玻璃钢在海洋环境下的腐蚀机制和性能演变规律
摘要
玻璃钢复合材料(FRP)以其优异的耐蚀性能在海洋领域中的应用正逐渐受到我国及世界科学家的重视,但是由于高分子材料的腐蚀问题不如金属材料腐蚀问题研究得那么深入和广泛,还有腐蚀数据的缺少等都限制了FRP在海洋领域上的应用。
本文通过整理和总结乙烯基树脂在海洋环境下使用的材料腐蚀基础理论,分析FRP发生腐蚀的形式和历程;模拟自然环境试验和加速试验认识腐蚀的规律和机理,着重于温差、湿度、盐度和渗透等因素对材料腐蚀性能的影响规律研究,既进行单因子(温度、盐度、湿度)模拟加速实验,又要分析多因素(应力+湿度)模拟加速实验,找出其单一作用机制及协同效应;通过材料表观状况、理化性能、微观结构的变化评价防腐性;在积累数据的基础上,建立FRP在海水环境下的腐蚀评价技术标准体系,为腐蚀试验、材料和工程设计提供依据和规范;根据腐蚀动力学方程和环境因子影响经验方程,适当选择和简化参量,建立腐蚀寿命预测数学模型,并进行验证。
试验结果表明,高聚物及其复合材料的腐蚀是一个弛豫过程。乙烯基树脂在海洋环境下主要受到湿气、溶胀、应力和化学腐蚀。湿气渗透作用遵循Fick第一定律的,并只与环境的湿度和高聚物的结构有关,而与温度等无关,试验材料的湿度影响因子f≈1。溶胀腐蚀使材料的体积变化较大,对材料的力学性能破坏是非常显著的,尤其是弹性模量,而且高聚物材料的溶胀速率是由材料内部空穴和大分子的扩散运动决定的,与介质小分子的扩散无关;用Fick第二定律的Guass解、橡胶弹性理论和高分子溶液理论解释溶胀的微观机理,计算出试验材料溶解度参数δ=20.2(J/cm3)1/2,与海水溶剂之间的相互作用参数χ= 0.55,这些试验结果与理论是比较吻合的。通过红外光谱分析,材料的化学腐蚀没有新的元素和结构的增加,主要的化学腐蚀形式是水解和氧化。应力腐蚀主要是减少了高聚物材料的应力松弛时间和蠕变时间,降低材料的使用寿命,同时应力对纤维的裂纹生长有决定的作用,加快了FRP断裂破坏速率。根据应力与湿气的协同作用的Wiederhorn经验公式建立了应力、湿度、时间和温度四个因素协同效应的FRP腐蚀寿命经验公式,最后建立了FRP在海洋环境下使用的腐蚀评价标准。
The glass fiber reinforced plastic compound material (FRP) by its outstanding resists corrosion the performance gradually is received by our country and the world scientist's value in the sea domain application,but to the high polymer material corrosion question research is inferior to the metal material corrosion question studies that thorough and widespread,and lack of corrode data the FRP in the field of marine applications.
Through summing up and sorting vinyl resins in the marine environment , using materials corrode basic theories about the FRP in the environment in the form of corrosion and corrosion of these forms of the course material damage; testing and simulating environment through accelerated testing to recognize the law and corruption mechanisms, focusing on temperature, humidity, salt, and other factors on the materials to the corrosive effects of research, for both single-factor (temperature, salinity, humidity) simulation acceleration experiments, but for many factors (stress + humidity) accelerated simulation experiments identify mechanisms and the role of its single synergy effects; materials damaged by the situation, the physical-chemical properties, micro-structural changes estimate FRP’s performance, a comprehensive study in the corrosive water course on corrosion mechanisms, clear picture of the mechanics of materials in the course of testing the performance changes; in the accumulation of data corruption on the basis of a reliable water FRP in the context of corrosion evaluation of technical standards for corrosion testing, materials and engineering design provide the basis and norms; According to corrosion dynamics equation and environmental factors affecting experience equation,appropriate selection and simplify parameter to build a projected life expectancy of ageing mathematical models and certification; address the basic problem is water environment science fibre glass corrosion universality, the main environmental impact factors, rapid corrosion mechanisms and the evolution of material performance.
