工业水玻璃制备SiO2/NR复合材料的研究

将超微细SiO2的制备工艺与天然橡胶（NR）的制备工艺相结合，以工业水玻璃为原料，采用溶胶-凝胶法制备SiO2溶胶和凝胶，再以天然鲜胶乳共沉-共凝制备SiO2／NR复合材料。实验结果表明：共沉-共凝法制备的SiO2／NR复合材料的综合力学性能明显优于机械共混法制备的复合材料；当SiO2质量分数为10％时，硫化胶的拉伸强度和撕裂强度分别比机械共混法制备的硫化胶提高了51％和49％，比纯NR硫化胶提高了88％和62％。复合材料拉伸断面电子扫描显微镜（SEM）观察表明，采用溶胶-凝胶法制备的超微细SiO2在NR硫化胶中的分散性较好，界面结合紧密，体现了超微细SiO2对NR具有较强的补强效果。     

原位表面改性纳米氧化锌对天然橡胶传统硫化体系硫化结构与性能的影响

采用溶胶-凝胶法制备了原位表面改性纳米Zn O,采用X射线衍射法(XRD)及透射电子显微镜(TEM)对其微观结构进行了表征,并用扫描电镜和X射线能谱仪(SEM with EDS)分析了ZnO在NR传统硫化体系(CV)硫化胶中的分散性。对比研究了使用原位表面改性纳米ZnO和普通ZnO的NR的CV硫化胶的硫化特性、拉伸性能和耐热氧老化性能,通过平衡溶胀法和化学探测剂法测定了硫化胶的硫化结构。研究结果表明,原位表面改性纳米ZnO在NR胶料中的分散性优于普通氧化锌。与加入5份普通ZnO的硫化胶相比,加入2份原位表面改性纳米ZnO的NR的CV硫化胶的拉伸强度和拉断伸长率分别提高了0.55%和10.34%。与此同时,硫化胶拉伸强度保持率和拉断伸长率保持率分别提高了35.85%和19.36%。     

壳聚糖改性二氧化硅/天然橡胶复合材料的性能

采用溶胶-凝胶法制备了壳聚糖改性二氧化硅,并采用共沉降法制备了壳聚糖改性二氧化硅/天然橡胶（NR）复合材料,考察了壳聚糖用量对复合材料硫化特性、拉伸性能、耐老化性能的影响,并用扫描电子显微镜观察了拉伸试样的断面形貌。结果表明,壳聚糖的加入使NR复合材料的性能得到明显改善,当其用量为0.5 g时,复合材料的硫化特性与拉伸性能最佳,正硫化时间为1.95 min,拉伸强度为24.01 MPa,扯断伸长率达到256%;当壳聚糖添加量为0.3 g时,硫化胶的拉伸强度与扯断伸长率的性能保持指数最高,耐老化性能最佳;经壳聚糖改性的二氧化硅在NR中的分散性得到改善。     

羧酸盐改性高龄土填充NB硫化胶的物理机械性能与形貌

乙酸钾和乳酸钾改性高岭土和NB乳液在碱性溶液中凝聚共沉，制备填充型NR，NR硫化胶的物理机械性能有大幅度提高。SEM研究表明，羧酸盐改性高岭土部分片层发生了卷曲；而且也酸钾改性高岭土/NR硫化胶的拉伸断面出现拉丝现象。     

纳米SiO2改性NR/SBR共混胶的结构与性能研究

研究了纳米SiO2加入方式及用量对NR/SBR共混胶的正硫化时间、力学性能的影响,并研究了纳米SiO2改性前后共混胶的耐热分解性能、耐热空气老化性能及微观形态结构.结果表明:纳米SiO2的加入对共混胶的正硫化时间、力学性能及耐热稳定性能有较大影响;当纳米SiO2加入量为7％(质量分数)并采用NR/SBR共混均匀后先加入纳米SiO2,再加入小料、硫磺的方式制备NR/SBR共混胶时,纳米SiO2通过使NR/SBR共混胶的分散相细化并使共混胶的整体交联密度提高,有效地提高了NR/SBR共混胶的综合力学性能和耐热稳定性能,达到了对NR/SBR共混胶良好的补强改性效果.     

