酸洗对ZTA15钛合金表面污染层及化学成分的影响

韩云飞; 孙冰; 刘义辉; 侯佩华; 袁兵兵; 乔海滨

doi:10.7513/j.issn.1004-7638.2023.03.011

酸洗对ZTA15钛合金表面污染层及化学成分的影响

doi: 10.7513/j.issn.1004-7638.2023.03.011

韩云飞^{1, 2,},
孙冰^{1, 2},
刘义辉^{1, 2},
侯佩华^{1, 2},
袁兵兵^{1, 2},
乔海滨^{1, 2}

1.
洛阳双瑞精铸钛业有限公司, 河南洛阳471000
2.
中国船舶集团有限公司第七二五研究所, 河南洛阳471000

基金项目: 国家重点研发计划项目（2020YFB2008300,2020YFB2008301）。

详细信息

作者简介:
韩云飞，1988年出生，男，河南南阳人，硕士，工程师，研究方向：铸造钛合金，E-mail: 337668161@qq.com

中图分类号: TF823
计量
- 文章访问数: 88
- HTML全文浏览量: 12
- PDF下载量: 9
- 被引次数: 0
出版历程
- 收稿日期: 2023-02-14
- 刊出日期: 2023-06-30

Effect of pickling on surface contamination layer and chemical composition of ZTA15 titanium alloy

Han Yunfei^{1, 2
,},
Sun Bing^{1, 2},
Liu Yihui^{1, 2},
Hou Peihua^{1, 2},
Yuan Bingbing^{1, 2},
Qiao Haibin^{1, 2}

1.
Luoyang Sunrui Titanium Precision Casting Co., Ltd., Luoyang 471000, Henan, China
2.
Luoyang Ship Material Research Institute, Luoyang 471000, Henan, China

摘要

摘要: 利用熔模精密铸造技术制备了ZTA15钛合金试棒。采用金相法观察和测定表面污染层厚度，制定酸洗量。酸洗前后，使用2点直径测量法和金相法确定污染层去除情况；酸洗后进行真空退火，从3种状态试棒表面取样进行化学成分试验，检测氢、氧含量的变化情况，研究了酸洗对ZTA15钛合金表面污染层及化学成分的影响。结果表明，ZTA15钛合金表面污染层厚度为0.1 ～0.2 mm，当酸洗液中氢氟酸、硝酸和热水按照30%∶30%∶40%的质量比配制、温度40～60 ℃、酸洗时间60 min以内、酸洗量0.25 mm±0.05 mm时，可以彻底去除硬度高、塑性低的α污染层，避免在后续变形或受力时导致脆化或产生裂纹，提高其使用性能。ZTA15钛合金酸洗后表面有轻微的吸氢，氧含量无明显变化，经真空退火后又有析氢，表面氢含量始终满足＜0.01%的要求，不会产生氢脆等对成分性能不利的情况。
- ZTA15钛合金 /
- 酸洗 /
- 表面污染层 /
- 化学成分
Abstract: The ZTA15 titanium alloy test bars were prepared by investment casting technology. The thickness of the surface contamination layer was observed and measured by metallography, and then the pickling amount was determined. Before and after pickling, the removal of the contaminated layer was determined by the two-point diameter measurement and metallographic method. After pickling treatment, vacuum annealing was also carried out. The chemical composition was tested from the surface of test bars in three states to detect the change of hydrogen and oxygen content. The effect of acid pickling on the surface contamination layer and chemical composition of ZTA15 titanium alloy was studied. The results show that the thickness of the contaminated layer on the surface of ZTA15 titanium alloy is 0.1～0.2 mm. When hydrofluoric acid, nitric acid and hot water in the pickling solution are prepared according to the mass ratio of 30%: 30%: 40%, the temperature is 40～60 ℃, the pickling time is within 60 min, and the pickling amount is (0.25±0.05 )mm, the α contaminated layer with high hardness and low plasticity can be completely removed to avoid embrittlement or crack during subsequent deformation or stress, and improve its service performance. After pickling, the surface of ZTA15 titanium alloy has slight hydrogen absorption, no obvious change in oxygen content. Hydrogen evolution occurs after vacuum annealing, but the hydrogen content on the surface always meets the requirement of <0.01%. Hydrogen embrittlement and other adverse conditions on the composition performance are not to be generated.
- ZTA15 titanium alloy /
- pickling /
- surface contamination layer /
- chemical composition

