate indices were decreased. Bound rubber was increased with increasing maleic anhydride content, indicating an increase of filler–rubber interaction. In case of the compounds without silane, the MNR with 6 phr of maleic anhydride showed the lowest filler–filler interaction as indicated by a decrease of storage modulus upon an increase of strain in the filled compound i.e., Payne effect. This MNR compound also yielded the optimum mechanical properties. It has been demonstrated that a use of MNR with appropriate maleic anhydride content can reduce filler–filler interaction dramatically and hence improve a silica dispersion, as confirmed by SEM micrographs, resulting in an enhancement of the mechanical and dynamical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of Carbon Black/Silica Hybrid Filler on Thermal Properties,Fatigue Life,and Natural Weathering of SBR/Recycled NBR Blends

The utilization of nitrile glove waste will spark a great deal of interest in the rubber industry in developing cost-effective techniques to convert waste and used rubber into a processable form. Blends of styrene butadiene rubber/recycled acrylonitrile butadiene rubber (SBR/NBRr) reinforced at 85/15 blend with different ratios of a carbon black/silica (CB/Sil) hybrid filler (50/0, 40/10, 30/20, 20/30, 40/10, 0/50 phr) were tested either with or without the silane coupling agent, Si69. Results showed that the increased thermal stability of blends with Si69 is highly related to the formation of crosslinks between the filler. Thermogravimetric (TG) thermograms showed that the percentage of char residue for blends with Si69 was higher than without Si69. The differential scanning calorimetry (DSC) thermograms of both blends revealed a glass transition temperature (Tg) between 65.0°C and 66.9°C. At all blend ratios, the fatigue life of blends with Si69 was better than blends without Si69. After six months’ exposure to natural weather, blends with Si69 exhibited better tensile properties, retention, and morphology compared to blends without Si69.     

The Effect of Silica on the Peel Adhesion of Epoxidized Natural Rubber-Based Adhesive Containing Coumarone-Indene Resin

The peel strength of silica filled on two grades of epoxidized natural rubber (ENR), i.e., ENR 25 and ENR 50 adhesive were investigated using coumarone-indene as the tackifying resin. Toluene was used as the solvent throughout the study. Result shows that peel strength increases with increase in silica loading due to the concentration effect of the filler. Peel strength, however, shows maximum value at 40 phr silica for both ENR 25 and ENR 50 an observation that is attributed to the maximum wettability and compatibility of adhesive on the substrate.     

Mechanical and morphological properties of cellular NR/SBR vulcanizates under thermal and weathering ageing

The effects of addition of two chemical blowing agents in cellular rubber blend of natural rubber (NR) and styrene‐butadiene rubber (SBR) at a fixed blend ratio of 1 : 1 on cure characteristics, and mechanical and morphological properties were invesigated. The chemical blowing agents used in this work were Oxybis (benzene sulfonyl) hydrazide (OBSH) and Azo dicarbonamide (ADC). Three different fillers, fly ash (FA) particles, precipitated silica, carbon black (CB) at their optimum concentrations of 40 phr were used, the FA and silica particles being chemically treated by bis‐(3‐triethoxysilylpropyl) tetrasulphide. The results suggested that the overall cure time decreased with OBSH and ADC contents. The OBSH was more effective in cure‐acceleration of the NR/SBR blend than the ADC. The NR/SBR vulcanized foams produced by OBSH and ADC agents had closed‐cell structures. The specific density and mechanical properties of the blend tended to decrease with increasing blowing agent content. The CB gave NR/SBR foams with smaller cell size, better cell dispersion, and higher mechanical properties than the precipitated silica and FA particles. The heat ageing and weathering resulted in an increase in tensile modulus and hardness, but lowered the tensile strength, ultimate elongation and tear strength. The elastic recovery for cellular NR/SBR vulcanizates with FA was superior to that with CB and silica, the elastic recovery of the blends decreasing with blowing agent content. Resilience property was improved by the presence of gas phases. The optimum concentration of OBSH and ADC to be used for NR/SBR vulcanizates was 4 phr. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of silane coupling agent on the chemorheological behaviour of epoxidised natural rubber filled with precipitated silica

