无机掺杂纳米粒子/天然乳胶纳米复合材料的制备及耐热老化性能研究

目前,有关纳米碳酸钙和纳米二氧化硅共同填充并协同增强天然乳胶(NRL)的研究鲜有报道。利用十二烷基三甲氧基硅烷(DDES)分别对纳米碳酸钙和纳米二氧化硅2种颗粒状无机纳米粒子进行表面改性,采用乳胶共混法制备改性无机纳米粒子/天然乳胶纳米复合材料,并对制备所得的复合材料进行不同时间的热氧老化。通过红外光谱(FTIR)、热重分析(TG)、接触角测定仪(CAMI)研究了改性前后纳米颗粒的结构和性能变化。采用橡胶加工分析仪(RPA)和扫描电镜(SEM)对天然乳胶复合材料的力学性能和微观结构进行了测试分析。结果表明:DDES的硅氧烷基团与颗粒状无机纳米粒子表面的羟基反应,在M-CaCO_3、M-SiO_2表面形成DDES接枝改性层,修饰后的纳米颗粒均匀地分散在天然乳胶中,并形成填料-乳胶交联网络结构;其中2种改性无机纳米粒子共同填充制备的CaCO_3/SiO_2/NRL样品性能较优,断面形貌均匀,储能模量(G')大;经70℃,480 h热氧老化后拉伸强度及撕裂强度保持率分别为81.45%、38.54%,表现出优异的耐热氧老化性能。     

硅烷偶联剂和马来酸酐对NBR/RHA复合涂层结构与性能的影响

以农业废弃物——谷壳灰(RHA)为填料,采用液态共混工艺(即将有机溶剂溶解的NBR生胶、改性谷壳灰和其他助剂混合形成混合胶液)制备了NBR/RHA复合涂层。用硅烷偶联剂Si69、KH550、KH560和马来酸酐(MAH)对谷壳灰进行改性,并研究了上述改性剂对谷壳灰分散性、结合胶以及NBR/RHA复合涂层结构和性能的影响。结果表明,在4种改性剂中,Si69的改性效果最好,经Si69改性后谷壳灰的分散性、谷壳灰与NBR相的界面作用,NBR/RHA复合涂层的力学性能、耐流体性能均最佳。     

稀土偶联剂REC对复合材料老化性能的影响

研究了用稀土偶联剂 (REC)处理的CaCO3、Mg (OH) 2 、BaSO4 与PP或ABS所形成复合体系的老化性能、力学性能及流动性。发现此偶联剂对这几种填料均有良好的改性作用 :力学性能显著提高 ,流动性明显改善。CaCO3、Mg (OH) 2 的加入对PP的光氧老化过程有加速作用 ,对热氧老化过程有不明显的阻滞作用 ;而BaSO4 则对ABS体系的光氧、热氧老化过程均有阻滞作用。新型偶联剂对各体系光氧老化过程有轻微的促进作用 ,而对热氧老化过程无明显影响 ,老化性能优于钛酸酯偶联剂     

甲基丙烯酸原位改性丁腈橡胶/谷壳灰复合发泡涂层

以农业废弃物谷壳灰(RHA)为填料,采用液态共混工艺,即将有机溶剂溶解的NBR生胶、谷壳灰和其他助剂混合形成混合胶液制备丁腈橡胶(NBR)/RHA复合发泡涂层,在混合胶液中添加甲基丙烯酸(MAA)对NBR/RHA复合发泡涂层进行原位改性。研究了MAA的用量对RHA分散性、RHA与NBR界面结合性、NBR/RHA复合发泡涂层泡孔形貌、力学性能、耐溶剂性能及热学性能的影响。结果表明,MAA作为界面改性剂,可改善RHA的分散性,增强RHA与NBR相的界面作用,改变NBR/RHA复合发泡涂层的泡孔形貌,对NBR/RHA复合发泡涂层具有补强效果。当MAA用量为10phr时,NBR/RHA复合发泡涂层的力学性能、耐流体性能、热学性能等较佳。     

四针状氧化锌晶须/天然橡胶抗菌医用复合材料的制备

将硬脂酸钠改性四针状氧化锌晶须(Sodium stearate-T-ZnOw)超声分散液引入天然胶乳(NRL)基体中,制备了绿色环保的Sodium stearate-T-ZnOw/橡胶(NR)抗菌医用复合材料。系统研究了Sodium stearate-T-ZnOw/NR复合材料的综合力学性能、抗菌性能和热稳定性能。结果表明:当Sodium stearate-T-ZnOw含量达3wt%时,Sodium sterate-T-ZnOw/NR复合材料的综合力学性能,相比纯胶,邵尔A硬度,300%定伸应力,拉伸强度,撕裂强度,断裂伸长率,提高了8.6%、25.4%、20.3%、25.6%、6.4%。此时,复合材料的热稳定性能也达到了最大值,相比纯胶,复合材料的起始热降解温度(T₀)和终止热降解温度(T_f)分别比纯胶的T₀和T_f提高了21.2℃和5.9℃。当Sodiumstearate-T-ZnOw含量超过3wt%时,其能在天然胶乳中充分发挥抑制大肠杆菌、金葡萄球菌、鲍曼不动杆菌、表皮葡萄球菌生长的能力,它可以进入细菌细胞,导致细胞壁被破坏,细胞内成分泄漏,细胞死亡。      