HTML全文

图 1 ZTA15钛合金铸态试棒

Figure 1. ZTA15 titanium alloy as-cast test bars

下载: 全尺寸图片幻灯片

图 2 ZTA15钛合金酸洗前表面污染层

(a)酸洗前−1，污染层120 μm;(b)酸洗前−2，污染层167 μm; (c)酸洗前−3，污染层96 μm; (d)酸洗前−4，污染层121 μm

Figure 2. Surface contamination layer of ZTA15 titanium alloy before pickling

下载: 全尺寸图片幻灯片

图 3 ZTA15钛合金酸洗后表面污染层

(a)酸洗后−1，污染层0 μm; (b)酸洗后−2，污染层0 μm; (c)酸洗后−3，污染层0 μm; (d)酸洗后−4，污染层0 μm

Figure 3. Surface contamination layer of ZTA15 titanium alloy after pickling

下载: 全尺寸图片幻灯片

表 1 试棒酸洗前后2点直径测量

Table 1. Diameter measurement at two points before and after pickling

试棒标记	酸洗前直径T₁/mm		酸洗后直径T₂/mm		酸洗量 (T₁-T₂)/mm		平均酸洗量[(T₁-T₂)/2]/mm
试棒标记	测点1	测点2	测点1	测点2	测点1	测点2	平均酸洗量[(T₁-T₂)/2]/mm
1	14.87	14.84	14.36	14.36	0.51	0.48	0.25
2	14.88	14.83	14.37	14.35	0.51	0.48	0.25
3	14.66	14.62	14.16	14.16	0.50	0.46	0.24
4	14.76	14.70	14.26	14.20	0.50	0.50	0.25

下载: 导出CSV

表 2 ZTA15钛合金酸洗前后及酸洗+退火后的表面氧氢化学成分

Table 2. Chemical composition of oxygen and hydrogen on the surface of ZTA15 titanium alloy before and after pickling and after pickling + annealing %

试棒标记	酸洗前		酸洗后		酸洗+退火后
试棒标记	氧	氢	氧	氢	氧	氢
1	0.127	0.0016	0.154	0.0053	0.118	0.0034
2	0.152	0.0022	0.160	0.0091	0.127	0.0015
3	0.160	0.0025	0.138	0.0039	0.153	0.0014
4	0.117	0.0021	0.141	0.0080	0.138	0.0035

下载: 导出CSV

参考文献(13)

