钛合金表面磷酸盐涂层的制备及在高温盐-水蒸气环境中的腐蚀行为研究

doi:10.11902/1005.4537.2023.064

中国腐蚀与防护学报

2024, Vol. 44

Issue (1): 159-166 CSTR: 32134.14.1005.4537.2023.064 DOI: 10.11902/1005.4537.2023.064

研究报告

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钛合金表面磷酸盐涂层的制备及在高温盐-水蒸气环境中的腐蚀行为研究

李建呈¹, 赵京², 谢新³, 王金龙¹(

), 陈明辉¹, 王福会¹

^1.东北大学沈阳材料科学国家研究中心腐蚀与防护研究部沈阳 110819
^2.中国核动力研究设计院成都 610213
^3.上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) 上海 200032

Preparation of Phosphate Coatings on Ti-alloy and Their Corrosion Behavior Beneath Salt-mixture in Water Vapor Flow at 650^oC

LI Jiancheng¹, ZHAO Jing², XIE Xin³, WANG Jinlong¹(

), CHEN Minghui¹, WANG Fuhui¹

^1.Corrosion and Protection Division, Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China
^2.Nuclear Power Institute of China, Chengdu 610213, China
^3.Shipbuilding Technology Research Institute (The 11th Institute of China State Shipbuilding Corporation), Shanghai 200032, China

引用本文:

李建呈, 赵京, 谢新, 王金龙, 陈明辉, 王福会. 钛合金表面磷酸盐涂层的制备及在高温盐-水蒸气环境中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2024, 44(1): 159-166.
Jiancheng LI, Jing ZHAO, Xin XIE, Jinlong WANG, Minghui CHEN, Fuhui WANG. Preparation of Phosphate Coatings on Ti-alloy and Their Corrosion Behavior Beneath Salt-mixture in Water Vapor Flow at 650^oC[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(1): 159-166.

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摘要:

以硅溶胶为成膜改性物，Al(H₂PO₄)₃为成膜物，陶瓷相为填料并辅以助剂设计了硅溶胶改性磷酸盐涂层。结果表明，硅溶胶对磷酸盐涂层固化过程中玻璃相的形成具有促进作用，当成膜物中硅溶胶与Al(H₂PO₄)₃质量比达到1∶1时，成膜物为完全的玻璃相，进而获得致密的磷酸盐涂层。以硅溶胶改性磷酸盐涂层作为钛合金的高温防护涂层，在650℃盐水蒸气介质中对其腐蚀行为进行了研究。结果表明，改性磷酸盐涂层为钛合金提供了优异的耐高温盐水蒸气腐蚀性能，成膜物和填料的化学稳定性是改性涂层耐蚀的根本因素。涂层在650℃盐水蒸气环境下腐蚀100 h后依然致密，未出现基体合金的腐蚀，填料中Al片及其腐蚀产物在涂层中平行于基体排列，可有效阻碍Cl^-等有害离子向基体的扩散，与Na₂SO₄反应则抑制了熔融盐向涂层内部的侵入及其对钛合金基体的侵蚀。

关键词 ：磷酸盐涂层, 改性, 钛合金, 高温腐蚀

Abstract：

Phosphate coatings, composed of silica sol modified Al(H₂PO₄)₃, ceramic fillers and additives, are prepared and then applied on Ti-6Al-4V alloy, which are further characterized by means of XRD and Fourier transform infrared spectrometer, as well as corrosion test beneath deposits of salt-mixture in vapor flow at 650^oC. The results show that silica sol can promote the formation of glass phase while the phosphate coating curing. When the mass ratio of silica sol to Al(H₂PO₄)₃ reaches 1∶1, the mixture of silica sol to Al(H₂PO₄)₃ may produce_{a film of complete glass phase which ensures the formation a completely dense phosphate coating. The modified phosphate coating provides excellent corrosion resistance to salt-mixture in vapor flow at 650^oC, and the chemical stability of the film and filler is the vital factor of the corrosion resistance of the modified coating. The coating is still dense after 100 h of corrosion at 650^oC in such environment, and rare corrosion products of elements of the matrix alloy appears. As one filler of small amount, the Al flakes and their corrosion products are arranged parallel to the matrix in the coating, which can effectively prevent the diffusion of harmful ions such as Cl^- to the matrix, meanwhile which can react with Na₂SO₄ so that inhibit the intrusion of molten salt into the coating and the corrosion of Ti-alloy matrix.}

Key words： phosphate coating modify Ti-alloy high temperature corrosion

收稿日期: 2023-03-10 32134.14.1005.4537.2023.064

ZTFLH:

TG174

通讯作者: 王金龙，E-mail：wangjinlong@mail.neu.edu.cn，研究方向为高温防护涂层

Corresponding author: WANG Jinlong, E-mail: wangjinlong@mail.neu.edu.cn

作者简介: 李建呈，男，1997年生，硕士，助理研究员

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表1 3种成膜物成分 (mass fraction / %)

图1 高温水蒸气腐蚀实验装置示意图

图2 3种比例的成膜物的红外吸收光谱

图3 PSi3，PSi2，PSi1成膜物的XRD

图4 制备态硅溶胶改性磷酸盐涂层的表面与截面微观形貌以及截面EDS元素面分析

图5 制备态硅溶胶改性磷酸盐涂层的XRD图谱

图6 未涂覆和涂覆硅溶胶改性磷酸盐涂层的Ti-6Al-4V合金试样原始态及650℃盐-水蒸气环境中腐蚀100 h后的宏观形貌

图7 未涂覆和涂覆硅溶胶改性磷酸盐涂层的Ti-6Al-4V合金试样在650℃盐-水蒸气环境中腐蚀100h的动力学曲线

图8 硅溶胶改性磷酸盐涂层650℃盐-水蒸气环境腐蚀100 h后XRD图谱

图9 硅溶胶改性磷酸盐涂层在650℃盐-水蒸气环境中腐蚀100 h后表面和截面微观形貌及截面EDS元素面分析

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