改性芳纶纤维/天然橡胶复合材料的制备及性能表征

采用傅里德-克拉夫茨反应原理在芳纶纤维表面接枝环氧氯丙烷,用偶联剂二次改性,研究表面接枝对芳纶纤维结构与性能的影响,并测试了改性芳纶纤维/炭黑/天然橡胶的力学性能。结果表明:改性后芳纶纤维表面的含氧量增加,偶联剂成功引入到芳纶表面,明显增加了芳纶的表面粗糙度和表面活性,降低了芳纶纤维的结晶度,但是对芳纶纤维晶体结构的影响不大,接枝环氧氯丙烷-偶联剂改性的芳纶纤维/炭黑/天然橡胶复合材料相比于未改性芳纶纤维/炭黑/天然橡胶复合材料力学性能有明显提高,橡胶加工流变性能分析表明芳纶纤维接枝环氧氯丙烷-偶联剂二次改性增大了复合材料的储能模量和损耗模量,减小了损耗因子从而改善了芳纶纤维与橡胶基体的界面结合强度。     

黄原酸酯基硅烷偶联剂的合成及在丁苯橡胶复合材料中的应用

采用相转移催化法制备了不同烷基链长的乙基黄原酸酯基丙基三乙氧基硅烷（EXS）和辛基黄原酸酯基丙基三乙氧基硅烷（OXS），利用2种黄原酸酯基硅烷偶联剂改性白炭黑并补强丁苯橡胶，研究了复合材料的加工性能、硫化性能、力学性能、耐磨性能、压缩生热、动态力学性能等，同时制备了双-[γ-(三乙氧基硅)丙基]四硫化物（Si-69）和封端型巯基硅烷偶联剂（NXT）改性的复合材料作为对比，探究了新型偶联剂取代NXT和Si-69在橡胶工业中应用的可行性。结果表明，长烷基链的OXS改性的复合材料门尼黏度最低，加工安全性高但硫化速度略慢；新型偶联剂改性的复合材料的力学性能、硬度和耐磨性都优于NXT改性的复合材料，同时滚动阻力较低；采用EXS改性的白炭黑在橡胶基体中的分散性较好，填料-橡胶间的相互作用较大。     

抗氧化剂对硫酸钙晶须/高密度聚乙烯复合材料性能的影响

高密度聚乙烯（HDPE）存在耐热老化性、耐候性不足和易变性等缺陷,为此通过共混挤出制备了偶联剂改性硫酸钙晶须（CSW）/HDPE复合材料,并添加抗氧化剂1010作用于力学性能较优异的复合体系。通过扫描电镜观察到添加1010可减少复合体系的表面裂纹;力学性能测试表明,抗氧化剂1010对复合体系的力学性能具有抗老化效果,氧化时间为40 d时,抗老化效果更佳,保有率差最高为6.41%;通过热失重分析和差示扫描量热分析研究复合体系的热性能和结晶性能,证实抗氧剂1010可有效抑制热氧老化对偶联剂改性CSW/HDPE复合材料的损耗程度,阻止复合体系前期的热降解,使热性能更稳定,并提高了复合体系的结晶度。     

RHA/NBR复合涂层的制备及结构与性能研究

以谷壳灰(RHA)为填料,采用液态共混工艺(即将已溶解的NBR生胶、改性谷壳灰和其他助剂在溶剂中混合形成混合胶液)制备了RHA/NBR复合涂层。用Si69对谷壳灰进行改性,考察了Si69含量对谷壳灰分散性、结合胶以及对RHA/NBR复合涂层的交联密度、微观形貌、耐流体性、热稳定性等多种性能的影响。结果表明:Si69含量对谷壳灰分散性、结合胶以及RHA/NBR复合涂层的结构和性能均有一定影响,且当Si69含量为20%时,谷壳灰的分散性、谷壳灰与NBR两相间相互作用,RHA/NBR复合涂层的耐流体性、热稳定性均较高。     