[1]	莫畏. 钛[M]. 北京: 冶金工业出版社, 2008. Mo Wei. Titanium[M]. Beijing: Metallurgical Industry Press, 2008.
[2]	谢成木. 钛及钛合金铸造[M]. 北京: 机械工业出版社, 2005. Xie Chengmu. Titanium and titanium alloy casting[M]. Beijing: China Machine Press, 2005.
[3]	王桂生. 钛的应用技术[M]. 长沙: 中南大学出版社, 2007. Wang Guisheng. Application technology of titanium[M]. Changsha: Central South University Press, 2007.
[4]	张喜燕, 赵永庆, 白晨光. 钛合金及应用[M]. 北京: 化学工业出版社, 2005. Zhang Xiyan, Zhao Yongqing, Bai Chenguang. Titanium alloy and its application[M]. Beijing: Chemical Industry Press, 2005.
[5]	周彦邦. 钛及钛合金铸造概论[M]. 北京: 航空工业出版社, 2000. Zhou Yanbang. Introduction to titanium alloy casting[M]. Beijing: Aviation Industry Press, 2000.
[6]	陶春虎, 刘庆, 曹春晓. 航空用钛合金的失效及其预防[M]. 北京: 国防工业出版社, 2002. Tao Chunhu, Liu Qing, Cao Chunxiao. Failure and prevention of titanium alloys for aviation[M]. Beijing: National Defense Industry Press, 2002.
[7]	Zhao Jiaqi, Wu Guoqing, Cheng Xiangjun, et al. Effect of α contamination layer on impact properties of as cast ZTC4 titanium alloy specimen[J]. Materials Engineering, 2013,(6):59−62. (赵嘉琪, 吴国清, 程祥军, 等. α污染层对ZTC4钛合金铸态试样冲击性能的影响[J]. 材料工程, 2013,(6):59−62. doi: 10.3969/j.issn.1001-4381.2013.06.012 Zhao Jiaqi, Wu Guoqing, Cheng Xiangjun, et al. Effect of α contamination layer on impact properties of as cast ZTC4 titanium alloy specimen[J]. Materials Engineering, 2013(6): 59-62. doi: 10.3969/j.issn.1001-4381.2013.06.012
[8]	Gaddam R, Antti M L, Pederson R. Influence of alpha-case layer on the low cycle fatigue properties of Ti-6Al-2Sn-4Zr-2Mo alloy[J]. Materials Science and Engineering A, 2014,599:51−56. doi: 10.1016/j.msea.2014.01.059
[9]	Wang Zhonghua. Pickling process of supper-long Gcr12 tube[J]. Rare Matals Letters, 2008,(2):31−33. (王中华. Gr12钛合金特长管酸洗工艺研究[J]. 稀有金属快报, 2008,(2):31−33. Wang Zhonghua. Pickling process of supper-long Gcr12 tube[J]. Rare Matals Letters, 2008(2): 31-33.
[10]	Guan Hongbo, Cheng Yuxin. Analysis of titanium alloy pickling bath solution[J]. Xifei Technology, 1999,(2):80−82. (关宏波, 程雨信. 钛合金酸洗槽液分析[J]. 西飞科技, 1999,(2):80−82. Guan Hongbo, Cheng Yuxin. Analysis of titanium alloy pickling bath solution[J]. Xifei Technology, 1999(2): 80-82.
[11]	Xu Yali, Lu Xiaoyang, Zhang Binbin, et al. α distribution analysis of hydrogen element in Ti-6Al-3Nb-2Zr-1Mo type titanium alloy[J]. Material Development and Application, 2020,35(6):7−12. (许亚利, 卢晓阳, 张斌斌, 等. 近α型钛合金Ti-6Al-3Nb-2Zr-1Mo中氢元素的分布分析[J]. 材料开发与应用, 2020,35(6):7−12. Xu Yali, Lu Xiaoyang, Zhang Binbin, et al. α distribution analysis of hydrogen element in Ti-6 Al-3 Nb-2 Zr-1 Mo type titanium alloy[J]. Material Development and Application, 2020, 35(6): 7-12.
[12]	Zhang Jiepin, Min Xinhua. Effect of impurity elements N, O, Fe on the properties and microstructure of TA15 titanium alloy[J]. Material Development and Application, 2013,28(2):83−86. (张捷频, 闵新华. 杂质元素N、O、Fe对TA15钛合金性能和组织的影响[J]. 材料开发与应用, 2013,28(2):83−86. doi: 10.19515/j.cnki.1003-1545.2013.02.019 Zhang Jiepin, Min Xinhua. Effect of impurity elements N, O, Fe on the properties and microstructure of TA15 titanium alloy[J]. Material Development and Application, 2013, 28(2): 83-86. doi: 10.19515/j.cnki.1003-1545.2013.02.019
[13]	Cheng Jingtao, Guo Tianwen. Pickling of pure titanium casting surface[J]. Journal of Modern Stomatology, 2000,14(5):323−325. (程静涛, 郭天文. 纯钛铸件表面的酸洗[J]. 现代口腔医学杂志, 2000,14(5):323−325. doi: 10.3969/j.issn.1003-7632.2000.05.015 Cheng Jingtao, Guo Tianwen. Pickling of pure titanium casting surface[J]. Journal of Modern Stomatology, 2000, 14(5): 323-325. doi: 10.3969/j.issn.1003-7632.2000.05.015