偶联剂Si69-纳米氧化锌改性槟榔纤维对天然橡胶复合材料性能的影响

以天然胶乳浸润槟榔纤维,制备天然橡胶(NR)复合材料,研究偶联剂Si69-纳米氧化锌改性槟榔纤维对NR复合材料性能的影响。结果表明:与未改性槟榔纤维的NR复合材料相比,偶联剂Si69-纳米氧化锌改性槟榔纤维的NR复合材料的物理性能、耐溶剂性能和抗湿滑性能改善,剪切模量减小,滚动阻力提高;偶联剂Si69-纳米氧化锌改性槟榔纤维的NR复合材料的综合性能优于偶联剂Si69和纳米氧化锌单独改性槟榔纤维的NR复合材料。     

硅烷偶联剂KH-550和Si-69增容粉煤灰/废胶粉复合材料

采用硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH-550)和双-[γ-(三乙氧基硅)丙基]四硫化物(Si-69)对粉煤灰(FA)/废胶粉(URP)复合材料进行增容,考察了偶联剂用量和加入方式对复合材料性能的影响,并对复合材料的结构和微观形貌进行了表征。结果表明,KH-550和Si-69均可以改善FA与URP的相容性,提高复合材料的力学性能;Si-69的增容效果好于KH-550,最佳的Si-69/FA/URP(质量比)为1.0/40/100。采用硅烷偶联剂与FA混合、再与URP混合的分步加入方式,与同步加入方式相比,制备的复合材料更易成型,且复合材料的力学性能、耐磨性能和耐热老化性能更好。与KH-550相比,用Si-69改性的FA/URP复合材料,其相界面更为模糊,无孔洞。硅烷偶联剂改性的FA/URP复合材料中有Si—O生成。     

Fly‐ash particles and precipitated silica as fillers in rubbers. II. Effects of silica content and Si69‐treatment in natural rubber/styrene–butadiene rubber vulcanizates

This article explored the possibility of using silica from fly‐ash particles as reinforcement in natural rubber/styrene–butadiene rubber (NR/SBR) vulcanizates. For a given silica content, the NR : SBR blend ratio of 1 : 1 (or 50 : 50 phr) exhibited the optimum mechanical properties for fly‐ash filled NR/SBR blend system. When using untreated silica from fly‐ash, the cure time and mechanical properties of the NR/SBR vulcanizates decreased with increasing silica content. The improvement of the mechanical properties was achieved by addition of Si69, the recommended dosage being 2.0 wt % of silica content. The optimum tensile strength of the silica filled NR/SBR vulcanizates was peaked at 10–20 phr silica contents. Most mechanical properties increased with thermal ageing. The addition of silica from fly‐ash in the NR/SBR vulcanizates was found to improve the elastic behavior, including compression set and resilience, as compared with that of commercial precipitated silica. Taking mechanical properties into account, the recommended dosage for the silica (FASi) content was 20 phr. For more effective reinforcement, the silica from fly‐ash particles had to be chemically treated with 2.0 wt % Si69. It was convincing that silica from fly‐ash particles could be used to replace commercial silica as reinforcement in NR/SBR vulcanizates for cost‐saving and environment benefits. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Fatigue resistance of silica‐filled natural rubber vulcanizates: comparative study of the effect of phosphorylated cardanol prepolymer and a silane coupling agent

The fatigue resistance of silica‐filled natural rubber (NR) mixes modified with phosphorylated cardanol prepolymer (PCP) was studied in comparison with similar compositions without PCP and with those containing the same dosage of a silane coupling agent (Si‐69). Considerable improvement in the fatigue resistance was observed for the PCP‐modified NR vulcanizate containing 20 phr of silica compared with the unmodified and Si‐69 modified vulcanizates. In addition, the tear strength of the PCP‐modified NR vulcanizate was higher than that of the others. Atomic force microscopy and the scanning electron microscopy of the vulcanizates showed better dispersion of silica particles in the NR matrix in the presence of PCP than in the unmodified and Si‐69‐modified NR vulcanizates. It is assumed that, at a dosage of 5 phr, PCP functions as a coupling agent between NR and the silica particles thereby improving the filler dispersion and consequently the mechanical properties of the vulcanizate. Copyright © 2005 Society of Chemical Industry     