Results of measurements of physical properties and solvent swelling of the extrudates indicate that epoxidised natural rubber (ENR) interacts chemically with precipitated silica when the mix of the two was extruded at 150–170°C in a Monsanto Processability Tester (MPT). The extent of interaction between the rubber and the filler depends on the extrusion time, the volume fraction of the filler, the shear rate and the addition of the silane coupling agent, namely N-3-(N-vinyl benzyl amino) ethyl-γ-amino propyl trimethoxy silane monohydrochloride. The activation energy of the chemical interaction between ENR and silica decreases on the addition of the silane coupling agent.     

Properties of styrene butadiene rubber (SBR)/recycled acrylonitrile butadiene rubber (NBRr) blends: The effects of carbon black/silica (CB/Sil) hybrid filler and silane coupling agent,Si69

The recycling or reuse of waste rubber by means of blending together with polymeric materials in addition of filler such as hybrid carbon black and silica (CB/Sil) to a polymer system can provides an opportunity to explore alternative product specifications. Therefore, in this work the investigation of recycled rubber blends based on styrene butadiene rubber/recycled acrylonitrile butadiene rubber (SBR/NBRr) blends reinforced with 50/0, 40/10, 30/20, 20/30, 40/10, 0/50 phr of carbon black/silica (CB/Sil) hybrid filler treated with and without silane coupling agent (Si69) were determined. Cure characteristics, tensile properties, and morphological behavior of selected SBR/NBRr blends at a fix 85/15 blend ratio were evaluated. Results showed that, cure time t₉₀, minimum torque (M_L), and maximum torque (M_H) of CB/Sil hybrid fillers filled SBR/NBRr blends with and without Si69 increased as silica content increased. However, t₉₀ and M_L of SBR/NBRr blends with Si69 were lower than without Si69 except for (M_H). The optimum scorch time (t_s2) of SBR/NBRr blends with and without Si69 was obtained at 30/20 phr of CB/Sil hybrid filler. However, t_s2 of SBR/NBRr blends with Si69 were longer than SBR/NBRr blends without Si69. The incorporation of Si69 has improved the tensile properties [(tensile strength, elongation at break (E_b), stress at 100% elongation (M100), and stress at 300% elongation (M300)] of CB/Sil hybrid fillers filled SBR/NBRr blends. These properties were influenced by the degree of crosslinked density as the silica content is increased. Scanning electron microscopy (SEM) of the tensile fracture surfaces indicated that, with the addition of Si69 improved the dispersion of hybrid fillers and NBRr in SBR/NBRr matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

THE COMPARISON PROPERTIES OF RECYCLE RUBBER POWDER,CARBON BLACK,AND CALCIUM CARBONATE FILLED NATURAL RUBBER COMPOUNDS

The effects of filler loading on the curing characteristics, swelling behavior, and mechanical properties of natural rubber compounds were studied using a conventional vulcanization system. Recycle rubber powder (RRP), carbon black (CB) (N550), and calcium carbonate (CaCO₃) were used as fillers and the loading range was from 0 to 50 phr. Results show that the scorch time, t ₂, and cure time, t ₉₀, decrease with increase in filler loading. At a similar filler loading, RRP shows shortest t ₂ and t ₉₀ followed by CB and calcium carbonate. The tensile strength, tensile modulus, and hardness increase with increase in CB loading, whereas elongation at break, resilience, and swelling properties show opposite trend. For RRP and calcium carbonate filled natural rubber compounds, the tensile strength increases up to 10 phr and starts to deteriorate at higher filler loading. The other properties such as tensile modulus, hardness, elongation at break, resilience, and swelling percentage show a small change (increase or decrease) with increase in RRP and calcium carbonate loading in natural rubber compounds. Overall results indicate that RRP can be used as a cheapener to replace calcium carbonate in natural rubber compounds where improved mechanical properties are not critical.     

