Lignocellulosic fibre mediated rubber composites: An overview

The rising concern towards the reduction in the use of petroleum-based, non-renewable resources and the need for more versatile polymer-based composite materials have led to increasing interests on natural polymer composites filled with natural organic fillers, i.e. coming from renewable and biodegradable sources. This paper reviews wood flour and other lignocellulosic fibres filled rubber composites, including cellulosic rubber composites, cellulosic thermoplastic elastomers, nanocellulose based rubber nanocomposites, with the aims at providing the most state of the art information for directing further scientific research, possible commercialization and design of cellulosic rubber composites. It has been found that 1) the surface properties of natural cellulose, hence the compatibility and interface of the natural cellulose and matrix rubber/plastics, are crucial for the successful development of the composites, such, physical and chemical modification and additives have been widely attempted to improve the incompatibility and poor interfacial adhesion between the filler and matrix; 2) the curing characteristics, mechanical properties, thermal stability and morphologies of the composites are complex but closely related to not only the interfacial properties, but also the compositions (e.g. the concentration of cellulosic materials) and other processing parameters; 3) the nature of hydrophilic cellulosic and hydrophobic matrix rubber and/or plastics requires an accurate introduction of coupling agent, one end of its structure shall be compatible to hydrophilic and the other to hydrophobic. The reviews on the main paths and results of study on the advanced nanocellulose reinforced rubber nanocomposites and sandwiches indicate much potentials and needs for further in-depth studies.     

经编间隔织物增强柔性复合材料冲击性能

针对传统个体防护材料刚硬、限制人体活动的缺点,设计了2种柔性复合材料: 剪切增稠液(STF)和硅橡胶填充经编间隔织物(WKSF)柔性复合材料,并对其冲击性能进行研究。WKSF具有上、下两个表层和间隔丝构成的间隔层,在其间隔层中加入STF和硅橡胶2种柔性材料。STF采用将纳米SiO₂分散于聚乙二醇(PEG)中制成,硅橡胶采用硅胶和固化剂混合而成。采用流变仪对STF的流变性能进行测试,采用Instron落锤冲击仪对WKSF及其复合材料的冲击性能进行测试。实验表明: STF在达到临界剪切速率后出现剪切增稠现象,纯织物的冲击过程可分为弹性、平台和压实3个阶段,且具有明显的平台阶段;经填充后所制成的2种复合材料的冲击过程与纯织物明显不同,其载荷-位移曲线呈线性;加入硅橡胶的复合材料刚度较大,没有应变率效应;加入STF的复合材料具有较好的能量吸收性能和明显的应变率效应。     

原位红外技术研究天然橡胶/粘土复合材料热降解产物

将粘土经还原剂及酸处理,再与天然胶乳共沉制备粘土胶复合材料, 用带原位样品池的傅立叶变换红外光谱仪动态研究粘土胶复合材料在不同温度下热降解气相产物。在低分解温度下,粘土胶分解产物主要是乙烯、低分子烯烃类及含羰基化合物;随分解温度升高,则低分子烯烃含量减少,较长链烯类生成,并同时产生大量烷烃类分解产物。随着粘土中Cu,Mn,Co,Fe等金属组分含量升高,粘土胶分解产物中含羰基氧化产物、烯烃及CO₂含量增加,说明金属组分对粘土胶降解氧化产生促进作用。     

Improvement of impact property of natural fiber–polypropylene composite by using natural rubber and EPDM rubber

In this research, vetiver grass was used as a filler in polypropylene (PP) composite. Chemical treatment was done to modify fiber surface. Natural rubber (NR) and Ethylene Propylene Diene Monomer (EPDM) rubber at various contents were used as an impact modifier for the composites. The composites were prepared by using an injection molding. Rheological, morphological and mechanical properties of PP and PP composites with and without NR or EPDM were studied. Adding NR or EPDM to PP composites, a significant increase in the impact strength and elongation at break is observed in the PP composite with rubber content more than 20% by weight. However, the tensile strength and Young’s modulus of the PP composites decrease with increasing rubber contents. Nevertheless, the tensile strength and Young’s modulus of the composites with rubber contents up to 10% are still higher than those of PP. Moreover, comparisons between NR and EPDM rubber on the mechanical properties of the PP composites were elucidated. The PP composites with EPDM rubber show slightly higher tensile strength and impact strength than the PP composites with NR.     