不同改性白炭黑增强天然橡胶复合材料的性能研究

采用不同硅烷偶联剂(Si69、KH560和NXT)对白炭黑进行改性处理来提高SiO_2/天然橡胶(SiO_2/NR)复合材料的性能。通过力学性能、结合胶含量、硫化性能和扫描电镜检测来分析不同改性白炭黑填充复合材料的影响。结果表明:白炭黑的改性处理改善了复合材料的强度、定伸应力等性能,提高了复合材料的结合胶含量;缩短了复合材料的硫化时间,降低了最小转矩,使混炼胶的流动性提高,减轻了填料网络结构;偶联剂的加入改善白炭黑与橡胶的相容性,使白炭黑分散均匀,从而提高了复合材料的性能。     

纳米介孔MCM-41-M/偶联剂体系对天然橡胶性能的影响

制备了天然橡胶(NR)/MCM-41-M、NR/偶联剂化学改性纳米介孔MCM-41-M、NR/MCM-41-M/偶联剂复合材料,研究了不同含量的MCM-41-M、不同种类偶联剂对MCM 41-M的改性以及偶联剂的添加方式对NR复合材料性能的影响.结果表明;MCM-41-M在NR中有明显的补强作用,当代替3份炭黑时NR基复合材料的拉伸强度达到最大值,比纯NR提高了12.7%。与MCM-41-M和KH-570直接添加到NR中相比,MCM-41-M经偶联剂KH-570改性使拉伸强度提高了50%。将MCM-41-M用偶联剂KH 570改性后添加到NR中,使NR的玻璃化转变温度升高、玻璃化转变区的损耗角减小、储能模量提高到最大。     

Incorporation of nano-sized mesoporous MCM-41 material used as fillers in natural rubber composite

The nano-sized mesoporous MCM-41 (without template), and the modification of MCM-41 (without template) were used to prepare natural rubber (NR) composites. The effects of coupling agents γ-aminopropyltriethoxysilane (KH-550), γ-methacryloxypropyltrimethoxysilane (KH-570), bis-(γ-triethoxysilylpropyl)-tetrasulfide (Si-69), isopropyl tri-(dioctylpyrophosphate)titanate (NDZ-201) on the mechanical properties of the composites were also investigated. The results showed that the tensile properties of Natural rubber/mesoporous MCM-41 nanocomposite were improved as compared with those of NR compound. KH-570 had good effect on enhancing the overall properties of the composites. Scanning electron microscopy (SEM) observations revealed that the modified nano-sized MCM-41 material was well dispersed in the polymer matrix and the enhancement of the interface between the matrix and fillers was obtained.     

碱式硫酸镁晶须/橡胶复合材料的制备

将超声分散后的硅烷偶联剂3-氨丙基三乙氧基硅烷改性碱式硫酸镁晶须（KH550-MgOS_W）分散液加入天然胶乳（NR）中,对其进行补强,制得绿色环保高性能的KH550-MgOS_W/NR复合材料。系统研究了KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能。结果表明,用KH550改性后的MgOS_W与橡胶基体具有很好的相容性。KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能均比纯胶有所提高。当KH550-MgOS_W与NR质量比为4%时,KH550-MgOS_W/NR复合材料的各项性能均达到最佳,300%定伸应力、拉伸强度、撕裂强度、断裂伸长率、交联密度比纯胶胶膜分别提高了25.0%、36.8%、37.3%、11.4%、44.2%,垂直燃烧等级由FV-1提高到了FV-0级,比纯胶的起始热降解温度（T₀）、最大热降解温度（T_p）和终止热降解温度（T_f）分别提高了6.2℃、5.2℃和4.1℃。     

纤维表面处理与基体改性对连续玻纤增强聚丙烯力学性能的影响

考察了连续玻纤的表面处理、基体的接枝改性及接枝单体的种类和接枝产物的加入量对连续玻纤毡增强聚丙烯(CGFRPP) 力学性能的影响, 并通过红外光谱、扫描电镜对CGFRPP 的界面化学作用及界面粘结进行了研究。结果表明, 马来酸酐接枝改性聚丙烯与未经偶联剂处理的玻纤不能形成有效的化学结合, 而与经硅烷偶联剂表面处理的玻纤可发生明显的化学作用, 形成良好粘结, 显著提高CGFRPP 的力学性能; 硅烷偶联剂的种类对以改性PP 为基体的CGFRPP 力学性能的影响不大; 马来酸酐接枝聚丙烯比丙烯酸接枝聚丙烯对CGFRPP 力学性能的改善更为有效。      

Tribological Properties of A356.2/RHA Composites

Rice husk ash (RHA) is one of the industrial waste byproduct available abundantly in the world. In the present work, an attempt is made to incorporate the RHA particles in the molten aluminum A356.2 alloy. The RHA particles were added into the matrix melt by creating a vortex with the help of a mechanical stirrer and the melt temperature was maintained between 800 and 850 C. Dry sliding wear experiments were performed in a pin on disc wear equipment against a chromium steel disc at 30 C. Scanning electron microscopy is used to study the wear characteristics of the unreinforced Al alloy and the A356.2/RHA composites. From the experiments it is observed that the composites exhibit higher hardness and resistance to wear as compared to unreinforced Al alloy.     

