改性聚乙烯火焰喷塑涂层研究
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摘要
火焰喷塑是一种环境污染极低的防腐和阻隔涂层制造技术，在航天航空、汽车、化工等行业有着极其广阔的应用前景。由于目前市场上大量使用的非极性聚乙烯的火焰喷塑涂层附着力较低，而一些附着力较高的涂层材料如：乙烯—甲基丙烯酸共聚物(EMAA)等需要进口，价格昂贵，因此，研究聚乙烯的改性方法和价格低廉的喷塑材料是本研究的主要目的。另外，研究改性聚乙烯火焰喷塑工艺条件以及喷塑涂层附着力测量时有效的粘结方法是本研究首先必须完成的任务。
采用掺混改性的方法，向聚乙烯火焰喷塑材料中加入带极性基团的物质可以增强聚乙烯涂层的极性，加入纳米材料可增强涂层的吸附能力，这两种方法可提高聚乙烯火焰喷塑涂层的附着力和多方面性能。本研究主要结论如下：
(1)用拉开法测量火焰喷塑涂层附着力时，有效的粘接方法是采用加热粘结，并在粘结柱头表面预涂EMAA涂层，该方法能保证良好的测量效果和试验的可重复性。
(2)乙烯—甲基丙烯酸共聚物(EMAA)的加入增强了聚乙烯材料的极性，在很大程度上提高了PE涂层的附着力，并能提高PE涂层的力学性能、耐化学腐蚀性能、耐盐雾腐蚀及光老化性能。在PE中加入25％EMAA能使涂层的附着力提高60％，涂层抗冲击强度增加58.3％。
(3)加入纳米TiO_2、SiO_(2-x)能提高聚乙烯火焰喷塑涂层的附着力、抗冲击性能及涂层的耐老化性能。含纳米Al_2O_3的涂层具有极高的耐冲刷磨损能力。
(4)在聚乙烯火焰喷塑材料中按重量百分比加入25％EMAA可以制成一种性能优良价格相对低廉的火焰喷塑材料。
Plastic flame spraying is one of the surface engineering techniques that have the slightest pollution of environment. The polymeric coatings are now widely used as the corrosion resistance, barrier coating in the fields of aircraft, automotive and chemical industry. Currently non-polar Polyethylene (PE) is the most popular materials in the market but the coating can not fit some special needs because its low adhesion. Other materials with high adhesion need to import from foreign countries at very high prices. Developing a modified PE method and a lower cost polymer used in the flame spraying are the objectives of this study. Improving the method of bonding stud with coating surface and studying the process conditions of PE flame spray are important tasks in this work.
In this paper the modified PE methods are presented. To improve adhesion and other properties of PE spray coatings, it is expected that the coatings blending PE with the polar polymer brings polar group into the materials of flame spraying or dispersing the nanosized materials in PE matrix improves the absorbability of coatings. The main results of this study are summarized as follows.
I To measure the adhesion of polymer coating to steel substrate by the direct pull-off technique, the most efficient way is heating the stud to 210癈 + 10 癈, use it fusion ethylene-methacrylic acid( EMAA) in it's surface then bonding it to the coating surface. This method can warrant effective results as well as experiment repeatability.
n The adhesion of PE flame spray coating is improved to a high level as well as the coatings properties such as mechanical property, corrosion-resistant property, salt spray test property and anti light-heat aging property by blending EMAA with PE. Blending
25% EMM with PE according to weight percentage can enhance the adhesion of the PE coating by 60% and the impacting height by 58.3%.
IJJ Dispersing nanosized TiO2, SiO2-x in PE matrix can improve the adhesion of the PE coating and the intensity of impacting . Nanocomposite coating has the powerful ability of anti light-heat aging. The AlO3 nanocomposite coating has excellent wear-resistance.
IV A flame spraying PE material with lower cost and fine properties can be produced by blending 25% EMAA to PE according to weight percentage.
