碳酸钙晶须表面处理及其对天然橡胶复合材料性能的影响

碳酸钙晶须用表面改性剂Si-69、硬脂酸钠、钛酸酯偶联剂NDZ101进行表面处理,并用于天然橡胶（NR）的补强。结果表明,表面处理后碳酸钙晶须的表面性能提高,与NR的界面作用增强,对NR起到明显的补强作用。表面处理后碳酸钙晶须的加入使改性碳酸钙晶须／NR复合材料的损耗因子tan艿降低,热稳定性提高。其中以Si-69改性碳酸钙晶须补强效果最优,Si-69改性碳酸钙晶须／NR复合材料300％定伸应力、拉伸强度、撕裂强度比未改性的分别提高36．9％、34．2％、24．7％。     

Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion

Filler dispersion is a critical factor in determining the properties of filled rubber composites. Silica has a high density of silanol groups on the surface, which lead to strong filler–filler interactions and a poor filler dispersions. A cure accelerator, N‐tert‐butyl‐2‐benzothiazole sulfenamide (TBBS), was found to improve filler dispersion in silica‐filled natural rubber (NR) compounds. For the silica‐filled NR compounds without the silane coupling agent, the reversion ratio generally increased with increase in TBBS content, whereas those of the silica‐filled NR compounds containing the silane coupling agent and carbon black‐filled NR compounds decreased linearly. The tensile strength of the silica‐filled NR vulcanizate without the silane coupling agent increased as the TBBS content increased, whereas carbon black‐filled samples did not show a specific trend. The experimental results were explained by TBBS adsorption on the silica surface and the improvement of silica dispersion with the aid of TBBS. Copyright © 2003 Society of Chemical Industry     

PROPERTIES OF POLYPROPYLENE/NATURAL RUBBER/RECYCLE RUBBER POWDER BLENDS

Thermoplastic elastomers have been prepared by blending polypropylene (PP), natural rubber (NR), and recycle rubber powder (RRP). The blends were melt-mixed using a Brabender Plasticorder torque rheometer at 190°C and 50 rpm. A fixed 70:30 blend ratio (wt%) of PP and rubber was prepared. The effect of partial replacement of NR with RRP at a fixed rubber content (NR+RRP), 30 wt% on mechanical properties, swelling behavior, torque development, and morphological properties of PP/NR/RRP blends was studied. Results show that the tensile strength, Young's modulus, and swelling resistance increase with increasing RRP content in the PP/NR/RRP blends whereas the stabilization torque and elongation at break exhibit opposite trend.     

Maleated Natural Rubber as a Coupling Agent for Recycled High Density Polyethylene/Natural Rubber/Kenaf Powder Biocomposites

Kenaf powder (KP) was incorporated into recycled high density polyethylene (rHDPE)/natural rubber (NR) blend using an internal mixer at 165°C and rotor speed of 50 rpm. The tensile strength and elongation at break of the composites decreased, while the tensile modulus increased with increasing filler loading. The water absorption was found to increase as the filler content increased. The maleic anhydride grafted natural rubber was prepared and used to enhance the composites performance. The addition of MANR as a coupling agent improved the tensile properties of rHDPE/NR/KP biocomposites. The water absorption was also reduced with the addition of MANR.     

碳酸钙晶须改性对其与天然橡胶复合材料性能的影响

采用Si-69、硬脂酸钠、NDZ101、硬脂酸和十八酸锌5种表面改性剂对碳酸钙晶须进行表面处理,研究了改性碳酸钙晶须对NR性能的影响。结果表明,选用Si-69改性碳酸钙晶须,且用量为5份时,复合材料的力学性能最好,300%定伸应力、拉伸强度、撕裂强度比未改性时分别提高了26.0%,21.1%和22.5%;复合材料的损耗因子(tanδ)最小,比纯胶降低了0.20,玻璃化转变温度(Tg)为-82.8℃,耐寒性最好。     

Maleated natural rubber prepared through mechanochemistry and its coupling effects on natural rubber/cotton fiber composites

Maleated natural rubber (MNR) was prepared by blending natural rubber (NR) and maleic anhydride (MA) in an internal mixer at 150 °C through mechanochemistry. The graft reaction of MA onto NR and the hydrogen bonding formed between fiber and MA were confirmed by Fourier transformation infrared spectrometer (FTIR). The quantity of grafted MA increased with increasing MA content. The composites showed better mechanical properties with MNR that contains higher MA content. The MNR with 20 phr MA was used as a coupling agent. Kraus equation showed the incorporation of MNR favored the reinforcement of fiber. The composites with MNR showed higher modulus and tensile strength than those without MNR. The coarse surfaces of the pullout fibers and the high storage modulus of composites with MNR implied the enhancement of interfacial adhesion.     

