玻璃钢在CO2环境中的腐蚀行为及其性能研究

Classified Index: TB332 U.D.C: 620
Dissertation for the Master Degree in Engineering
THE RESEARCH OF CORROSION BEHAVIOR AND ITS PROPERTIES OF GFRP IN CO2 ENVIRONMENT
-I-
哈尔滨工业大学工学硕士学位论文
Abstract
Glass fiber reinforced plastic (GFRP) is widely used as pipes for gathering and transportation of oil and gas by its excellent comprehensive properties. However, there are few research and related reports on the corrosion problems of GFRP pipes for transport medium containing CO2 in oil and gas engineering. Therefore this study of corrosion behavior and its properties of GFRP pipes in CO2 medium enviromental conditions is provided with significance. In this paper, aromatic amine curing and anhydride curing epoxy GFRP pipes as pipes were choosed for corrosion tests in medium containing crude oil, CO2 and water in laboratory. The change in the functionl groups located in the inner surface of the two kinds of GFRP pipes before and after corrosion were analyzed by IR. The change in the elements and functionl groups of the two kinds of GFRP pipes before and after corrosion were analyzed by XPS. The change in the thermal effects and Tg of the two kinds of GFRP pipes before and after corrosion were analyzed by DTA. The change in morphology of the surface and morphology of different delamination depth of the two kinds of GFRP pipes before and after corrosion were analyzed by SEM. The change in the ring stiffness, barcol hardness, resin content, degree of curing, density and other properties of the two kinds of GFRP pipes before and after corrosion were analyzed. By the results of these analyses to explore chemical corrosion reactions and physical corrosion process of the two kinds of GFRP pipes in CO2 corrosion environment. To study the influence of different pressures on the corrosion extent and physical and mechanical properties of the two kinds of GFRP pipes in CO2 corrosion environment. The results showed that the number of hydroxy (-OH) decreased and the number of C-O-C increased of aromatic amine curing and anhydride curing epoxy GFRP pipes, and the number of carbonyl (C=O) of anhydride curing epoxy GFRP pipes decreased slightly, but the change in the number of these functional groups were not large. Peviously, either of the two kinds of GFRP pipes suffered a chemical corrosion in the CO2 corrosion environment, but not serious. It is inferred that chemical corrosion mainly were CO2 with the hydroxy (-OH) of the surface of the pipes occured the chemical reaction, to produce the C-O-C at the same time also had water, and the part of the carbonyl (C=O) of the anhydride curing GFRP pipe occured the reaction too. The SEM analysis showed that the two kinds of GFRP pipes suffered a physical corrosion in CO2 medium environment. The inner surface of the corroded pipes were rough, uneven, more defects appeared, the defects became lager, deeper, even micro-cracks appeared, the resin sheded and the fiber exposed out, and ring stiffness, barcol hardness, degree of curing, resin content, density and Tg had a certain degree of reduction. It is inferred that
硕士学位论文
玻璃钢在 CO2 环境中的腐蚀 行为及其性能研究
THE RESEARCH OF CORROSION BEHAVIOR AND ITS PROPERTIES OF GFRP IN CO2 ENVIROMENT
周立娜
哈尔滨工业大学 2012 年 7 月
国内图书分类号：TB332 国际图书分类号：620
Candidate： Supervisor： Academic Degree Applied for： Speciality： Affiliation： Date of Defence： Degree-Conferring Institution：
Zhou Lina Associate Prof. Ju Chunhua Master of Science in Engineering Materials Science School of Material Sci. & Eng. July, 2012 Harbin Institute文
摘
要
玻璃钢(以下简称 GFRP, Glsss Fiber Reinforced Plastic)，由于其优异的综合性 能而被广泛用做石油天然气的集输管材，但关于输送含 CO2 介质油气管材腐蚀问 题的研究及相关报导尚少。因此关于 GFRP 管材在 CO2 介质环境条件下的腐蚀行 为及其性能的研究具有重要意义。 本文采用芳胺固化和酸酐固化两种固化类型的环氧玻璃钢管材为试验研究对 象，在实验室的条件下进行 GFRP 管材在含有原油、CO2 和水介质中的腐蚀试 验。利用红外光谱分析腐蚀前后两种 GFRP 管材的内表面树脂官能团的变化；利 用 XPS 分析两种 GFRP 管材腐蚀前后元素及其官能团的变化；利用 DTA 分析两 种 GFRP 管材腐蚀前后的热效应和 Tg 的变化；利用 SEM 分析两种 GFRP 管材腐 蚀前后的表面形貌变化和不同剥层深度处的形貌变化；测定分析两种 GFRP 管材 腐蚀前后的环刚度、巴氏硬度、树脂含量、固化度、密度等性能的变化。通过这 些分析结果来探讨两种 GFRP 管材在 CO2 环境中化学腐蚀反应及物理腐蚀过程； 研究不同的压力对两种 GFRP 管材在 CO2 腐蚀环境中的腐蚀程度和物理力学性能 的影响。 试验研究表明，芳胺固化和酸酐固化两种环氧玻璃钢管材的羟基 (-OH) 减 少，C-O-C 官能团有所增加，且酸酐固化 GFRP 管材的羰基(C=O)数量也略有减 少，但是这些官能团的数量变化不大。可见在 CO2 腐蚀环境中，两种玻璃钢管材 发生了化学腐蚀反应，但是化学腐蚀作用非常微弱。推断化学腐蚀主要是 CO2 与 管材表面的羟基(-OH)发生化学反应，产生了 C-O-C 官能团，同时有水的产生； 而且酸酐固化 GFRP 管材的部分羰基(C=O)也发生了反应。扫描电镜分析表明两 种 GFRP 管材在 CO2 介质环境中发生了物理腐蚀现象。腐蚀后管材内表面粗糙、 不平整，缺陷数量增加、增大、变深，甚至出现了微裂纹，表面的树脂发生脱 落，纤维裸露出来，环刚度、巴氏硬度、固化度、树脂含量、密度和玻璃化转变 温度 Tg 均有一定程度的降低。推断物理腐蚀作用主要有介质渗透扩散作用、CO2 “气体炸弹”效应、应力腐蚀效应、流体冲蚀作用等。压力是一个非常重要的环 境因素，具有加速腐蚀的作用。随着压力的增大，两种 GFRP 管材的腐蚀程度越 来越严重，性能也降低得越多。 关键词：GFRP；CO2；腐蚀行为；压力；腐蚀性能