Test results show that vinyl resins mainly eroded by the humidity、swell、stress and chemical in the marine environment. Moisture infiltration followed Fick No1 law, and only with the environmental humidity and polymer structure,
本文通过整理和总结乙烯基树脂在海洋环境下使用的材料腐蚀基础理论,分析FRP发生腐蚀的形式和历程;模拟自然环境试验和加速试验认识腐蚀的规律和机理,着重于温差、湿度、盐度和渗透等因素对材料腐蚀性能的影响规律研究,既进行单因子(温度、盐度、湿度)模拟加速实验,又要分析多因素(应力+湿度)模拟加速实验,找出其单一作用机制及协同效应;通过材料表观状况、理化性能、微观结构的变化评价防腐性;在积累数据的基础上,建立FRP在海水环境下的腐蚀评价技术标准体系,为腐蚀试验、材料和工程设计提供依据和规范;根据腐蚀动力学方程和环境因子影响经验方程,适当选择和简化参量,建立腐蚀寿命预测数学模型,并进行验证。
试验结果表明,高聚物及其复合材料的腐蚀是一个弛豫过程。乙烯基树脂在海洋环境下主要受到湿气、溶胀、应力和化学腐蚀。湿气渗透作用遵循Fick第一定律的,并只与环境的湿度和高聚物的结构有关,而与温度等无关,试验材料的湿度影响因子f≈1。溶胀腐蚀使材料的体积变化较大,对材料的力学性能破坏是非常显著的,尤其是弹性模量,而且高聚物材料的溶胀速率是由材料内部空穴和大分子的扩散运动决定的,与介质小分子的扩散无关;用Fick第二定律的Guass解、橡胶弹性理论和高分子溶液理论解释溶胀的微观机理,计算出试验材料溶解度参数δ=20.2(J/cm3)1/2,与海水溶剂之间的相互作用参数χ= 0.55,这些试验结果与理论是比较吻合的。通过红外光谱分析,材料的化学腐蚀没有新的元素和结构的增加,主要的化学腐蚀形式是水解和氧化。应力腐蚀主要是减少了高聚物材料的应力松弛时间和蠕变时间,降低材料的使用寿命,同时应力对纤维的裂纹生长有决定的作用,加快了FRP断裂破坏速率。根据应力与湿气的协同作用的Wiederhorn经验公式建立了应力、湿度、时间和温度四个因素协同效应的FRP腐蚀寿命经验公式,最后建立了FRP在海洋环境下使用的腐蚀评价标准。
The glass fiber reinforced plastic compound material (FRP) by its outstanding resists corrosion the performance gradually is received by our country and the world scientist's value in the sea domain application,but to the high polymer material corrosion question research is inferior to the metal material corrosion question studies that thorough and widespread,and lack of corrode data the FRP in the field of marine applications.
Through summing up and sorting vinyl resins in the marine environment , using materials corrode basic theories about the FRP in the environment in the form of corrosion and corrosion of these forms of the course material damage; testing and simulating environment through accelerated testing to recognize the law and corruption mechanisms, focusing on temperature, humidity, salt, and other factors on the materials to the corrosive effects of research, for both single-factor (temperature, salinity, humidity) simulation acceleration experiments, but for many factors (stress + humidity) accelerated simulation experiments identify mechanisms and the role of its single synergy effects; materials damaged by the situation, the physical-chemical properties, micro-structural changes estimate FRP’s performance, a comprehensive study in the corrosive water course on corrosion mechanisms, clear picture of the mechanics of materials in the course of testing the performance changes; in the accumulation of data corruption on the basis of a reliable water FRP in the context of corrosion evaluation of technical standards for corrosion testing, materials and engineering design provide the basis and norms; According to corrosion dynamics equation and environmental factors affecting experience equation,appropriate selection and simplify parameter to build a projected life expectancy of ageing mathematical models and certification; address the basic problem is water environment science fibre glass corrosion universality, the main environmental impact factors, rapid corrosion mechanisms and the evolution of material performance.
