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- 2017
硅藻土/硅橡胶可陶瓷化复合材料的制备及性能
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Abstract:
硅橡胶耐热性不佳严重制约着其在耐高温领域的应用。针对这一问题，分别采用低熔点氧化物Sb2O3和Bi2O3作为助溶剂，研究其对硅藻土/硅橡胶复合材料可瓷化性能的影响。采用TG分析Sb2O3和Bi2O3对硅藻土/硅橡胶复合材料的热稳定性影响，万能力学试验仪测试热解后试样的弯曲强度，场发射扫描电镜（FESEM）和能谱仪（EDS）分析热解产物的微观形貌和成份，XRD探索复合材料的可瓷化机制。结果表明：Sb2O3和Bi2O3金属氧化物会加速硅橡胶的分解，但可以明显提高热解后试样的弯曲强度。FESEM观测到Sb2O3和Bi2O3有助于复合材料在热解过程中形成连续的桥连结构，通过EDS分析计算可知，Sb2O3与SiO2，Bi2O3与SiO2在热解过程中可能发生共熔反应，有助于陶瓷化结构的形成。XRD表明，加入助溶剂后的硅藻土/硅橡胶复合材料的热解后形成非晶相结构，提高陶瓷层的强度。 The poor heat resistance of silicone rubber seriously restricts its application in the field of high temperature resistance. To solve this problem, low melting oxide Sb2O3 and Bi2O3 were used as fluxing agent to study the effects on the ceramizable properties of diatomite/silicone rubber composites. The thermal stability of Sb2O3 and Bi2O3 on diatomite/silicone rubber composites was analyzed by TG, the bending strength after pyrolysis was tested by universal mechanical testing apparatus, field emission scanning electron microscope (FESEM) and energy dispersive spectrometer (EDS) were used to analyze the microstructure and composition of the pyrolysis products, and ceramic mechanism was studied by XRD. The results show that metal oxide of Sb2O3 and Bi2O3 can accelerate the decomposition of silicone rubber, but they can obviously improve the bending strength of the specimen after pyrolysis. Bi2O3 and Sb2O3 are contribute to the formation of a continuous bridge structure in the process of composites pyrolysis by FESEM. Through EDS analysis, eutectic phenomenon may be occurring between SiO2 and Sb2O3, Bi2O3 and SiO2 in the process of composites pyrolysis and help to form a ceramic structure. XRD show that the amorphous phase structure is formed after the addition of fluxing agent to diatomite/silicone rubber composite, which can improve the strength of the ceramics. 国家自然科学基金（51003084）
| [1] | 黄海明, 杜善义, 吴林志, 等. C/C复合材料烧蚀性能分析[J]. 复合材料学报, 2001, 18(3):76-80.HUANG H M, DU S Y, WU L Z, et al. Analysis of the ablation of C/C composites[J]. Acta Materiae Compositae Sinica, 2001, 18(3):76-80(in Chinese). |
| [2] | 梁军, 周振功, 杜善义. 树脂基材料的高温烧蚀变形[J]. 复合材料学报, 2002, 19(3):83-87.LIANG J, ZHOU Z G, DU S Y. Behavior of the ablative deformation of resin matrix materials at high temperature[J]. Acta Materiae Compositae Sinica, 2002, 19(3):83-87(in Chinese). |
| [3] | 谢文峰, 李云霞, 秦岩, 等. 有机硅聚合物复合材料陶瓷化研究进展[J]. 武汉理工大学学报, 2013, 35(2):53-56.XIE W F, LI Y X, QIN Y, et al. Organic silicon polymer ceramic chemical research progress[J]. Journal of Wuhan University of Technology, 2013, 35(2):53-56(in Chinese). |
| [4] | 聂梅, 范召东. 阻燃防火硅橡胶研究进展[J]. 化工新型材料, 2008, 36(2):8-9.NIE M, FAN Z D. Advance in the research and application of flame-retardant and fireproof silicone rubber[J]. New Chemical Materials, 2008, 36(2):8-9(in Chinese). |
| [5] | 杨洪, 申屠宝卿. 硅橡胶的耐热稳定性[J]. 合成橡胶工业, 2005(3):229-233.YANG H, SHENTU B Q. Heat stability resistance of silicone rubber[J]. China Synthetic Rubber Industry, 2005(3):229-233(in Chinese). |
| [6] | 田挺胜, 张军. 低熔点玻璃粉/硅橡胶可瓷化复合材料的制备与性能[J]. 橡胶工业, 2015(5):273-277.TIAN T S, ZHANG J. Preparation and properties of low melting point glass powder/silicone rubber ceramifying composites[J]. China Rubber Industry, 2015(5):273-277(in Chinese). |
| [7] | MANSOURI J, BURFORD R, CHENG Y B. Pyrolysis behaviour of silicone-based ceramifying composites[J]. Materials Science and Engineering A-Structural, 2006, 425(1-2):7-14. |