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。     

The Effect of Rice Husk Powder on Standard Malaysian Natural Rubber Grade L (SMR L) and Epoxidized Natural Rubber (ENR 50) Composites

The effects of rice husk powder (RHP) loading and two types of natural rubber matrix (SMR L and ENR 50) on curing characteristics and mechanical properties were studied. The scorch time and cure time decreased with increasing RHP loading whereas maximum torque showed an increasing trend. SMR L composites possessed longer scorch time and cure time than ENR 50 composites. Incorporation of RHP into both rubbers improved tensile modulus significantly but decreased tensile strength and elongation at break. SMR L composites exhibited the lower tensile modulus and higher tensile strength and elongation at break than ENR 50 composites.     

Carbon nanotubes/carbon black synergistic reinforced natural rubber composites

Abstract

Carbon black (CB) and carbon nanotubes (CNTs) filled natural rubber (NR) composites were prepared. In order to overcome the dispersion of CNTs in rubber matrix, the surface modification of CNTs with bis-(γ-triethoxysilylpropyl)-tetrasulphide (Si-69) was undertaken, and a two-step mixing process, i.e. the use of twin roll mill followed by mixing in a Haake Banbury mixer (TR-THM) was used. The structure and mechanical properties were investigated. The results show that the Si-69 treated CNTs (S-CNTs) were dispersed in the rubber matrix uniformly. Compared with CB/NR composites without CNTs, the S-CNTs/CB/NR composites have better mechanical properties. When the ratio of S-CNTs/CB/NR was 5 : 20 : 100, the tear strength was improved by ～60%, and the mechanical properties reached a maximum. Dynamical mechanical analysis (DMA) reveals that with increasing content of CNT, the elastic modulus of composites at room temperature increases, and the maximum loss tangent and the corresponding glass transition temperature of composites decrease.     

Curing characteristics and mechanical properties of rattan‐powder‐filled natural rubber composites as a function of filler loading and silane coupling agent

Curing characteristics, tensile properties, morphological studies of tensile fractured surfaces using scanning electron microscopy (SEM), and the extent of rubber filler interactions of rattan‐powder‐filled natural rubber (NR) composites were investigated as a function of filler loading and silane coupling agent (CA). NR composites were prepared by the incorporation of rattan powder at filler loading range of 0–30 phr into a NR matrix with a laboratory size two roll mill. The results indicate that in the presence of silane CA, scorch time (t_s2), and cure time (t₉₀) of rattan‐powder‐filled NR composites were shorten, while, maximum torque (M_H) increased compared with NR composites without silane CA. Tensile strength and tensile modulus of composites were enhanced whereas elongation at break reduced in the presence of silane CA mainly due to increase in rubber‐filler interaction. It is proven by SEM studies that the bonding between the filler and rubber matrix has improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cure characteristics,mechanical, thermal,and coloring properties of natural rubber/dye‐loaded shell powder composites

To explore the application of shell powder (SP) in rubber, a dye‐loaded SP (DSP) bio‐filler based on SP and Congo red was incorporated into natural rubber (NR). The adsorption experiments demonstrated that the maximum monolayer adsorption capacity of Congo red onto SP was 69.3 mg/g. The effect of aluminate coupling agent and DSP was investigated by evaluating the cure characteristics, mechanical, thermal, and coloring properties of NR/DSP composites. It was suggested that the optimum amount of aluminate coupling agent was 2 wt %, and the best tensile strength (24.80 MPa) of vulcanizates was achieved at the DSP content of 20 phr, while other mechanical properties such as tear strength kept increasing with the addition of DSP. Furthermore, the improved thermal stability and uniform color distribution of the NR composites was obtained. The results indicate that DSP is promising to become a low‐cost filler and pigment for rubber materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45750.     