A discussion of the paper “Physico-mechanical properties of aerated cement composites containing shredded rubber waste” by A. Benazzouk,O. Douzane,K. Mezreb and M. Quéneudec

This discussion focuses on the composite behavior, utilization of waste rubber and examination of the test results. In experimental studies, six cement–rubber composite (CRC) and six aerated cement–rubber composite (ACRC) specimen were prepared, respectively to investigate the physico-mechanical properties of cement–rubber composites.     

周期载荷下聚酯/橡胶复合材料和人造丝/橡胶复合材料的热生成对疲劳行为的影响

以单向帘线增强橡胶复合材料为研究对象,研究了周期载荷作用下橡胶复合材料的热生成对疲劳行为的影响。橡胶复合材料在疲劳过程中伴随较多的热生成,SEM观察表明:热生成温度与断裂表面密切联系。橡胶复合材料的滞后损失并不是全部转换为热,而是其中一部分被内能变化所消耗,不转换为有效热生成的滞后损失与疲劳损伤导致的结构变化有关。在疲劳试验中,直到疲劳破坏所消耗的平均有效能耗与疲劳寿命之间存在定量关系。     

单向帘线增强橡胶复合材料在周期载荷下的动态粘弹性

研究了橡胶复合材料的疲劳行为，发现：橡胶复合材料在疲劳过程中具有明显的非线性粘弹性，材料的动态粘弹性在疲劳初期和末期表现出不同的趋势，与其他脆性复合材料不同，橡胶复合材料在疲劳过程中伴有较高的热生成，橡胶复合材料的滞后损失愈大，实际热生成温度愈高，其疲劳寿命降低愈明显。     

环保型水切割胶粉对天然橡胶力学性能和动态性能的影响

采用环保型水切割胶粉及力化学改性胶粉（MRP）与天然橡胶（NR）复合制备胶粉-NR复合胶,并探讨了胶粉用量对复合胶力学性能和动态性能的影响。通过红外和热失重分析确定了胶粉的主要成分为NR和丁苯橡胶（SBR）,且改性后胶粉大分子链结构未发生明显变化。通过橡胶加工分析仪研究了胶粉用量及改性对复合胶加工性能的影响。采用炭黑分散仪研究并观察了胶粉在NR中的分散情况。结果表明,胶粉改性后与NR的相容性提高,二者界面结合力增大,MRP-NR复合胶加工性能改善。炭黑分散结果表明,胶粉用量越多,其分散性越差,改性后胶粉的分散性提高,MRP-NR复合胶的力学性能最优,拉伸强度为27.9 MPa。     

导电炭黑填充硅橡胶的电阻温度系数

以炭黑(CB3100)为导电相,硅橡胶为基质制备导电复合材料。研究导电橡胶中炭黑质量分数对电阻温度系数的影响,并用填料对电阻温度系数的影响。以隧道效应理论为基础,给出了导电炭黑填充橡胶的电阻温度系数计算模型,结合实验得到温度对导电炭黑/硅橡胶电阻温度系数的影响主要体现在对其电阻率的影响;基体的体积热膨胀提高复合材料的电阻率,提高了正电阻温度系数;炭黑粒子间的隧道效应降低复合材料的电阻率,增强了负电阻温度系数;在炭黑/硅橡胶中加入少量碳纳米管,利用碳纳米管和炭黑的协同补强效应,使复合材料的导电性和稳定性提高。     

丁腈橡胶/导电粒子复合材料的正温度系数(PTC)特性

将导电粒子碳黑和铜粉分别与丁腈橡胶混合制备导电聚合物复合材料，其中碳黑（Ｎ５５０）／丁腈橡胶复合材料的电阻率随温度的变化呈现较强的正温度系数（ＰＴＣ）效应。讨论了掺入导电粒子浓度、结构和表面性质以及混炼硫化工艺等对该类材料的室温电阻率及ＰＴＣ效应的影响。     

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。     

透明LED石墨烯/苯基硅橡胶复合封装材料

采用化学接枝技术,利用硅烷偶联剂γ-氨丙基三乙氧基硅烷（KH-550）、水合肼改性氧化石墨烯（GO）制备功能型石墨烯（FG）。将FG与苯基硅橡胶混合,采用氢化硅烷化法,在铂催化剂作用下制备了一种发光二极管（LED）封装用FG/苯基硅橡胶复合材料,考察了改性后FG结构、表面官能团变化以及其用量对FG/苯基硅橡胶复合材料力学性能及光学性能的影响,并分析了FG/苯基硅橡胶复合材料的微观相态及其热稳定性。结果表明:经KH-550改性后的FG表面附有特殊官能团,能提高其在苯基硅橡胶中的分散性。当苯基硅橡胶中引入0.010 0wt% FG时,FG/苯基硅橡胶复合封装材料的透光率仍可达到85%以上,耐紫外老化性能和力学性有明显提高。FG/苯基硅橡胶复合材料的热分解温度为690 ℃、GO/苯基硅橡胶复合材料的热分解温度为623 ℃,而纯苯基硅橡胶的热分解温度为491 ℃,且FG/苯基硅橡胶复合材料的放热量始终比纯苯基硅橡胶略低。苯基硅橡胶中引入0.010 0wt% 改性的FG,材料热分解温度提高了200 ℃,放热量有所减少,能更好满足功能型LED复合封装材料热稳定性能要求。      

Partial replacement of silica with microcrystalline cellulose in rubber composites

Microcrystalline cellulose (MCC) was investigated to partially replace silica in rubber composites. The partial replacement of silica with MCC significantly reduced the energy required for dispersion of fillers in rubber matrix and lowered the internal temperature during the compounding. Moreover, the partial replacement of silica with MCC reduced Mooney viscosity, apparent shear stress, and apparent shear viscosity of the rubber composites, which facilitated the manufacturing process of the rubber composites. The replacement of up to 18% silica with MCC did not negatively affect the mechanical properties of the unaged and aged rubber composites. The partial replacement of silica with MCC also improved the heat resistance, did not significantly change the tan δ of rubber composites containing up to 11.8% of MCC at low temperature and decreased the tan δ of all rubber composites at high temperature. However, addition of MCC slightly decreased tear strength and hot tear strength of the rubber composites.     

双马来酰亚胺树脂增韧及用作先进复合材料基体的发展

本文综述了耐热耐湿和加工性优良的双马来酰亚胺(BMI)型先进复合材料(ACM)树脂基体改性的近年发展。着重介绍了BMI通过与烯丙基苯基化合物共聚,与芳香二胺的链延长和合成新型链延长BMI,与热塑性树脂共混等获得增韧的方法及若干树脂体系、牌号和性能,表明BMI的增韧改性对被着重发展为ACM的热固性树脂基体的技术关键性。      

玄武岩短纤维-芳纶浆粕/氯丁橡胶复合材料的制备与性能

以氯丁橡胶（CR）为基体,改性玄武岩短纤维（BSF）和芳纶浆粕（AP）作为增强相,制备了高强度、高模量的BSF-AP/CR复合材料,系统地研究了BSF和AP对BSF-AP/CR复合材料基本物理性能、动态力学性能和动刚度的影响。采用超声波辅助γ-氨丙基三乙氧基硅烷（KH550）对BSF进行了改性,通过FTIR测试显示KH550与BSF表面基团发生了反应。通过SEM观察发现,改性BSF与CR界面相容性较好,易于分散和取向,而AP锚固在CR基体中,取向度不如BSF高;随着BSF与AP质量比值减小,BSF-AP/CR复合材料的拉伸强度、拉断伸长率和屈挠性能降低,耐撕裂性能和耐磨性能变好。采用弹性体材料测试系统（MTS）测试复合材料的动刚度。结果表明,BSF与AP质量比越小,BSF-AP/CR复合材料的动刚度越大,说明AP对BSF-AP/CR复合材料动刚度贡献大。动态力学性能显示,AP用量越多,BSF-AP/CR复合材料的储能模量（G'）越高,Payne效应越明显,而阻尼因子越小,说明AP有良好的模量-滞后平衡效应。当BSF与AP质量比为10:10时,BSF-AP/CR复合材料的综合性能较好。      