偶联剂Si 69对NR/BR/NBR共混硫化胶性能的影响

研究了偶联剂Si 69对NR／BR／NBR共混胶体系的硫化特性、交联密度和硫化胶的物理机械性能及动态力学性能的影响。结果表明，偶联剂Si 69在共混硫化胶中可以起到提高聚合物与填料间的相互作用和交联密度的作用，它在白炭黑增强硫化胶中对性能的改善比在炭黑增强硫化胶中的改善更显著。     

Interfacial adhesion and molecular diffusion in melt lamination of wood sawdust/ebonite NR and EPDM

Adhesion mechanisms and peel strengths of wood/ebonite NR‐EPDM laminates were investigated. Three different chemical coupling agents: namely; N‐(β aminoethyl)‐γ‐aminopropyl‐triethoxysilane (AAS), 3‐methacryloxypropyl trimethoxysilane (ACS), and Bis‐(3‐triethoxylpropyl) tetrasulfan (Si69) were introduced into the wood/NR composites to enhance an interaction between wood sawdust (SD) particles and NR molecules, and to improve the adhesion strength between the SD/NR and EPDM layers. The quantitative evidences were given to explain the changes in the adhesion or peel strengths of the SD/NR‐EPDM laminates through scanning electron microscopy with energy dispersive X‐ray analysis (SEM‐EDS). The experimental results indicated that the suitable cure time and cure temperature for SD/NR‐EPDM melt‐laminates were the tc₉₀ of SD/NR composites and 140°C, respectively. The Si69 coupling agent was found to be the most effective coupling agent as compared with AAS and ACS coupling agents. The Si69 of 0.5 wt% was recommended for the optimizations of the tensile modulus of the SD/NR composites and the peel strength of the SD/NR‐EPDM laminates. The diffusion level between the SD/NR and EPDM layers could be quantitatively substantiated by determining the sulfur content transfer from the SD/NR layer to the EPDM layer. The diffusion and entanglement of molecular chains from the SD/NR to the EPDM layer initiated the co‐crosslinking reaction which played an important role on the changes in the interfacial strength in the SD/NR‐EPDM melt‐laminates. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Influence of silane coupling agents on vulcanised natural rubber: dynamic properties and heat buildup

We explore the influence of surface modification of SiO₂ on dynamic properties and heat buildup of semi-ef?cient vulcanisates filled by both SiO₂ and carbon black. Compared with untreated-SiO₂-filled natural rubber (NR), vulcanisates reinforced by modified-SiO₂ presents not only better filler dispersity, mechanical properties and dynamic properties, as confirmed by scanning electron microscope and rubber processing analyser, but also lower heat buildup. Fourier infrared spectroscopy and cure characteristics indicates that silane coupling agent molecules grafted on the silica surface provoke an enhanced mobility of rubber chain and adsorb onto filler surface and then decrease the barrier of crosslink reaction. Moreover, composites with Si69-modified-SiO₂ show obviously the highest tear strength and lowest heat buildup attributed to that more sulphur released by Si69 also participate the vulcanisation reaction.     

The Effect of Ethylene Diamine Dilaurate and Silane Coupling Agent on Cure Characteristics,Mechanical, and Thermal Properties of Silica-Filled Natural Rubber Composites