Test results show that vinyl resins mainly eroded by the humidity、swell、stress and chemical in the marine environment. Moisture infiltration followed Fick No1 law, and only with the environmental humidity and polymer structure,
引文
1 材料科学技术百科全书编辑委员会. 材料科学技术百科全书. 中国大百科全书出版社, 1995:1~12
2 黄建中, 左禹. 材料的耐蚀性和腐蚀数据. 化学工业出版社, 2002, (6):1~3
3 白新德. 材料腐蚀与控制. 清华大学出版社, 2005(1):177~198
4 O. P. Gillat, L. J. Broutman. Moisture in Epoxy Resin Composites. J. Adhesion. 1981, (6):153~155
5 Adamson, J. Michael. A Conceptual Model of the Thermal-Spike Mechanism in Graphite/Epoxy laminates. Long-Term Behavior of Composites, ASTM STP
813, T. K. Brien. Ed. ASTM, Philadelphia. 1983:77~81
6 Shanker et al. Hygrothermal Effects on Chopped Fiber/Woven fabric Reinforced Epoxy Composites PartA:Moisture Absorption Characteristics. J. of Reinforced Plastic Composites. 1996:446~456
7 David Fred, McBagonluri-Nuun. Simulation of Fatigue Performance and Creep Rupture of FRC for Infrastrcture Applications. Master of Science in Engineering Mechanics. Blackbury, Virginia. 1998:17~21
8 R. F. Regester. The effect of water on Glass-reinforced platic. Corrosion-NACE. Vol.25, No.4, April, 1969:7~12
9 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Fatigue Behavior of High Performance Polymeric Composites in a Simulated Seawater Environment. Progress Report to National Institute for Standard and Technology, Gaithersburg, MD, Dec, 1997:217~219
10 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Durability of E-glass Vinyl Faster an Elevated Temperature Simulated Sea Water Environment. Proceedings of the Seventh International Conference on Marine Applications of Composite Materials, Melbourne, Fl, March, 1998:17~19
11 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Durability of E-glass Vinyl Faster an Elevated Temperature Simulated Sea Water Environment. Proceedings of the American Society of Mechanical Engineers Conference. Dallas, TX, Nov, 1997:15~18
12 M. D. Hayes, K. Garcia, N. Verghese, J. J. Lesko. The Effects of Moisture on the Fatigue Behavior of Glass/Vinyl Ester Composite. Fibre Composites in Infrastructure. 1998, (1):5~7
13 N. Fried. The effect of water on Glass-reinforced platic. Mechanics of Composite Materials. Naval Structural Mechanics. 1967:813~837
14 Tsai, W. Stephen. Environmental Factors in the Design of Composite Materials. Mechanics of Composite Materials. 1970:749~767
15 A. G.. Metcalfe, G. K. Schmitz. Mechanism of Stress Corrosion in E-glass Filaments. Glass Technology. Feb, 1972:15~20
16 G. Lewis, S. W. Bedder, I. Reid. Stress Corrosion of Glass Fibers in Acid Environments. Journal of Materials science Letters. 1984, (3):723~728
17 S. J. Zhou, W. A. Curtin. Failure of Composites:A Lattice Function Model. Acta metall. Mater. Vol.43, No.8, 1995:3069~3104
18 S. M. Wiederhorn. Stress Corrosion in E-glass Filaments. [J]. Am. Ceram. Soc. 1967, (50):47~53
19 翁子樊. 乙烯基酯树脂的发展及其性能. 全面腐蚀控制. 2005,(5):47~48
20 Lan Kummerow et al. Design and Development of 7th International Conference on Marine Applications of Composites Materials. Melbourne, Fl, March, 1998:17~19
21 R. C. Roberts. The Effect of Chemical Environments on the Mechanical. Properties of GRP. Symposium on Reinforce Plastics in Anti-corrosion Application. National Engineering Laboratory, East Kibride. September, 1979:26~27
22 Ronnal Reichard. Composite Super Structure System for Ships. Proceedings 7th International Conference on Marine Applications of Composites Materials. Melbourne, Fl, March, 1998:27~38