共混比对预硫化多官能化丁基橡胶/天然橡胶共混胶性能的影响

研究了预硫化工艺下不同共混比对多官能化丁基橡胶/天然橡胶(MFIIR/NR)共混胶硫化特性、力学性能、耐老化性能以及微观形貌的影响,同时与传统工艺制备的共混胶的性能进行了对比。结果表明,当MFIIR作为主要组分时,预硫化法混炼胶的正硫化时间随MFIIR/NR共混比(质量比)的增大而缩短,最高转矩、最高转矩与最低转矩之差都随共混比的增大而呈现变小的趋势;随着预硫化法共混胶共混比的增大,共混胶的力学性能降低,耐老化性能提高,但都明显高于传统法共混胶的力学性能;预硫化共混胶拉伸断面的致密程度较传统法共混胶高,且随共混比的增大,拉伸断面的形貌趋于平坦。     

木质素-蒙脱土复合物代替三角带底胶中炭黑的应用研究

通过共沉淀-脱水法制备了木质素-蒙脱土复合物填料,并湿法混炼制备了木质素-蒙脱土复合物填充三角带底胶试验胶。研究了硫磺和促进剂的量、天然橡胶(NR)和顺丁橡胶(BR)的质量比对三角带底胶试验胶的硫化特性和力学性能的影响。并将木质素-蒙脱土复合物填充三角带底胶与炭黑填充的三角带底胶进行了比较。结果表明:增加硫磺和促进剂的量,提高了三角带底胶试验胶的硬度和300%定伸应力。增加天然橡胶和顺丁橡胶的质量比提高了三角带底胶试验胶的拉伸强度。调整配方后三角带底胶试验胶的综合性能已与N330填充胶料相当。     

离子液体与白炭黑的相互作用及其对天然橡胶性能的影响

采用离子液体氯化1-烯丙基-3-甲基咪唑(AMI)改性白炭黑,用傅里叶变换红外光谱和固体核磁共振研究了AMI与白炭黑的相互作用,研究了离子液体用量对改性白炭黑填充天然橡胶(NR)的硫化特性、力学性能和动态力学性能的影响。结果表明,AMI与白炭黑表面之间具有氢键作用,能够明显提高白炭黑在NR中的分散性。AMI能改变白炭黑填充胶料的硫化速率,AMI用量越多,NR胶料的硫化速率越大。随着AMI用量的增加,改性白炭黑填充NR硫化胶的拉伸性能和撕裂性能提高,当AMI用量为1.0份时,NR硫化胶的拉伸强度达到最大值23.95 MPa; 当AMI为2.0份时,NR硫化胶的撕裂强度达到最大值71.47 k N/m,与填充未改性白炭黑的NR硫化胶相比,分别提高了102.28%和41.83%。随着AMI用量的增加,NR硫化胶的玻璃化转变温度下降。     

纳米SiO2／胶清橡胶复合材料力学性能的研究

采用乳液共混法,研究了纳米SiO2/胶清橡胶复合材料的力学性能.结果表明,采用乳液共混法制备纳米SiO2/胶清橡胶复合材料的力学性能优于机械共混法.纳米SiO2改性剂(硅烷偶联剂 TESPT)用量为7.5%～10%,搅拌时间为30min,纳米SiO2用量为20～30份,可制备出力学性能较好的纳米SiO2/NR复合材料.     