Effects of industrial scale production on the chemical composition of novel coupling agents and its relationship to the mechanical properties of chopped glass fibre mat reinforced thermoset composites

Previously successfully applied polyalkenyl-poly(maleic-anhydride)-ester/amide type additives synthesized in laboratory scale have gone through selection steps then the selected coupling additives were produced in industrial scale process. Additives have been applied for treating the surfaces of glass fibres with and then mechanical properties of the laminated polyester and vinyl–ester based composites have been determined. Results have been focussed on the effect of the size increasing of additive production on the final properties of the laminates. The structures of the additives have been compared based on their FT-IR spectra. Improvement of mechanical properties of composites treated by coupling additives has been found manufactured in industrial scale either. Tensile properties could be improved by 3.2–51.3% with additives from industrial scale related to the same properties of untreated laminates. The Charpy impact strength of laminates treated with coupling agents from industrial scale was higher than that of from lab scale. Fibre–matrix interaction has been studied on SEM micrographs of the fractured faces of the composites. Similarly, the unfavourable results had been caused by the fibres slipping out of the ester matrix.     

高岭土/白炭黑并用填充天然橡胶复合材料的性能

以高岭土和白炭黑作为增强剂,采用熔融共混法制备了一系列的天然橡胶(NR)复合材料,并对其微观结构、气体阻隔性能和力学性能进行了表征.结果表明,改性高岭土(MK)以片层结构,白炭黑(PS)以球状结构,均匀分散于NR基体之中;MK与PS单独填充NR时,随着MK填充量的增加,NR复合材料的气体阻隔性能逐渐提高,而且MK的增强...     

改性白炭黑/天然橡胶复合材料的制备及性能

采用双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙基三甲氧基硅烷(11-100)对白炭黑进行表面改性,并制备改性白炭黑/天然橡胶复合材料。利用红外光谱(FT-IR)、热重分析(TG)、扫描电镜、橡胶加工分析仪等测试手段对改性白炭黑及改性SiO_2/NR复合材料的结构与性能进行了表征,并研究其硫化性能及力学性能。结果表明,经FT-IR、TG分析,3种硅烷偶联剂已成功接枝到白炭黑表面;改性SiO_2/NR复合材料相对于未改性SiO_2/NR,焦烧时间变长,正硫化时间缩短,结合胶含量增大;改性SiO_2/NR与未改性SiO_2/NR相比其定伸应力、撕裂强度明显提高,但断裂伸长率有所减小;改性白炭黑在天然橡胶基体中的分散性明显提高,其中Si69-SiO_2在天然橡胶基体中的分散性最好;Si69-SiO_2/NR复合材料的滚动阻力与生热最低;改性后的SiO_2/NR复合材料的拉伸断面粗糙程度增加。     

Effect of coupling agents on the crystallinity and viscoelastic properties of composites of rice hull ash-filled polypropylene

This paper focuses on the application of silica rich, rice hull ash (RHA) from the rice industry as filler in polypropylene (PP). The dynamic rheological behaviour and the crystallinity of its composites with semi-amorphous polypropylene were used as performance indicators. The effect of coupling agents on RHA/PP compatibility was also investigated. Addition of RHA increased storage modulus (G′), and the onset (T _co) and peak (T _c) crystallinity temperatures, and decreased the degree of crystallinity of the system. Two coupling agents, maleated polypropylene (MAPP) and an amino functional silane, were used to improve the interfacial adhesion of RHA and PP. Addition of MAPP increased G′, T _c and T _co and the crystalline phase of the system. Addition of silane had mixed effects. It increased the rheological properties at higher concentrations, it increased T _c and T _co at all the concentrations and increased crystallinity at lower concentrations and decreased it at higher concentrations. Results from a thermogravimetric analyser were useful in revealing the mechanism by which silane bond to RHA and its effect on the rheology and crystallisation behaviour of the composites.     

不同维数填料对橡胶Payne效应的影响

在变外力作用下,填充橡胶的动态模量会随着应变的增加而急剧下降的现象称为Payne效应。研究填充橡胶的Payne效应可以保证橡胶制品在使用过程中的安全性和可靠性,同时获得具有良好力学性能的橡胶制品。文中通过胶乳-双辊连用法制备了炭黑/天然橡胶复合材料(RCB)、碳纳米管/天然橡胶复合材料(RCNT)和石墨烯/天然橡胶复合材料(RGE)。扫描电镜和透射电镜图像显示,该方法可以将填料均匀分散在橡胶基体中。Mooney-Rivlin曲线和动态力学性能测试显示RGE复合材料的Payne效应最强,RCB复合材料的Payne效应最弱。