23 Sven-Erik Hellbratt et al. Advanced Composites-The future Material in both Naval and Commercial shipbuilding, Design and Development of a Composites Marine supeerstructure for a Fast Catamaran Ferry. Proceedings of 7th International Conference on Marine Applications of Composites Materials. Melbourne Fl, March, 1998:7~13
24 过梅丽, 阳芳, 范欣愉等. 聚合物基复合材料的湿扩散参数研究. [J]. 复合材料学报. 2001, 18(1):34~37
25 刘乃伦, 李浩. 乙烯基酯树脂的耐蚀性能和应用. 热固性树脂. 2001, (9):25~27
26 周润培. 环氧乙烯基酯树脂(Ⅱ)环氧乙烯基酯树脂在酸、碱、盐溶液中的稳定性. 热固性树脂. 2003, (9):40~42
27 陆士平, 王天堂. 溴化环氧乙烯基酯树脂的性能与应用. 玻璃钢/复合材料. 2002, (9):35~37
28 符若文, 李谷, 冯开才. 高分子物理. 化学工业出版社, 2005:203~239
29 F. J. Fischer, M. M. Salama. Emerging and Potential Composites Applications for Deepwater Operations. Composites Engineering and Applications Center for Petroleum Exploration and Production. 2005:35~37
30 肖纪美, 曹楚南. 材料腐蚀原理. 化学工业出版社, 2002, (9):181~183
31 曹楚南. 中国材料的自然环境腐蚀. 化学工业出版社, 2005, (1):185~198
32 N. S. Newman. Steric Effects in Organic Chemistry. [M]. Mechanics of Composite Materials. 1956:13~18
33 张以康. 环氧乙烯基酯树脂在复合材料工业中的应用. 纤维复合材料. 1998, (6):49~52
34 周润培, 侯锐钢等. MFE乙烯基酯树脂及其在防腐蚀领域的应用研究(Ⅰ). 玻璃钢/复合材料. 2002, (7):92~97
35 方征平, 宋义虎, 沈烈. 高分子物理. 浙江大学出版社, 2005:135~171
36 林尚安, 陆耘, 梁兆熙. 高分子化学. 科学出版社, 2000, (11):675~679
37 D. Kalish, B. K. Tariyal. Stress Corrosion of Glass Fibers in Acid Environments. [J]. Am. Ceram. Soc, 1978, (6):578~581
38 P. A. Small. The effect of water on Glass-reinforced platic. [J]. Appl. Chem. 1953, (3):71~75
39 周润培. 环氧乙烯基酯树脂:环氧乙烯基酯树脂在有机溶剂中的稳定性. 热固性树脂. 2003, (5):37~39
40 张华. 现代有机波谱分析. 化学工业出版社, 2005:286~320
41 常建华, 董绮功. 波谱原理及解析. 科学出版社, 2001:76~91
42 虞英军, 吴今培, 陈世权. 模糊系统与数学. 科学出版社, 1999:41~45
43 傅立. 灰色系统理论及其应用. 北京科学技术出版社, 1985:141~153
44 S. W. Wiederhorn et al. An Error Analysis of Failure Prediction Techniques Derived from Fracture Mechanics. J. Am. Cream. Soc, 1976:403~411
2 黄建中, 左禹. 材料的耐蚀性和腐蚀数据. 化学工业出版社, 2002, (6):1~3
3 白新德. 材料腐蚀与控制. 清华大学出版社, 2005(1):177~198
4 O. P. Gillat, L. J. Broutman. Moisture in Epoxy Resin Composites. J. Adhesion. 1981, (6):153~155
5 Adamson, J. Michael. A Conceptual Model of the Thermal-Spike Mechanism in Graphite/Epoxy laminates. Long-Term Behavior of Composites, ASTM STP
813, T. K. Brien. Ed. ASTM, Philadelphia. 1983:77~81
6 Shanker et al. Hygrothermal Effects on Chopped Fiber/Woven fabric Reinforced Epoxy Composites PartA:Moisture Absorption Characteristics. J. of Reinforced Plastic Composites. 1996:446~456
7 David Fred, McBagonluri-Nuun. Simulation of Fatigue Performance and Creep Rupture of FRC for Infrastrcture Applications. Master of Science in Engineering Mechanics. Blackbury, Virginia. 1998:17~21
8 R. F. Regester. The effect of water on Glass-reinforced platic. Corrosion-NACE. Vol.25, No.4, April, 1969:7~12
9 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Fatigue Behavior of High Performance Polymeric Composites in a Simulated Seawater Environment. Progress Report to National Institute for Standard and Technology, Gaithersburg, MD, Dec, 1997:217~219
10 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Durability of E-glass Vinyl Faster an Elevated Temperature Simulated Sea Water Environment. Proceedings of the Seventh International Conference on Marine Applications of Composite Materials, Melbourne, Fl, March, 1998:17~19
11 Fred. McBagonluri, M. Hayes, K. Garcia, J. J. Lesko. Durability of E-glass Vinyl Faster an Elevated Temperature Simulated Sea Water Environment. Proceedings of the American Society of Mechanical Engineers Conference. Dallas, TX, Nov, 1997:15~18