Dynamic mechanical properties and hysteresis loss of epoxidized natural rubber chemically bonded to the silica surface

High‐temperature (180°C) molding of epoxidized natural rubber (ENR) filled with precipitated silica leads to chemical bond formation between epoxy groups of ENR and silanol groups of silica. The extent of chemical bond formation is further enhanced in the presence of the silane coupling agent N‐3‐N‐(vinyl benzyl amino)ethyl‐γ‐amino‐propyl trimethoxy silane mono hydrogen chloride (trade name Z‐6032). The results of hysteresis loss measurements show that hysteresis loss increases with increase in coupling agent loading as a result of the higher modulus of the compounds compared to that of the ENR–silica mix. The dynamic mechanical property measurements show that the addition of coupling agent increases the glass‐transition temperature. Whereas strain‐dependent dynamic mechanical properties show that filler structure breakdown increases with increasing loading of coupling agent. Sulfur‐cured systems show higher filler structure breakdown compared to that of nonsulfur systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2171–2177, 2002     

One‐step latex compounding method for producing composites of natural rubber/epoxidized natural rubber/aminosilane‐functionalized montmorillonite: enhancement of tensile strength and oil resistance

Montmorillonite (Mt) was intercalated with cetyltrimethylammonium bromide and functionalized with three types of aminosilane (3‐aminopropyltrimethoxysilane, n‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane and 3‐[2‐(2‐aminoethylamino)ethylamino]propyltrimethoxysilane). The modified Mt was compounded with natural rubber (NR)/epoxidized natural rubber (ENR) via one‐step latex compounding. The effect of the modified Mt content on the oil resistance and mechanical properties of the NR/ENR/modified Mt composites was investigated. The X‐ray diffraction patterns of the composites showed partial intercalation/exfoliation of the modified Mt in the rubber matrix. Cryogenic fracture and X‐ray fluorescence results revealed highly dispersed modified Mt in the composites in the presence of 10 phr ENR. All three aminosilane groups slightly improved the oil resistance, with the long‐alkyl‐length group producing the greatest improvement. The addition of a small amount of modified Mt improved both oil resistance and tensile strength by increasing in the average diffusion path length in the NR matrix and enhancing the interaction between the modified Mt and the epoxide groups in ENR. The addition of 1.0 phr of modified Mt increased the tensile strength by 18% and decreased the elongation at break by 12% compared with a neat NR/ENR blend. © 2017 Society of Chemical Industry     

Co-compatibilising effect of carbon nanotubes and liquid isoprene rubber on carbon black filled natural rubber/polybutadiene rubber blend

Abstract

Bis-(triethoxysilylpropyl)-tetrasulfane functionalised carbon nanotubes (t-CNTs) were used as compatibiliser along with liquid isoprene rubber (LIR) in the natural rubber (NR)/polybutadiene rubber (BR) blend. Their reinforcing and compatibilising effects were evaluated by mechanical, fatigue crack growth resistance properties and blend homogeneity. Scanning electron microscope and transmission electron microscope showed enhanced interfacial adhesion between the binary rubber phases and improved dispersion of the minor phase in the rubber blend respectively with the co-existence of LIR and carbon nanotubes. The tensile strength of the carbon black (CB) filled NR/BR blend reached its optimum when 3 phr CB was replaced with an equal amount of t-CNTs in the presence of 7 phr LIR, while the fatigue crack growth resistance property achieved its maximum in the presence of 3 phr LIR. This interesting co-compatibilisation behaviour of t-CNTs and LIR suggests that t-CNTs have a better effect than CB with the assistance of LIR, which is an effective plasticiser in the NR/BR blend.