The influence of a new coupling agent, ethylene diamine dilaurate (EDD) and a commercial silane coupling agent, (Si-69) on the cure characteristics, mechanical and morphological properties of silica-filled natural rubber (NR) composites was studied. The results show that scorch time and cure time decreased with an increase in both coupling agents' content, but maximum and minimum torques exhibit the opposite trend. The mechanical properties such as tensile strength and tensile modulus, M100 and M300, increased with increasing both coupling agents' content but at a similar coupling agent content, silica-filled natural rubber composites with Si-69 exhibit better tensile strength (more than 2 phr) and tensile modulus than does EDD. Elongation at break (Eb) of silica-filled natural rubber increased with increasing EDD content but Si-69 exhibits the opposite trend. Scanning electron microscopy (SEM) study of tensile fracture surfaces shows the better tensile strength of silica-filled natural rubber composites with Si-69 and EDD over control composites (without EDD or Si-69). Thermogravimetric analysis (TGA) results indicate that silica-filled NR composites with EDD have higher thermal stability than Si-69. Fourier transform infrared spectra (FTIR) provided an evidence of interaction between EDD and Si-69 with silica in NR composites.     

Effect of a coupling agent on the properties of hemp‐hurd‐powder‐filled styrene–butadiene rubber

Styrene–butadiene rubber (SBR) composites filled with hemp hurd powder (HP) were prepared with bis(3‐triethoxysilylpropyl) tetrasulfide (Si69) as a coupling agent. The effects of the filler content and coupling agent on the curing characteristics and dynamic mechanical properties of the composites were studied. The results indicate that with increasing filler loading, the torque values increased and the curing time decreased. The mechanical properties improved with increasing filled HP content up to 60 phr. Usually, long fibers led to a sharp decrease in the toughness of the composites, whereas short fibers, such as HP, had a positive effect on the elongation at break within the loading range studied. The extent of the filler–matrix interaction and the scanning electron micrographs of the fractured surfaces confirmed that the addition of Si69 improved the interfacial interaction between HP and the SBR matrix, which led to an increase in the maximum torque and the mechanical properties. Moreover, the coupling agent was helpful in dispersing the filler in the rubber matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The combination of montmorillonite and silica in styrene–butadiene rubber/polybutadiene rubber tread compounds

Montmorillonite and silica were used as fillers combined with Si69 as their coupling agent in styrene–butadiene rubber/polybutadiene rubber tread compounds to evaluate their interaction and influences on structure and properties of nanocomposites. Microstructure, filler dispersion, curing properties, and tire performance of the compounded rubber were investigated with the aid of X‐ray diffraction, transmission electron microscopy, rheometer, and dynamic‐mechanical analysis, respectively. The results showed that montmorillonite could react with coupling agent and their reaction rate was higher than silica/Si69. The dispersion and exfoliation was promoted by the existence of silica. Fully exfoliated montmorillonite were formed when the montmorillonite/silica ratio was 14 or lower, and the as‐prepared rubber compounds displayed well‐balanced properties. Additionally, coupling agent also influenced the curing kinetics, dynamic, and mechanical properties of the tread compounds. But the structure was not affected by the usage amount of Si69. POLYM. COMPOS., 38:918–926, 2017. © 2015 Society of Plastics Engineers     

Synergistic effect of carbon black and carbon–silica dual phase filler in natural rubber matrix

In this article, the synergistic effects of carbon black (CB) and modified carbon–silica dual phase filler (MCSDPF) on the properties of natural rubber (NR) were investigated. MCSDPF was prepared by modifying carbon–silica dual phase filler (CSDPF) with bis(3‐triethoxysilylpropyl)tetrasulphane (Si‐69). Fourier transform infrared spectroscopy and thermogravimetric analyzer analyses revealed that Si‐69 was successfully grafted to CSDPF. NR‐based compounds containing various combinations of MCSDPF and CB were prepared through a mechanical mixing. Investigations of mechanical properties, ageing resistance, abrasion resistance, dynamic mechanical properties, and morphology of tear fractured surface of MCSDPF/CB/NR vulcanizates were conducted. Our study shows that adding MCSDPF led to significant improvement in the tear resistance, fatigue life, and elongation at break of MCSDPF/CB/NR vulcanizates. Optimum stoichiometric combination of MCSDPF and CB inside the NR matrix was derived (ratio of MCSDPF and CB in wt% = 15/50), which showed synergistic effects of MCSDPF upon CB that was ultimately reflected in their tensile strength, wet skid resistance, and rolling resistance. POLYM. COMPOS., 35:1466–1472, 2014. © 2013 Society of Plastics Engineers     