Author: Xiong Haiping (Material Science) Directed by: Xiao Yide (Professor) Wu Jianhua (Professor)
采用掺混改性的方法，向聚乙烯火焰喷塑材料中加入带极性基团的物质可以增强聚乙烯涂层的极性，加入纳米材料可增强涂层的吸附能力，这两种方法可提高聚乙烯火焰喷塑涂层的附着力和多方面性能。本研究主要结论如下：
(1)用拉开法测量火焰喷塑涂层附着力时，有效的粘接方法是采用加热粘结，并在粘结柱头表面预涂EMAA涂层，该方法能保证良好的测量效果和试验的可重复性。
(2)乙烯—甲基丙烯酸共聚物(EMAA)的加入增强了聚乙烯材料的极性，在很大程度上提高了PE涂层的附着力，并能提高PE涂层的力学性能、耐化学腐蚀性能、耐盐雾腐蚀及光老化性能。在PE中加入25％EMAA能使涂层的附着力提高60％，涂层抗冲击强度增加58.3％。
(3)加入纳米TiO_2、SiO_(2-x)能提高聚乙烯火焰喷塑涂层的附着力、抗冲击性能及涂层的耐老化性能。含纳米Al_2O_3的涂层具有极高的耐冲刷磨损能力。
(4)在聚乙烯火焰喷塑材料中按重量百分比加入25％EMAA可以制成一种性能优良价格相对低廉的火焰喷塑材料。
Plastic flame spraying is one of the surface engineering techniques that have the slightest pollution of environment. The polymeric coatings are now widely used as the corrosion resistance, barrier coating in the fields of aircraft, automotive and chemical industry. Currently non-polar Polyethylene (PE) is the most popular materials in the market but the coating can not fit some special needs because its low adhesion. Other materials with high adhesion need to import from foreign countries at very high prices. Developing a modified PE method and a lower cost polymer used in the flame spraying are the objectives of this study. Improving the method of bonding stud with coating surface and studying the process conditions of PE flame spray are important tasks in this work.
In this paper the modified PE methods are presented. To improve adhesion and other properties of PE spray coatings, it is expected that the coatings blending PE with the polar polymer brings polar group into the materials of flame spraying or dispersing the nanosized materials in PE matrix improves the absorbability of coatings. The main results of this study are summarized as follows.
I To measure the adhesion of polymer coating to steel substrate by the direct pull-off technique, the most efficient way is heating the stud to 210癈 + 10 癈, use it fusion ethylene-methacrylic acid( EMAA) in it's surface then bonding it to the coating surface. This method can warrant effective results as well as experiment repeatability.
n The adhesion of PE flame spray coating is improved to a high level as well as the coatings properties such as mechanical property, corrosion-resistant property, salt spray test property and anti light-heat aging property by blending EMAA with PE. Blending
25% EMM with PE according to weight percentage can enhance the adhesion of the PE coating by 60% and the impacting height by 58.3%.
IJJ Dispersing nanosized TiO2, SiO2-x in PE matrix can improve the adhesion of the PE coating and the intensity of impacting . Nanocomposite coating has the powerful ability of anti light-heat aging. The AlO3 nanocomposite coating has excellent wear-resistance.
IV A flame spraying PE material with lower cost and fine properties can be produced by blending 25% EMAA to PE according to weight percentage.
Author: Xiong Haiping (Material Science) Directed by: Xiao Yide (Professor) Wu Jianhua (Professor)
引文
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[38] 王国英，费小非．乙烯—甲基丙烯酸共聚物及其盐的光散射研究[J]．厦门大学学报(自然科学版)，1997，36(2)：257～261．
[39] Berndt C C. Thermal Spray 2001:New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio,USA, 307～313.
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[43] Berndt C C. Thermal Spray 2001:New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio, USA, 327～330.
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[2] 李雨康．火焰喷塑技术进展[J]．造船技术，1998，(2)：30～32．
[3] Fauchais P, Vardelle A. Thermal Spray 2001: New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio,USA, 1～32.
[4] Berndt C C. Thermal Coatings in Europe: a business prospective in Thermal Spray 2001: New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio, USA, 1267～1271.
[5] 徐滨士，韩文政．火焰塑料粉末喷涂和喷涂层机械性能研究[J]．表面工程，1989，(1)：15～21．
[6] Bishop J. The Facility of Thermal spray plastic coatings [J]. Surfacing Journal International, 1986,1 (3):97～99.
[7] 黄小鸥．浮光掠影话埃森——2002年国际热喷涂大会(ITSC’02)述评[R]．2002，中国农机表面工程研究所，鞍山，1～10．
[8] 马小雄，伍建华，陈惠国．国内外火焰喷塑文集汇编[C]．1993，武汉材料保护研究所，湖北，21～27．
[9] 伍建华．第四届国际热喷涂研讨会(ITSS’2000)暨第五届全国热喷涂年会(CNTS’2000)论文集[C]．2000，黑龙江人民出版社，哈尔滨，291～293．
[10] 伍建华．第一届国际机械工程学术会议论文集[C]．2000，机械工业出版社，北京，35～38．
[11] 殷凤仕，姜学波．非金属材料学[M]．1999，机械工业出版社，北京，17～35．
[12] Mckinney, Osborne K. Poluolefin Flame Spraying Method[P].United States Patent:5221900,May 18,1993.
[13] Loustaunau P L, Douglas Horton. EMAA Thermoplastic Powder Coatings in Shop and Field Applications [J]. Material Performance, 1994,(7):32～35.
[14] Geroge E R, Reimer J. Flame sprayed Thermoplastic Powder Coatings[J].Polymer Engineering and Science, 1991,31 (11):789.