Effect of a silane coupling agent on the properties of white rice husk ash–polypropylene/natural rubber composites

White rice husk ash (WRHA)–polypropylene (PP)/natural rubber (NR) composites were prepared using a Brabender Plasticorder at 180 °C and a rotor speed of 50 rev min^?1. The mechanical and water‐absorption properties were studied. The incorporation of WRHA into the PP/NR matrix has resulted in the improvement of the tensile modulus; however, the tensile strength, elongation at break and stress at yield decreased with increasing WRHA loading. Poor filler matrix interactions are believed to be responsible for the decrease in the properties. Incorporation of a silane coupling agent, 3‐aminopropyl triethoxysilane (3‐APE), improved tensile modulus, tensile strength and stress at yield of the composites. Water‐absorption studies indicate that the use of the coupling agent reduced the amount of water absorbed by the composites. © 2001 Society of Chemical Industry     

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     

Preparation,characterization, and application of NR/SBR/Organoclay nanocomposites in the tire industry

The natural rubber/styrene butadiene rubber/organoclay (NR/SBR/organoclay) nanocomposites were successfully prepared with different types of organoclay by direct compounding. The optimal type of organoclay was selected by the mechanical properties characterization of the NR/SBR/organoclay composites. The series of NR/SBR/organoclay (the optimal organoclay) nanocomposites were prepared with various organoclay contents loading from 1.0 to 7.0 parts per hundreds of rubber (phr). The nearly completely exfoliated organoclay nanocomposites with uniform dispersion were confirmed by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results of mechanical properties measurement showed that the tensile strength, tensile modulus, and tear strength were improved significantly when the organoclay content was less than 5.0 phr. The tensile strength and the tear strength of the nanocomposite with only 3.0 phr organoclay were improved by 92.8% and 63.4%, respectively. It showed organoclay has excellent reinforcement effect with low content. The reduction of the score and cure times of the composites indicated that the organoclay acted as accelerator in the process of vulcanization. The incorporation of a small amount of organoclay greatly improved the swelling behavior and thermal stability, which was attributed to the good barrier properties of the dispersed organoclay layers. The outstanding performance of co‐reinforcement system with organoclay in the tire formulation showed that the organoclay had a good application prospect in the tire industry, especially for the improvement of abrasion resistance and the reduction of production cost. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

碳纳米管预处理方法对天然橡胶/纯化碳纳米管复合材料力学性能的影响

纯化后的碳纳米管(CNT)分别经过球磨、表面活性剂十二烷基苯磺酸钠或分散-黏合体系预处理,再与100份(质量)天然橡胶(NR)混炼,可制备NR/纯化CNT复合材料。结果表明,纯化CNT直接与NR混炼,前者在NR中的分散效果不好,二者的界面结合欠佳。纯化CNT经球磨后,团聚程度增加,对复合材料力学性能影响不大。经表面活性剂十二烷基苯磺酸钠处理后的纯化CNT,内聚能下降,用差示扫描量热法(DSC)测定复合材料的DSC曲线表明,复合材料的结晶熔融峰面积增大,力学性能降低。用分散-黏合体系处理纯化CNT,可同时提高纯化CNT在橡胶中的分散效果及界面黏合性,试样结晶熔融峰变得不明显,因此该复合材料的邵尔A型硬度提高,拉伸强度、300％定伸应力和撕裂强度等优于其他试样。     

离子液体与偶联剂并用对白炭黑填充NR性能的影响

本文用偶联剂Si-69、B-69和离子液体[溴化1-丁基-3-甲基咪唑(BMIM)]单独改性白炭黑,同时用两种偶联剂分别与离子液体BMIM并用改性白炭黑,对比研究了其对NR性能的影响。结果表明,与未改性白炭黑相比,Si-69、B-69和BMIM改性白炭黑后,填充NR的硫化速率加快,Payne效应减弱,力学性能改善,滚动阻力降低;其中,BMIM改性白炭黑填充NR的综合性能最优,其拉伸强度和撕裂强度比未改性白炭黑填充NR提高了一倍。与偶联剂单独改性白炭黑相比,偶联剂与BMIM并用改性白炭黑后,填充NR的t90进一步缩短,填料-橡胶相互作用更强,交联密度更大,力学性能进一步提高,滚动阻力变得更低。     