| [8] | MANSOURI J, BURFORD R, CHENG Y B, et al. Formation of strong ceramified ash from silicone-based compositions[J]. Journal of Materials Science, 2005, 40(21):5741-5749. |
| [9] | HANU L G, SIMON G P, CHENG Y B. Thermal stability and flammability of silicone polymer composites[J]. Polymer Degradation and Stability, 2006, 91(6):1373-1379. |
| [10] | ANYSZKA R, BIELINSKI D M, PEDZICH Z, et al. Influence of surfaces of modified montmorillonites on properties of silicone rubber-based ceramizable composites[J]. Journal of Thermal Analysis and Calorimetry, 2015, 119(1):111-121. |
| [11] | KIERSTEN L S. Flame resistant silicone rubber wire and cable coating composition. US, 6239378 B1[P]. 2001-05-29. |
| [12] | 亢庆卫, 罗权. 以三氧化二锑为协效剂的复合阻燃剂对MVQ硫化胶阻燃性能的影响[J]. 橡胶工业, 2004, 51(11):651-654.KANG Q W, LUO Q. Effects of compound flame retardants with Sb2O3 on Flame retardance of MVQ vulcanizate[J]. China Rubber Industry, 2004, 51(11):651-655(in Chinese). |
| [13] | ALLEN N S, EDGE M, CORRALES T, et al. Ageing and stabilisation of filled polymers:an overview[J]. Polymer Degradation and Stability, 1998, 61(2):183-199. |
| [14] | 江红涛. 硅酸铋粉体制备和熔体性能研究[D]. 陕西科技大学, 2013.JIANG H T. Research on powder preparation and melt properties of bismuth silicate[D]. Shanxi University of Science and Technology, 2013(in Chinese). |
| [15] | 翁俊梅, 姜胜林, 许毓春, 等. 氧化铋氧化锑热处理对氧化锌压敏电阻的影响[C]. 中国电子学会敏感技术分会电压敏专业学部第十八届学术年会论文集, 2011:33-37.WENG J M, JIANG S L, XU Y C, et al. Effects of heat-treating Bi2O3 and Sb2O3 on the characteristics of ZnO varistors[C]. Chinese Institute of Electronics Technology Branch Voltage Sensitivity of Sensitive Professional Eighteenth Annual Conference, 2011:33-37(in Chinese). |
| [16] | 粱敬魁, 张玉苓, 方兴. Bi2O3-Sb2O3二元系的研究[J]. 低温物理学报, 1992, 14(3):161-166.LIANG J K, ZHANG Y L, FANG X. The studies on Bi2O3-Sb2O3 binary system[J]. Chinese Journal of Low Temperature Physics, 1992, 14(3):161-166(in Chinese). |
| [17] | THOMSON K, SHANKS R, GENOVESE A. New ceramifying polymer materials for passive fire protection applications[J]. Journal of ASTM International, 2007, 4(7):1-8. |
| [18] | 邵海彬, 张其土, 吴丽, 等. 可瓷化硅橡胶的制备与性能[J]. 南京工业大学学报(自然科学版), 2011, 33(1):48-51.SHAO H B, ZHANG Q S, WU L, et al. Preparation and properties of ceramifying silicone rubber[J]. Journal of Nanjing University of Technology(Natural Science Edition), 2011, 33(1):48-51(in Chinese). |
| [19] | 李跃. 硅橡胶复合材料的导电响应行为和可陶瓷化性能的研究[D]. 上海交通大学, 2013.LI Y. Study on conductive response behaviors and ceramifiable properties of silicone rubber composites[D]. Journal of Shanghai Jiaotong University, 2013(in Chinese). |
| [20] | HANU L G, SIMON G P, CHENG Y B. Preferential orientation of muscovite in ceramifiable silicone composites[J]. Materials Science and Engineering A-Structural, 2005, 398(1-2):180-187. |
| [21] | MANSOURI J, WOOD C A, ROBERTS K, et al. Investigation of the ceramifying process of modified silicone-silicate compositions[J]. Journal of Materials Science, 2007, 42(15):6046-6055. |
| [22] | 苏柳梅, 樊星, 尤红梅等. 硅橡胶/黏土可瓷化复合材料的热行为及微观形貌[J]. 粉末冶金材料科学与工程, 2011, 16(6):856-863.SU L M, FAN X, YOU H M, et al. Thermal behavior and microstructure of ceramifiable polymer composites[J]. Materials Science and Engineering of Powder Metallurgy, 2011, 16(16):856-863(in Chinese). |
| [23] | HSHIEH F Y. Shielding effects of silica-ash layer on the composition of silicones and their possible applications on the fire retardancy of organic polymers[J]. Fire and Materials, 1998, 22(2):69-76. |