The role of interlayer grafting on the mechanical properties of magadiite/styrene‐butadiene rubber composites

This work examines the mechanisms by which magadiite (MGD), a synthetic layered silicate, acts as an active filler to provide high levels of mechanical reinforcement in styrene‐butadiene rubber (SBR) composites. Cetyltrimethylammonium (CTA⁺) expands the MGD layer spacing and promotes intercalation of SBR and silane coupling agent (Si69); the resulting CMGD/SBR composites have greater tensile moduli than comparable silica/SBR composites. CMGD was reacted in solution with Si69 (or MPTES) to prepare “pre‐grafted” MGD with varying levels of interlayer silane functionalization (SMGD). If the silane graft density is relatively low, the resulting SMGD/SBR composite has mechanical properties comparable to CMGD composites prepared with Si69 added during batch mixing. However, SMGD with high silane graft density does not permit SBR intercalation and produces composites with inferior mechanical properties, demonstrating the necessity of silane‐mediated interlayer grafting. Omitting Si69 from the formulation dramatically reduces the level of mechanical reinforcement as measured by DMA and tensile testing. Adding extra bulk sulfur (to replace sulfur omitted with Si69) does not produce composites with mechanical properties comparable to CMGD/SBR or SMGD/SBR prepared with Si69. This work demonstrates that silane‐mediated SBR‐MGD grafts within the MGD interlayer space are essential for achieving high levels of mechanical reinforcement in MGD/SBR composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45025.     

Mechanical,thermal, morphological,and curing properties of geopolymer filled natural rubber composites

The main objective of this work was to investigate influence of natural rubber (NR) types on mechanical, thermal, morphological, and curing properties together with relaxation behavior of geopolymer filled NR composites with and without bis(triethoxysilylpropyl) tetrasulfide (TESPT) silane coupling agent. Three alternative types of NR: unmodified NR, and epoxidized NR with 25 (ENR-25) or 50 mol % epoxide (ENR-50) were exploited. Rubber compounds filled with GP particles were prepared in an internal mixer at 60 °C and 130–150 °C for the ones with and without TESPT, respectively. It was found that incorporation of GP significantly affected cure characteristics and mechanical properties of the rubber composites. That is, decreasing cure time was observed from 11.6, 3.2, and 7.0 min in gum NR, ENR-25, and ENR-50 to 6.9, 2.1, and 5.0 min in NR/GP, ENR-25/GP, and ENR-50/GP compounds, respectively. Furthermore, the ENR-25/GP and ENR-50/GP composites showed finely dispersed GP particles which indicate high filler–rubber interactions. The in situ silanization with TESPT in rubber composites enhanced the mechanical properties of NR/GP and ENR-25/GP composites but no such enhancement was found in the ENR-50/GP composite. This matched the observations of Payne effect, maximum tan δ, and stress relaxation properties of the composites. We found that the ENR-25/GP composites exhibited the best overall properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47346.     

Viscoelastic,mechanical, and thermal characterization of fly ash‐filled ABS composites and comparison of fly ash surface treatments

In the present investigation, viscoelastic, mechanical, thermal properties, and microstructural analysis of ABS reinforced with various surface treated fly ash (FA) has been studied. FA particles were surface treated with various chemical reagents, i.e., Ca(OH)₂, NaOH, and Bis(3‐triethoxysilylpropyl)tetrasulfane (Si69) to improve the interfacial adhesion between ABS and FA. DMA tests confirmed an increase in the stiffness in the surface treated composites. Hybrid ABS/FA composites showed optimum storage modulus and T_g as compared with the virgin matrix. TGA analysis also showed higher thermal stability of ABS/FA composites than virgin matrix with the surface treatments of FA. The treated FA composites also show improved mechanical properties compared to untreated FA composite. The morphology of virgin matrix, untreated and treated FA composites was studied employing SEM. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

偶联剂Si69原位改性淀粉/NR复合材料的性能研究

采用原位法制备偶联剂Si69改性淀粉/NR复合材料,并研究偶联剂Si69对复合材料性能的影响.结果表明:采用偶联剂Si69对淀粉进行原位改性可以增强淀粉与NR的界面相互作用,改善淀粉在NR中的分散性;偶联剂Si69与淀粉发生了化学作用,并参与了NR的硫化,从而提高复合材料的物理性能.     