[15] Brogan J, Berndt C C. The Mechanical Properties of Combustion-Sprayed Polymers and Blend. In Thermal Spray: Practical Solutions for Engineering
Problems[C]. 1996, ASM International Material Park, OH, USA, 221～227.
[16] BroganJ, Berndt C C. EMAA Thermoplastic Powder Coating[J].Polymer Engineering and Science, 1998,38(11): 1866～1812.
[17] Brogan J, Berndt C C. Development of Recycled Polymer Blends for Thermal Spray Applications [R]. USA:US Army Corps of Engineers,Dec. 1997,1～76.
[18] Brogan J, Berndt C C. The Coalescence of Combustion-Sparyed Ethylene Methacrylic Acid Copolymer[J].J Material Sci, 1997,(4):2099～2106.
[19] Sugama T, Kawase R. An Evaluation of Methacrylic Acid-modified Polyethylene Coatings Applied by Flame-spray Technology[J].Progress in Organic Coatings, 1994,25(2):205～216.
[20] Mckinney, Osborne K. Polyolefin Flame Spraying Method and Apparatus[P].WO93/02802,Feb. 1993.
[21] Sun L,Berndt C C. Thermal Spray2001:New Surfaces for a New Millennium[C].2001, ASM International, Materials Park, Ohio,USA, 321～326.
[22] 李华阳，魏德卿．低分子量聚乙烯双单体非均相共接枝[J]．合成化学，2002，10(1)：25～29．
[23] 张卫勤，李光宪，左红军．聚乙烯接枝改性及其与铝的粘接性[J]．塑料加工，2001，31(3)：27～30．
[24] Blackmore C E. Nylon Powders and their as Surface Coatings Using Flame Spraying[J]. Surface Engineering, 1987,3(1):29～34.
[25] Bao Y, Gawne D T. Production of Polymer Matrix Composite Coatings by Thermal Spraying [J].Trans. I. M. F, 1994,72(2):110～113.
[26] Bao Y, Gawne D. Plasma Spray Deposition of Nylon11 Coatings [J].Trans. Inst Metal, 1991,69(3):80～85.
[27] Berndt C C. Thermal Spray 2001:New Surface for New Millennium [C]. 2001, ASM International Materials Park, OH,USA,337～346.
[28] Berndt C C. Thermal Spray 2001:New Surface for New Millennium[C]. 2001, ASM International Materials Park, OH,USA, 331～336.
[29] Coddet C. Thermal Spraying:Meeting the Challenges of the 21st Century[C]. 1998, ASM International Material Park, USA, 19～24.
[30] LiaoH, Beche E. On the Microstructures of Thermally Sprayed PEEK Polymer[R].Nice,France, 1998.25～29.
[31] Berndt C C. Thermal Spray Science & Technology[C]. 1995, ASM International Proceedings, Houston,USA,521～526.
[32] Berndt C C. Thermal Spray: Practical Solutions for Engineering Problems[C]. 1996, ASM International Material Park, OH,USA, 245～255
[33] 尚清泉，徐滨士．聚醚醚酮(PEEK)粉末火焰喷涂技术初探[J]．表面工程，1990，(2)：38～41．
[34] Coddet C. Thermal Spraying: Meeting the Challenges of the 21st Century[C]. 1998, ASM International Material Park, USA ,629～634.
[35] Kawase R, Nakano A. Production of Heat and Corrosion-Resistant Plastic Coatings. In Thermal Spray: Practical Solution for Engineering Problems[C], 1996, ASM International, Materials Park, OH, USA,257～261.
[36] Brogan J,Berndt C C. Physical and Relaxation Properties of Flame-sprayed Ethylene-Methacrylic Acid Copolymer[J]. Polymer Engineering and Science, 1998,38(11): 1873～1881.
[37] Liao H,Coddet Christian. Mechanical Properties of Thermal Spray PEEK. Coatings.In Thermal Spray 2001:New Surface for New Millennium[C], 2001, ASM International, Materials Park, OH, USA,315～320.
[38] 王国英，费小非．乙烯—甲基丙烯酸共聚物及其盐的光散射研究[J]．厦门大学学报(自然科学版)，1997，36(2)：257～261．
[39] Berndt C C. Thermal Spray 2001:New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio,USA, 307～313.
[40] 霍金斯．聚合物的稳定性能[M]．1981，轻工业出版社，北京，222～284．
[41] 张玉龙，李长德．纳米技术与纳米塑料[M]．2002，中国轻工业出版社，北京，168～252．
[42] Berndt C C. Thermal Spray: A United Forum for Scientific and Technological Advances[C]. 1997, ASM International, Materials Park, OH,USA, 877～883.
[43] Berndt C C. Thermal Spray 2001:New Surface for New Millennium[C]. 2001, ASM International, Materials Parks, Ohio, USA, 327～330.
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