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无机材料学报

无机材料学报 ›› 2023, Vol. 38 ›› Issue (5): 553-560.DOI: 10.15541/jim20220513

• 研究论文 • 上一篇    下一篇

Ca-B-Si体系LTCC材料腐蚀行为及腐蚀机理

罗淑文1,2(), 马名生2(), 刘峰2, 刘志甫2()   

  1. 1.上海师范大学 化学与材料科学学院, 上海 200234
    2.中国科学院 上海硅酸盐研究所, 上海 201899
  • 收稿日期:2022-09-02 修回日期:2022-10-10 出版日期:2022-12-27 网络出版日期:2022-12-27
  • 通讯作者: 马名生, 副研究员. E-mail: mamingsheng@mail.sic.ac.cn;
    刘志甫, 研究员. E-mail: liuzf@mail.sic.ac.cn
  • 作者简介:罗淑文(1998-), 女, 硕士研究生. E-mail: 1000497469@smail.shnu.edu.cn
  • 基金资助:
    国家自然科学基金(61971407);上海市青年科技启明星计划(20QA1410200)

Corrosion Behavior and Mechanism of LTCC Materials in Ca-B-Si System

LUO Shuwen1,2(), MA Mingsheng2(), LIU Feng2, LIU Zhifu2()   

  1. 1. College of Chemistry and Materials Science, Shanghai Normal University, Shanghai 200234, China
    2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
  • Received:2022-09-02 Revised:2022-10-10 Published:2022-12-27 Online:2022-12-27
  • Contact: MA Mingsheng, associate professor. E-mail: mamingsheng@mail.sic.ac.cn;
    LIU Zhifu, professor. E-mail: liuzf@mail.sic.ac.cn
  • About author:LUO Shuwen (1998-), female, Master candidate. E-mail: 1000497469@smail.shnu.edu.cn
  • Supported by:
    National Natural Science Foundation of China(61971407);Shanghai Rising-Star Program(20QA1410200)

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摘要：

LTCC材料在电镀和化学镀工艺中对酸/碱镀液的耐蚀性是低温共烧陶瓷(Low Temperature Co-fired Ceramics, LTCC)材料在实际应用中需要关注的重要特性。本工作研究了HCl、H2SO4和NaOH溶液(0.01~2.00 mol/L)和浸泡时间(10~300 min)对Ca-B-Si体系LTCC材料腐蚀行为的影响规律。结果表明，LTCC材料在不同的酸溶液中浸泡相同时间, 样品的腐蚀失重量会随着酸溶液浓度增大呈现出先增大后减小的趋势, 而在碱溶液中并未观察到明显的腐蚀现象。当盐酸溶液浓度为1.00 mol/L时, LTCC材料的失重最大为54.96%。当硫酸溶液浓度为0.10 mol/L时, LTCC材料的失重最大为8.80%LTCC材料中的CaB2O4和CaSiO3晶相会与酸溶液发生溶解反应进而造成腐蚀, 并且随着酸溶液浓度增大, 反应后样品表面富Si蚀变层的形成速度更快, 进而使LTCC材料在较高浓度酸溶液中的浸泡失重量减小。LTCC材料在1 mol/L 盐酸溶液和0.1 mol/L硫酸溶液中溶解反应的表观活化能分别为20.38、5.43 kJ/mol, 故盐酸溶液对LTCC材料的腐蚀速率大于硫酸溶液。结合化学腐蚀反应动力学和热力学分析, 揭示了LTCC材料在酸溶液中以离子交换和水解反应占主导的腐蚀机理。

关键词: 低温共烧陶瓷, 硼硅酸盐玻璃, 浸泡, 腐蚀机理

Abstract:

The corrosion resistance of LTCC (Low Temperature Co-fired Ceramics, LTCC) materials to acid/alkali bath in electroplating and electroless plating is an important characteristic that needs to be paid attention to in practical application. In this work, the effects of HCl, H2SO4 and NaOH concentration and immersion time on the corrosion behavior of Ca-B-Si based LTCC materials were studied. The results show that when LTCC samples are soaked in acid solution, the weight loss of samples increases firstly and then decreases with the increase of acid solution concentration. The weight loss in 1.00 mol/L hydrochloric acid solution is up to 54.96%, while that in 0.10 mol/L sulfuric acid solution is only 8.80%. However, no obvious corrosion is observed in the alkaline solution. The crystal phase of CaB2O4 and CaSiO3 in LTCC material dissolves in the acid solution to induce corrosion. With the increase of acid solution concentration, formation of Si-rich alteration layer on the surface of the sample after corrosion becomes faster, while the passivation alteration layer makes the weight loss in higher concentration of acid solution relatively low. Apparent activation energies of LTCC material in 1 mol/L hydrochloric acid solution, and 0.1 mol/L sulfuric acid solution are 20.38, 5.43 kJ/mol, respectively, indicating the corrosion rate of LTCC material in hydrochloric acid solution is higher than that in sulfuric acid solution. Combined with chemical corrosion reaction kinetics and thermodynamic results, this study reveales that the corrosion mechanism of LTCC materials in acid solution is dominated by ion exchange and hydrolysis reaction.

Key words: low temperature co-fired ceramics, borosilicate glass, soak, corrosion mechanism

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