预硫化时间对MFIIR／NR并用胶性能的影响

采用预硫化工艺,制备了MFIIR／NR并用胶。研究了预硫化时间和温度对并用胶硫化特性、力学性能和拉伸断面形貌的影响。结果表明,随着预硫化时间的延长,并用胶的焦烧时间和正硫化时间延长,拉伸强度呈先增加后减少的趋势,最大达到10．60MPa（大于传统工艺的4．46MPa）,但并用胶的拉伸断面具有较高致密程度,出现明显的脊状线和均匀的外观;不同预硫化温度下,并用胶的最佳力学性能基本相同。     

就地反应法制备天然橡胶/二氧化硅复合材料

在天然胶乳与Na2SiO3水溶液的混合体系中滴加盐酸,就地生成SiO2粒子,并与天然橡胶(NR)同时发生凝聚共沉,获得了NR/SiO2透明复合材料。用扫描电子显微镜和分光光度计分析了材料的结构,测定了硫化胶的力学性能。结果表明,SiO2的粒径随混合体系中Na2SiO3投料量的提高而增大,并均匀分布于NR基体中;当复合材料中SiO2用量为25～54份时,SiO2的粒径为100～200nm;在SiO2用量适宜的条件下,复合材料硫化胶具有良好的力学性能;硫化胶片具有一定的透明性,在波长为600～800nm时,其透光率为50%～72%。     

Mechanical properties and crosslink density of rare earth‐modified high‐abrasion furnace‐filled powdered natural rubber

High‐abrasion furnace‐filled powdered natural rubber [P(NR/HAF)] has more advantages than traditional HAF‐filled bale NR (NR/HAF) because of its better environmental performance and easier processing quality, but its lower mechanical properties are disadvantageous. To improve the mechanical properties, rare earth‐modified HAF‐filled powdered NR [P(NR/HAF‐Ln)] (Ln = Sm,La,Pr) was prepared by means of coacervation–coprecipitation, using rare earth‐modified HAF as separant and filler. The effect on mechanical properties of P(NR/HAF‐Ln) vulcanizate exerted by the emulsifier/HAF ratio, powdering temperature, Ln/HAF ratio and type of Ln, and HAF content were studied. The results indicated that when optimum formulation, the mechanical properties of P(NR/HAF‐Ln) vulcanizate were better than P(NR/HAF) vulcanizate. In addition, the relationship of the apparent crosslink density and HAF content of P(NR/HAF‐Ln), P(NR/HAF), NR/HAF vulcanizates was also investigated, along with their SEM microphotographs of tensile fracture surface, which indicated that the excellent mechanical properties of P(NR/HAF‐Ln) vulcanizate was attributed to correct amount of Ln that could increase crosslink density and reinforce the interface structure of NR matrix/HAF‐Ln particle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1755–1762, 2006     

Nano ZnO as cure activator and reinforcing filler in natural rubber

Zinc oxide (ZnO) nanoparticles of size 20–90 nm and surface area 9.56 m²/g were synthesized from ZnCl₂ and Chitosan and characterized by X‐ray diffraction, high resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM). Natural rubber (NR) vulcanizates containing nano ZnO was prepared by mill mixing and characterized by SEM, energy dispersive X‐ray analysis (EDAX), and HRTEM. Cure characteristics, free volume studies, bound rubber, crosslink density, and dynamic mechanical properties were evaluated and compared with that of NR vulcanizate containing conventional micro ZnO. Considering the cure characteristics, it was found that NR vulcanizate with 0.5 phr (parts per 100 g rubber) of nano ZnO showed low values of optimum cure time (t₉₀) and very high cure rate index compared with 5 phr of conventional micro ZnO. The study shows that micro ZnO can be successfully replaced with nano ZnO for accelerated sulfur vulcanization process in NR, and preparation of vulcanizate containing nano ZnO with better properties as that of micro ZnO. The optimum dosage of nano ZnO as a cure activator in NR vulcanization was found to be 0.5 phr compared with conventional grade micro ZnO. This will lead to substantial cost reduction in the manufacture of rubber products and alleviate environmental pollution due to excess ZnO in rubber compounds. POLYM. ENG. SCI., 2013 © 2013 Society of Plastics Engineers     