改性淀粉对炭黑填充丁苯橡胶/顺丁橡胶并用胶性能的影响

用改性淀粉替代部分炭黑填充丁苯橡胶(SBR)/顺丁橡胶(BR)并用胶,考察了改性淀粉用量及偶联剂种类对混炼胶硫化特性及硫化胶物理机械性能和动态力学性能的影响.结果表明,用改性淀粉替代部分炭黑可对SBR/BR混炼胶的硫化产生明显的延迟作用,但改性淀粉用量的变化对焦烧时间与正硫化时间影响不大;添加偶联剂KH-570或NDZ-201延迟了混炼胶的硫化过程,KH-550能大幅度地促进硫化作用,Si-69对于体系的硫化性能略有影响;随着改性淀粉用量的增加,SBR/BR硫化胶的拉伸性能、耐磨耗性均有所降低,但弹性、动态生热和滞后性能得到了明显改善,改性淀粉最佳用量为5～8份;各种偶联剂均可提高SBR/BR硫化胶的拉伸性能,硅烷偶联剂Si-69和KH-570对弹性和动态生热也略有改善,添加偶联剂KH-550改善了SBR/BR硫化胶的抗湿滑性能,但滞后性能变差,添加偶联剂KH-570或Si-69对SBR/BR硫化胶动态力学性能的影响较小,综合考虑,以添加偶联剂KH-570较好.     

Effects of palm ash loading and maleated natural rubber as a coupling agent on the properties of palm‐ash‐filled natural rubber composites

Natural rubber composites were prepared by the incorporation of palm ash at different loadings into a natural rubber matrix with a laboratory‐size two‐roll mill (160 × 320 mm²) maintained at 70 ± 5°C in accordance with the method described by ASTM D 3184–89. A coupling agent, maleated natural rubber (MANR), was used to improve the mechanical properties of the natural rubber composites. The results indicated that the scorch time and cure time decreased with increasing filler loading, whereas the maximum torque exhibited an increasing trend. Increasing the palm ash loading increased the tensile modulus, but the tensile strength, fatigue life, and elongation at break decreased. The rubber–filler interactions of the composites decreased with increasing filler loading. Scanning electron microscopy of the tensile fracture surfaces of the composites and rubber–filler interaction studies showed that the presence of MANR enhanced the interfacial interaction of the palm ash filler and natural rubber matrix. The presence of MANR also enhanced the tensile properties and fatigue life of palm‐ash‐filled natural rubber composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

硅烷偶联剂对白炭黑填充溴化丁基橡胶/天然橡胶并用胶性能的影响

试验研究硅烷偶联剂Si69,Si75和KH560对白炭黑填充溴化丁基橡胶(BIIR)/天然橡胶(NR)并用胶性能的影响。结果表明:随着硅烷偶联剂Si75或KH560用量的增大,胶料的挤出膨胀率呈增大趋势,门尼粘度和F;减小,Payne效应减弱,定伸应力和拉伸强度呈增大趋势,拉断伸长率和撕裂强度呈减小趋势,加工性能和老化后耐屈挠性能改善;硅烷偶联剂Si75和KH560能够明显改善白炭黑填充BIIR/NR并用胶的加工性能和老化后的耐屈挠性能。     

Effects of partial replacement of commercial fillers by recycled poly(ethylene terephthalate) powder on the properties of natural rubber composites

Commercial fillers, including carbon black (N550), halloysite nanotubes (HNTs), and precipitated silica, were replaced by recycled poly(ethylene terephthalate) powder (R‐PET) in natural rubber (NR) composites. Five different compositions of NR/N550/R‐PET, NR/HNTs/R‐PET, and NR/silica/R‐PET compounds, i.e., 100/20/0, 100/15/5, 100/10/10, 100/5/15, and 100/0/20 parts per hundred rubber (phr), were prepared on a two‐roll mill. The curing behavior, tensile properties, and morphological characteristics of the natural rubber composites were investigated. The results indicated that the replacement of carbon black, HNTs, and silica by R‐PET decreased the tensile strength and tensile modulus, such that NR/silica/R‐PET composites showed the lowest effect, followed by NR/HNTs/R‐PET and NR/N550/R‐PET composites. The negative effect on these properties can be explained by the decrease of crosslink density. The curing results revealed that with the replacement of carbon black by R‐PET, the scorch time and cure time decreased, but that the NR/HNTs/R‐PET and NR/silica/R‐PET composites exhibited the opposite trend. Scanning electron microscopy investigation of tensile fracture surfaces confirmed that the co‐incorporation of N550/R‐PET improved the dispersion of R‐PET and enhanced the interaction between the fillers and NR matrix more than R‐PET and silica/R‐PET hybrid fillers. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers