橡胶纳米复合材料研究进展

对蒙脱土的结构、纳米材料的制备及橡胶纳米复合材料的一些特性作了简要介绍。分析了橡胶增强中几个主要因素的作用和地位,认为粒径是橡胶增强的第一要素,粒径因素包括部分表面活性因素和结构性因素,纳米增强是橡胶高效增强的必要条件,并指出炭黑和白炭黑增强橡胶属于纳米复合材料范畴。以橡胶纳米复合材料的制备方法(主要有：插层复合法、溶胶～凝胶法、原位分散法、和纳米直接共混法)为线索综述了橡胶基纳米复合材料的研究进展,分析了各种方法的优缺点及对其应用前景进行了展望。     

橡胶纳米复合材料研究进展

橡胶纳米复合材料因其优异的性能而目前材料科学研究的热点。本文论述了橡胶／粘土、橡胶／纳米SiO2、氢化NBR／丙烯酸金属盐、橡胶／纳米炭黑和白炭黑、橡胶／纳米纤维等橡胶基纳米复合材料的制备方法、机理、力学性能、工业应用领域等,讨论了层状硅酸盐粘土的表面修饰,提出了插层剂的选择原则,评价了各种合成技术的优缺点及工业价值,提出了橡胶纳米复合材料的发展趋势。     

橡胶纳米复合材料研究进展

综述了国内外炭黑／橡胶、白炭黑／橡胶和黏土／橡胶三大类橡胶纳米复合材料的研究进展，对材料的性能特点和制备技术的优缺点进行了总结。     

黏土/SBR纳米复合材料的加工性能

采用橡胶加工分析仪(RPA)和孟山都毛细管流变仪研究了黏土／SBR纳米复合材料的Payne效应和流变性能。并同炭黑(N330)与微米级黏土橡胶复合材料进行了对比。结果表明，黏土／SBR纳米复合材料的流变规律与传统填充体系的流变规律类似，其弹性模量均随着填料用量的增加而增大，填料之间形成拟网络结构，在加工过程中，具有Payne效应；纳米分散的黏土具有更大的宽厚比和各向异性，对橡胶分子链限制作用更强。网构化程度更高，在相同的应变和频率下，与炭黑和黏土直接混炼填充SBR体系相比，黏土／SBR纳米复合材料的弹性模量更高；纳米化程度越高，网构化程度也越高；在相同的毛细管剪切速率下，黏土／SBR纳米复合胶料的黏度略高于炭黑体系；在黏土／SBR纳米复合胶料中，加入界面剂改善界面强度和改进工艺增加增强单元数目，胶料弹性模量提高；黏土／SBR纳米复合胶料具有出口膨胀小．吃粉快。挺性好的良好加工性能。     

黏土/天然橡胶纳米复合材料的制备及性能

利用乳液插层法制备了黏土／天然橡胶纳米复合材料，研究了该复合材料的力学性能、应力应变行为、耐磨性、气体阻隔性和耐老化性能。结果表明，黏土／天然橡胶纳米复合材料与高耐磨炭黑(N330)、白炭黑增强橡胶相比，邵尔A型硬度、定伸应力和撕裂强度较高，拉伸强度相当。黏土、N330以及白炭黑对天然橡胶的拉伸结晶有影响，填料用量对材料拉伸强度的影响存在最佳值。黏土／天然橡胶纳米复合材料具有良好的耐磨性、气体阻隔性和耐老化性能。     

湿法/干法共混制备石墨烯/炭黑/丁腈橡胶纳米复 合材料

采用湿法/干法两步共混的方法制备了石墨烯/炭黑/丁腈橡胶纳米复合材料。将二维纳米片层状石墨烯与炭黑形成共增强体系,提高丁腈橡胶的力学性能及耐磨性。选用质量比分别为1/39、2/38、3/37、4/36和5/35石墨烯/炭黑对丁腈橡胶进行增强,采用橡胶加工分析仪研究了复合材料的动态力学性能。结果表明,石墨烯和炭黑与橡胶基体之间形成二次网络结构,使得橡胶的储能模量呈增加趋势。当石墨烯/炭黑的质量比为4/36时,储能模量显著提高,拉伸强度为26.59 MPa,Arkon耐磨指数达到319.1%,综合性能优异,增强效果最佳。     

粘土/炭黑/NR纳米复合材料的性能研究

在乳液插层法制备的粘土／NR纳米复合材料中加入炭黑，制得粘土／炭黑／NR纳米复合材料，并对其微观结构和性能进行研究。结果表明，炭黑的加入并没有影响粘土在NR基体中的分散状态，粘士炭黑和在NR基体中均达到纳米级分散；炭黑的加入削弱了粘土所形成填料网络的强度，从而改善了复合材料的加工性能；与粘土／NR纳米复合材料相比，粘土／炭黑／NR纳米复合材料的综合物理性能较好。     

粘土/橡胶纳米复合材料老化性能研究

研究粘土 /SBR及粘土 /NR纳米复合材料的耐热氧老化和耐臭氧老化性能 ,并考察粘土 /SBR纳米复合材料的热失重和气体阻隔性。结果表明 ,粘土 /SBR纳米复合材料的耐热氧老化和耐臭氧老化性能均优于炭黑 /SBR复合材料 ;粘土 /NR纳米复合材料的耐热氧老化性能略优于炭黑 /NR复合材料 ,耐臭氧老化性能与炭黑 /NR复合材料相差不大 ;均匀分散的纳米粘土可提高橡胶的热稳定性和气体阻隔性 ,减缓氧及臭氧在橡胶中的扩散 ,降低橡胶分子链受攻击的几率 ,有利于提高橡胶耐热氧老化和耐臭氧老化性能     

环氧树脂纳米复合材料研究进展

综述了近年来国内外制备纳米SiO2/环氧树脂、纳米TiO2／环氧树脂以及纳米Al2O3/环氧树脂复合材料的研究现状。纳米粒子粒径小,表面能大,容易发生团聚,成为影响复合材料性能的关键。纳米粒子的粒径大小、几何形状等形态参数和添加量对纳米复合材料性能的影响程度。以及纳米复合材料的相界面结构和增韧增强机理都是亟待解决和完善的研究热点。     

纳米碳酸钙/炭黑并用对丁苯橡胶性能的影响

研究了纳米碳酸钙／N330炭黑并用比对丁苯橡胶性能的影响。结果表明，随着CaCO3／N330并用比的改变，材料的强度有了显著的提高，特别是CaCOa／N330并用比为20／30(质量份)时复合材料的拉伸强度达到了20MPa以上，同时材料具有较好的弹性和较低的硬度；两种处理剂相比，树脂酸处理的碳酸钙具有较好的性能；表面处理的纳米炭酸钙与炭黑并用，可以降低炭黑填充橡胶的动态滞后，表面处理的纳米碳酸钙的加工性能比纳米炭黑好，可以通过并用纳米碳酸钙来改善炭黑胶料的加工性能。     

淀粉功能化改性及在补强橡胶中的研究进展

淀粉作为补强填料替代部分炭黑或白炭黑可以改善橡胶轮胎的抗湿滑性和滚动阻力,且淀粉来源广,成本低,无污染,有望成为新型橡胶补强填料。但淀粉极性强,与橡胶相容性差,直接使用无法起到补强效果。本文综述了淀粉细微化、酯化改性、接枝改性、原位改性这四种改性淀粉的方法。这些方法通过减小淀粉颗粒尺寸和引入其他分子链或基团等途径,改善淀粉在橡胶中的分散性及其与橡胶的相容性,使淀粉能够成为橡胶轮胎的优质补强填料。     

Contribution of physico-chemical properties of interfaces on dispersibility, adhesion and flocculation of filler particles in rubber

Reinforcing fillers are added to elastomeric compounds to improve and adjust several mechanical, dynamical, tribological, etc. properties with respect to different applications, i.e. for automotive tires, or technical rubber goods. Carbon black and precipitated silica are widely used as rubber reinforcing fillers; however, some new classes of nanosized substances like organophilic modified clay or carbon nanotubes are presently intensive studied as possible future filler systems in combination with carbon black or silica.An important parameter for the dispersibility and compatibility of the filler in the polymer matrix of rubber compounds is the surface energy and surface polarity of the solid filler particles. Therefore, we systematically measured and compared the dynamic contact angles of a collection of different filler types (carbon blacks, silica, carbon nanotubes and organoclays) using the Wilhelmy method, whereby the particles were fixed as a thin layer at a double-sided adhesive tape. From the contact angle values the polar and disperse part of the surface energies of the filler particles were calculated by fitting Fowkes formula. For an estimation of the compatibility of the fillers with different types of rubber polymers we additionally analyzed the surface energy and polarity of the gum (unfilled) elastomers. From the evaluated surface energies and polarities, thermodynamic predictors for the dispersibility (enthalpy of immersion), the adhesion between filler particles and polymer matrix in the nanocomposite, and for the flocculation behaviour of the particles in a rubber matrix (difference in the works of adhesion) were derived. These thermodynamic predictors improve considerably the compounding process of novel rubber nanocomposites with respect to target-oriented adjustment of rubber properties.     

聚苯胺改性蒙脱土/天然橡胶纳米复合材料的制备与性能

采用原位聚合法制备了聚苯胺质量分数为20%的聚苯胺改性蒙脱土,并以此作为增强剂利用机械混炼法制备了聚苯胺改性蒙脱土(PANI-MMT)/天然橡胶(NR)纳米复合材料。使用X射线衍射仪、傅里叶变换红外光谱仪及扫描电镜等对PANI-MMT和PANI-MMT/NR复合材料的结构进行了表征,并考察了PANI-MMT/NR复合材料的力学性能。结果表明,PANI-MMT/NR复合材料形成了插层型纳米结构;与普通的有机蒙脱土/NR复合材料相比,PANI-MMT/NR复合材料的力学性能明显提高,PANI-MMT添加质量为20份时其力学性能达到最好,并超过了添加40份炭黑N 660的NR的力学性能。     

Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2'-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles, and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites, followed by HF etching. Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated. N₂ adsorption-desorption, scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials. Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles. The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm. The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%. The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.     

用溶胶—凝胶法原位生成SiO2增强橡胶

介绍了用溶胶－产法原位生成ＳｉＯ２纳米粒子增强橡胶的技术,以及该技术的３种不同方法：（１）在硫化胶中生成原位ＳｉＯ２;（２）在非硫化胶中生成原位ＳｉＯ２;（３）在硫化反应中生成原位ＳｉＯ２。同时对溶胶－凝胶技术的反应原理和影响因素作的探讨。总结了原位ＳｉＯ２增强橡胶复合材料的结构特征（粒径及其分布、分散性、界面状态）主由此导致的物理机械性能。分析了这种技术的优缺点及其在橡胶工业中的应用前景。     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Vulcanization accelerator functionalized nanosilica: Effect on the reinforcement behavior of SSBR/BR

The application of nanosilica in high performance tire highly depends on its uniform dispersion in rubber matrix. A series of dispersible nanosilica (denoted as DNS) modified by diphenyl guanidine (denoted as DPG, a vulcanization accelerator) were synthesized by liquid phase in situ surface chemical modification. The structure of the as‐obtained DNS‐DPG fillers was investigated in relation to Fourier transform infrared spectrometric analysis, thermogravimetric analysis, dynamic light scattering test, and transmission electron microscopic observation. It was found that the rubber vulcanization accelerator DPG was successfully grafted onto the surface of nanosilica, thereby effectively preventing the silica nanoparticles from agglomeration and significantly reducing the average particle size. The reinforcing effect of the DPG‐modified DNS nano‐fillers for the solution polymerized styrene butadiene rubber/butadiene rubber (denoted as SSBR/BR) was dependent on the fraction of the modifier DPG; in particular, when the amount of modifier DPG is 135.25 mmol/kg (denoted as DNS‐DPG‐3), silica exhibited very homogeneous dispersion in the SSBR/BR matrix, which contributed to significantly enhancing the filler‐rubber compatibility. As a result, SSBR/BR/DNS‐DPG‐3 nanocomposite exhibited the best mechanical properties, integrated high abrasion resistance and low rolling resistance. The modified silica not only possessed the effect of accelerating the crosslinking reaction, but also showed the reinforcing effect. This could make it feasible for SSBR/BR/DNS‐DPG nanocomposite to find promising application in green tire tread. POLYM. ENG. SCI., 59:1270–1278 2019. © 2019 Society of Plastics Engineers     

二氧化硅增强双烯类非极性橡胶的研究进展

介绍了SiO2增强非极性橡胶的2种方法:机械混炼法和原位改性法,分析了2种方法制备SiO2增强橡胶的结构性能特点,指出原位改性法可以实现SiO2粒子均匀分散且粒径大小可控,具有更好的改性效果.并对SiO2增强橡胶的研究方向做出展望.