张秀丽,冯如康,吴永玲,刘志兰,吴棣本,郑宏宇.溶胶凝胶法制备橡胶模具表面涂层及其防粘性能[J].表面技术,2024,53(16):229-239. ZHANG Xiuli,FENG Rukang,WU Yongling,LIU Zhilan,WU Diben,ZHENG Hongyu.Preparation and Anti-sticking Properties of Rubber Mold Surface Coating by Sol-gel Method[J].Surface Technology,2024,53(16):229-239 |
溶胶凝胶法制备橡胶模具表面涂层及其防粘性能 |
Preparation and Anti-sticking Properties of Rubber Mold Surface Coating by Sol-gel Method |
投稿时间:2023-09-03 修订日期:2024-01-05 |
DOI:10.16490/j.cnki.issn.1001-3660.2024.16.020 |
中文关键词: 溶胶凝胶法 涂层 橡胶模具 防粘性 耐久性 |
英文关键词:sol-gel method coating rubber mold anti-sticking property durability |
基金项目:国家自然科学基金(51905317);山东省自然科学基金(ZR2020ME047) |
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Author | Institution |
ZHANG Xiuli | School of Mechanical Engineering, Shandong University of Technology, Shandong Zibo 255000, China;Shandong Provincial Key Laboratory of Precision Manufacturing and Non-traditional Machining, Shandong Zibo 255000, China |
FENG Rukang | School of Mechanical Engineering, Shandong University of Technology, Shandong Zibo 255000, China |
WU Yongling | School of Mechanical Engineering, Shandong University of Technology, Shandong Zibo 255000, China;Shandong Provincial Key Laboratory of Precision Manufacturing and Non-traditional Machining, Shandong Zibo 255000, China |
LIU Zhilan | Shandong Provincial Key Laboratory of Core Tire Mold Technology, Shandong Gaomi 261000, China |
WU Diben | Shandong Provincial Key Laboratory of Core Tire Mold Technology, Shandong Gaomi 261000, China |
ZHENG Hongyu | School of Mechanical Engineering, Shandong University of Technology, Shandong Zibo 255000, China |
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中文摘要: |
目的 针对目前45钢橡胶模具易粘污、寿命低,而氟树脂涂层模具成本高等问题,基于溶胶凝胶法制备防粘涂层,研究涂层的防粘性能和耐久性。方法 以硅溶胶、甲基三乙氧基硅烷(MTES)、氟硅烷为主要原料,采用空气喷涂法在45钢模具试样表面制备溶胶凝胶涂层、氟硅烷改性溶胶凝胶涂层和氟硅烷表面处理涂层,通过硫化脱模试验,并利用扫描电子显微镜和能谱仪观察分析试样表面微观形貌和元素组成随硫化试验次数的变化,研究涂层对橡胶的防粘性和耐久性,探究橡胶在涂层表面的黏附过程。结果 溶胶凝胶涂层由O、Si、C、Ti 4种元素组成,成膜性好,硫化脱模力约为20 N,与PTFE涂层相近,并具有较好的防橡胶粘污性能,相较45钢模具可多硫化约300次,模具连续使用寿命提高2~3倍。氟硅烷改性溶胶凝胶涂层增加了F元素,但其与基底结合力降低;而氟硅烷表面处理虽能降低表面能,减小脱模力,但在橡胶硫化过程中容易被粘掉,污染制品。橡胶污染物在模具表面的黏附积累与橡胶的流动有关。在橡胶流动较小的区域,橡胶污染物微观形貌呈现纹理状;而在流动区域,橡胶污染物初期为片状,随硫化次数增加逐渐增厚,随后沿流动方向产生裂纹,发展为块状。结论 溶胶凝胶涂层具有较好的防粘性和耐久性,同时环境友好,成膜温度低、成本低、易清洗,在橡胶模具上具有广阔的应用前景。 |
英文摘要: |
As the type 45 steel rubber mold is easy to be contaminated and the fluororesin coated mold is expensive, the work aims to prepare the anti-sticking coating on rubber mold based on the sol-gel method, and investigate the anti-sticking property and durability of the coating. With silica sol and methyl triethoxysilane (MTES) as the main raw materials, sol-gel coating was prepared on the type 45 steel mold samples. Fluoroalkyl silane modified sol-gel coating and fluoroalkyl silane surface treatment coating were also prepared for comparison with the non-fluorine sol-gel coating. The anti-sticking property and durability of the coatings were investigated by rubber vulcanization tests. The changes of surface micro morphology and element composition of the samples with the number of vulcanization tests were studied by scanning electron microscope and energy dispersive spectrometer. The adhesion process of rubber on the coating surface was investigated. The results showed that the sol-gel coating was composed of O, Si, C, and Ti, with good film forming property. Its vulcanization release force was about 20 N, similar to that of the PTFE coating. The element composition changed little after 10 vulcanization tests, indicating that it had good anti-fouling performance. The fluoroalkyl silane modified sol-gel coating was composed of O, Si, C, Ti, and F. The element F reduced the adhesion between the coating and the substrate, which might lead to cracking and spalling of the coating during the vulcanization tests. The fluoroalkyl silane surface treatment coating could reduce the surface energy and the release force, but the fluoroalkyl silane film was easy to stick to the rubber and pollute the products. The sol-gel coating was more applicable to rubber molds compared with the fluoroalkyl silane modified sol-gel coating and fluoroalkyl silane surface treatment coating. The results of the durability test showed that the type 45 steel surface became yellow after 100 vulcanization tests, with different brightness at different positions, and turned brown after 300 tests. However, the surface color of the sol-gel coating changed little after 200 vulcanization tests, turned light yellow after 300 tests, and became brown after 500 tests. The variation of Zn element mass content with the number of vulcanization tests indicated that the sol-gel coating could be used approximately 300 times more than the type 45 steel mold for rubber vulcanization, increasing the continuous service life of the mold 2-3 times. The adhesion and accumulation of rubber contaminants on the surface of the mold were related to the flow of rubber during vulcanization. In areas where the rubber flow speed was low, the micro morphology of rubber pollutants appeared as a textured pattern. While in the high flow rate area, rubber pollutants initially appeared as flakes, gradually thickened with increasing vulcanization times, and then cracked along the flow direction, developing into blocks. The different micro morphologies led to the different appearance at different positions, and affected the surface quality of the rubber products. Thus, reducing the rubber flow will improve the surface brightness uniformity of the products. Although the service life of the sol-gel coating is shorter than that of the fluororesin anti-sticking coating, it has the advantages of environmental friendliness (free of toxic and refractory substances such as perfluorooctanoic acid), low film forming temperature, low carbon consumption, low cost, and easy cleaning. The sol-gel coating has broad application prospects in rubber molds. |
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