针状硅酸盐的表面改性及其橡胶复合材料的力学性能

考察了不同改性剂及其用量对针状硅酸盐(FS)表面改性和FS／橡胶复合材料力学性能的影响。结果表明,FS存在结构羟基,其中一些羟基具有化学反应活性。硅烷偶联剂、钛酸酯偶联剂和十六烷基三甲基溴化铵对FS具有较好的改性效果。硅烷偶联剂Si69改性FS增强效果最好,其最佳用量为2．4质量份;改性FS用量的增加改善了复合材料的力学性能;改性FS对丁苯橡胶、三元乙丙橡胶、丁腈橡胶、羧基丁腈橡胶具有良好的增强效果。     

气膜包覆法制备Si69改性淀粉/天然橡胶复合材料的性能

采用气膜包覆法制得双(3 -三乙氧基硅烷丙基)四硫化物(简称Si 69)改性淀粉,然后与天然橡胶(NR)共混制得Si 69改性淀粉/NR复合材料,研究了Si 69改性淀粉的疏水性,考察了Si 69用量对复合材料硫化特性、物理机械性能、加工性能及动态性能的影响,并表征了复合材料的相态结构.结果表明,经气流粉碎后淀粉的平均...     

Preparation of nano‐reinforced thermal conductive natural rubber composites

Natural rubber (NR) composites highly filled with nano‐α‐alumina (nano‐α‐Al₂O₃) modified in situ by the silane coupling agent bis‐(3‐triethoxysilylpropyl)‐tetrasulfide (Si69) were prepared. The effects of various modification conditions and filler loading on the properties of the nano‐α‐Al₂O₃/NR composites were investigated. The results indicated that the preparation conditions for optimum mechanical (both static and dynamic) properties and thermal conductivity were as follows: 100 phr of nano‐α‐Al₂O₃, 6 phr of Si69, heat‐treatment time of 5 min at 150°C. Furthermore, two other types of fillers were also investigated as thermally conductive reinforcing fillers for the NR systems: (1) hybrid fillers composed of 100 phr of nano‐α‐Al₂O₃ and various amounts of the carbon black (CB) N330 and (2) nano‐γ‐Al₂O₃, the particles of which are smaller than those of nano‐α‐Al₂O₃. The hybrid fillers had better mechanical properties and dynamic performance with higher thermal conductivity, which means that it can be expected to endow the rubber products serving under dynamic conditions with much longer service life. The smaller sized nano‐γ‐Al₂O₃ particles performed better than the larger‐sized nano‐α‐Al₂O₃ particles in reinforcing NR. However, the composites filled with nano‐γ‐Al₂O₃ had lower thermal conductivity than those filled with nano‐α‐Al₂O₃ and badly deteriorated dynamic properties at loadings higher than 50 phr, both indicating that nano‐γ‐Al₂O₃ is not a good candidate for novel thermally conductive reinforcing filler. POLYM. COMPOS., 37:771–781, 2016. © 2014 Society of Plastics Engineers     

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     

纳米氧化铝/天然橡胶复合材料的性能研究

采用原位改性纳米氧化铝制备纳米氧化铝/天然橡胶(NR)复合材料,研究纳米氧化铝用量及原位改性时间、偶联剂Si69用量对纳米氧化铝/NR复合材料的物理性能、动态力学性能和导热性能的影响。结果表明:随着纳米氧化铝用量的增大,复合材料的拉伸强度减小,热导率和压缩疲劳温升增大。原位改性可以提高纳米氧化铝与NR之间的界面结合作用。随着原位改性时间的延长或随着偶联剂Si69用量的增大,复合材料的拉伸强度和热导率均先增大后减小,压缩疲劳温升逐渐减小。