12 M. D. Hayes, K. Garcia, N. Verghese, J. J. Lesko. The Effects of Moisture on the Fatigue Behavior of Glass/Vinyl Ester Composite. Fibre Composites in Infrastructure. 1998, (1):5~7
13 N. Fried. The effect of water on Glass-reinforced platic. Mechanics of Composite Materials. Naval Structural Mechanics. 1967:813~837
14 Tsai, W. Stephen. Environmental Factors in the Design of Composite Materials. Mechanics of Composite Materials. 1970:749~767
15 A. G.. Metcalfe, G. K. Schmitz. Mechanism of Stress Corrosion in E-glass Filaments. Glass Technology. Feb, 1972:15~20
16 G. Lewis, S. W. Bedder, I. Reid. Stress Corrosion of Glass Fibers in Acid Environments. Journal of Materials science Letters. 1984, (3):723~728
17 S. J. Zhou, W. A. Curtin. Failure of Composites:A Lattice Function Model. Acta metall. Mater. Vol.43, No.8, 1995:3069~3104
18 S. M. Wiederhorn. Stress Corrosion in E-glass Filaments. [J]. Am. Ceram. Soc. 1967, (50):47~53
19 翁子樊. 乙烯基酯树脂的发展及其性能. 全面腐蚀控制. 2005,(5):47~48
20 Lan Kummerow et al. Design and Development of 7th International Conference on Marine Applications of Composites Materials. Melbourne, Fl, March, 1998:17~19
21 R. C. Roberts. The Effect of Chemical Environments on the Mechanical. Properties of GRP. Symposium on Reinforce Plastics in Anti-corrosion Application. National Engineering Laboratory, East Kibride. September, 1979:26~27
22 Ronnal Reichard. Composite Super Structure System for Ships. Proceedings 7th International Conference on Marine Applications of Composites Materials. Melbourne, Fl, March, 1998:27~38
23 Sven-Erik Hellbratt et al. Advanced Composites-The future Material in both Naval and Commercial shipbuilding, Design and Development of a Composites Marine supeerstructure for a Fast Catamaran Ferry. Proceedings of 7th International Conference on Marine Applications of Composites Materials. Melbourne Fl, March, 1998:7~13
24 过梅丽, 阳芳, 范欣愉等. 聚合物基复合材料的湿扩散参数研究. [J]. 复合材料学报. 2001, 18(1):34~37
25 刘乃伦, 李浩. 乙烯基酯树脂的耐蚀性能和应用. 热固性树脂. 2001, (9):25~27
26 周润培. 环氧乙烯基酯树脂(Ⅱ)环氧乙烯基酯树脂在酸、碱、盐溶液中的稳定性. 热固性树脂. 2003, (9):40~42
27 陆士平, 王天堂. 溴化环氧乙烯基酯树脂的性能与应用. 玻璃钢/复合材料. 2002, (9):35~37
28 符若文, 李谷, 冯开才. 高分子物理. 化学工业出版社, 2005:203~239
29 F. J. Fischer, M. M. Salama. Emerging and Potential Composites Applications for Deepwater Operations. Composites Engineering and Applications Center for Petroleum Exploration and Production. 2005:35~37
30 肖纪美, 曹楚南. 材料腐蚀原理. 化学工业出版社, 2002, (9):181~183
31 曹楚南. 中国材料的自然环境腐蚀. 化学工业出版社, 2005, (1):185~198
32 N. S. Newman. Steric Effects in Organic Chemistry. [M]. Mechanics of Composite Materials. 1956:13~18
33 张以康. 环氧乙烯基酯树脂在复合材料工业中的应用. 纤维复合材料. 1998, (6):49~52
34 周润培, 侯锐钢等. MFE乙烯基酯树脂及其在防腐蚀领域的应用研究(Ⅰ). 玻璃钢/复合材料. 2002, (7):92~97
35 方征平, 宋义虎, 沈烈. 高分子物理. 浙江大学出版社, 2005:135~171
36 林尚安, 陆耘, 梁兆熙. 高分子化学. 科学出版社, 2000, (11):675~679
37 D. Kalish, B. K. Tariyal. Stress Corrosion of Glass Fibers in Acid Environments. [J]. Am. Ceram. Soc, 1978, (6):578~581
38 P. A. Small. The effect of water on Glass-reinforced platic. [J]. Appl. Chem. 1953, (3):71~75
39 周润培. 环氧乙烯基酯树脂:环氧乙烯基酯树脂在有机溶剂中的稳定性. 热固性树脂. 2003, (5):37~39
40 张华. 现代有机波谱分析. 化学工业出版社, 2005:286~320
41 常建华, 董绮功. 波谱原理及解析. 科学出版社, 2001:76~91
42 虞英军, 吴今培, 陈世权. 模糊系统与数学. 科学出版社, 1999:41~45
43 傅立. 灰色系统理论及其应用. 北京科学技术出版社, 1985:141~153
44 S. W. Wiederhorn et al. An Error Analysis of Failure Prediction Techniques Derived from Fracture Mechanics. J. Am. Cream. Soc, 1976:403~411