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。     

Preparation of zinc‐oxide‐free natural rubber nanocomposites using nanostructured magnesium oxide as cure activator

The effect of sol–gel synthesized magnesium oxide (MgO) nanoparticles as cure activator is studied for the first time in the vulcanization of natural rubber (NR) and compared with conventional zinc oxide (ZnO) in terms of cure, mechanical, and thermal properties. The NR vulcanizate with 1 phr (Parts per hundred parts of rubber) nano MgO shows an excellent improvement in the curing characteristics and the value of cure rate index is about 400% greater for NR vulcanizate containing 1 phr nano MgO in comparison to the NR vulcanizate with 5 phr conventional ZnO. Both mechanical and thermal properties of NR vulcanizate are found to be satisfactory in the presence of 1 phr nano MgO as cure activator in comparison to conventional NR vulcanizate. This study shows that only 1 phr nano MgO can successfully replace 5 phr conventional ZnO with better resulting properties in the sulfur vulcanization of NR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42705.     

原位生成甲基丙烯酸锌对填充天然橡胶力学性能的影响

考察了氧化锌用量和碳酸钙用量对原位生成甲基丙烯酸锌增强天然橡胶的力学性能的影响,以及甲基丙烯酸锌对白炭黑填充天然橡胶和胶粉填充天然橡胶力学性能的影响。研究表明,原位生成甲基丙烯酸钙的增强作用比甲基丙烯酸锌差,与前者的交联反应热很小有关;甲基丙烯酸锌能够大大加快白炭黑填充天然橡胶的硫化速度,对胶粉填充天然橡胶具有明显的增强作用。     

掺杂氧化钐的炭黑用量对粉末天然橡胶性能的影响

高耐磨炉黑(HAF)填充型粉末天然橡胶(NR)[P(NR/HAF)]硫化胶的缺点是300%定伸应力低,因此,采用Sm2O3掺杂HAF(HAF-Sm),用凝聚共沉法制备了掺杂Sm2O3的HAF填充型粉末天然橡胶(NR)[P(NR/HAF-Sm)],研究了其硫化胶的力学性能与Sm2O3及HAF用量之间的关系。结果表明:在炭黑用量为10~100份,当炭黑用量相同、Sm2O3的质量分数为HAF的3%时,其P(NR/HAF-Sm)硫化胶的300%定伸应力显著高于P(NR/HAF)硫化胶,而与块状NR(MNR)/HAF机械混炼胶料硫化胶的相近;其拉伸强度、100%定伸应力和撕裂强度明显高于P(NR/HAF)及MNR/HAF硫化胶。这说明适量的Sm2O3掺杂HAF可显著提高炭黑填充型粉末NR硫化胶的300%定伸应力及其他力学性能。     

纳米氧化锌母炼胶对NR性能的影响

将纳米氧化锌制成纳米氧化锌母炼胶，研究纳米氧化锌母炼胶对NR硫化胶物理性能的影响及纳米氧化锌的减量机理。试验结果表明，与加5份普通氧化锌相比，加2份纳米氧化锌母炼胶，硫化胶的拉伸强度提高，其它物理性能相近。透射电镜分析表明，纳米氧化锌母炼胶在NR胶料中不存在团聚现象，其分散性优于普通氧化锌和纳米氧化锌。在热力学理论分析基础上提出了纳米氧化锌在橡胶硫化过程中的作用机理。为纳米氧化锌减量60％替代普通氧化锌提供了理论依据。     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

SBR粘土纳米复合材料的气密性

对乳液法制备的SBR粘土纳米复合材料的气密性进行了研究,结果表明：SBR粘土纳米复合材料的气密性优于传统填料填充的硫化胶,且随温度的变化较小;填料的用量、形状以及与橡胶的结合性是影响气密性的主要因素;填充20份粘土的纳米复合材料气密性优于NR／SBR内胎,比IIR内胎差。