单向聚酯帘线增强橡胶材料疲劳特性研究

利用自行建立的试验系统, 首次对单向聚酯帘线增强橡胶材料进行了疲劳测试, 研究了应变、频率和温度对疲劳损伤累积的影响, 并给出了疲劳寿命预报方程, 为评价轮胎的疲劳特性、预报轮胎的疲劳寿命提供了有效的手段。      

碳纳米管/天然橡胶复合材料的制备及性能

对碳纳米管/天然橡胶复合材料的制备工艺和材料性能进行了研究。碳纳米管与天然橡胶复合后,橡胶DSC曲线中结晶熔融峰变小,硫化返原现象减轻,焦烧时间略有缩短。经过分散-粘合体系处理,碳纳米管在橡胶中的分散程度及界面粘合状况改善,复合材料的整体力学性能提高,与炭黑增强样品相比,碳纳米管复合材料在回弹及动态压缩性能方面占有优势,动态模量和玻璃化转变温度高,热降解稳定性较好。      

废橡胶胶粉/HDPE/POE热塑性弹性体的动态硫化

以过氧化二异丙苯(DCP)为硫化剂,研究了废橡胶胶粉／高密度聚乙烯(HDPE)／乙烯-辛烯共聚物(POE)(50/25/25)热塑性弹性体的动态硫化．考察了过氧化二异丙苯(DCP)用量对该共混物力学性能的影响．结果表明,加入DCP后,废橡胶胶粉／HDPE／POE共混物的交联度增加。动态硫化提高了共混物的力学性能,DCP用量为0．5份时．共混物具有最大的拉伸强度(8．01MPa)和断裂伸长率(225％)．扫描电镜观察结果表明,动态硫化后共混物的界面结合更加紧密．有利于力学性能的提高。废橡胶胶粉／HDPE／POE热塑性弹性体具有良好的耐老化性和再加工性．可以循环使用。     

碳纳米管/天然橡胶复合材料的红外光谱和DSC分析

将催化裂解法制得的碳纳米管进行氢氟酸和混酸处理后，碳纳米管的纯度和团聚程度增大，热处理后碳纳米管的聚集情况略有改善。碳纳米管表面官能团与橡胶分子间可以形成氢键，并对天然橡胶的分子运动产生影响，随着碳纳米管的进一步处理，混炼胶的Tg有所升高，DSC曲线中的结晶熔融峰面积减小，热处理后碳纳米管填充胶料的Tg略有下降，结晶熔融峰面积增大。氢氟酸处理碳纳米管填充天然橡胶材料的力学性能较好。     

Styrene-butadiene rubber/halloysite nanotubes composites modified by epoxidized natural rubber

The reinforcement effects of halloysite nanotubes on styrene-butadiene rubber and the modification effect of epoxidized natural rubber on styrene-butadiene rubber/halloysite nanotubes composites were studied. The structure, morphology and properties of styrene-butadiene rubber/halloysite nanotubes composites before and after the incorporation of epoxidized natural rubber were investigated. The results indicated that epoxidized natural rubber can promote the dispersion and orientation of halloysite nanotubes in styrene-butadiene rubber matrix at nanoscale and strengthen interfacial combination between halloysite nanotubes and styrene-butadiene rubber by the formation of covalent bonds and hydrogen bonds between epoxidized natural rubber and halloysite nanotubes. Consequently epoxidized natural rubber can improve the mechanical properties of the vulcanizates of styrene-butadiene rubber/halloysite nanotubes composites. Besides epoxidized natural rubber can decrease the rolling resistance of the vulcanizates and increase the wet grip property of the vulcanizates.