微量元素La和Al-5Ti-1B复合细化Al-Cu机理

杨林洁; 张丽丽; 江鸿翔; 何杰; 赵九洲

doi:10.7498/aps.72.20222334

摘要

实验研究了复合添加微量元素La和Al-5Ti-1B对Al-Cu合金凝固组织的影响, 发现与单独添加Al-5Ti-1B相比, 复合添加Al-5Ti-1B和微量La可进一步细化Al-Cu合金凝固组织, 降低α-Al的形核过冷度. 结合高分辨透射电镜表征和理论计算, 探明了复合添加微量元素La和Al-5Ti-1B对Al-Cu合金凝固组织的细化机理: 经Al-5Ti-1B细化处理的Al-Cu合金凝固时, Cu富集于α-Al与TiB₂粒子的界面处, 增加了α-Al与TiB₂粒子间的错配度, 降低了TiB₂粒子对α-Al的异质形核能力; 添加微量的La能有效降低α-Al与TiB₂粒子间的错配度, 减小TiB₂粒子和α-Al间的界面能及接触角, 从而提高TiB₂粒子促进α-Al的异质形核能力和Al-5Ti-1B对Al-Cu合金晶粒的细化效果.

关键词:

晶粒细化 /
微量元素 /
富集 /
铝合金

Abstract

Grain refinement of aluminium alloys can not only reduce the defects (such as segregation and hot tearing) but also improve the mechanical properties. Adding Al-5Ti-1B master alloy to the melt has become a common method to refine the solidification microstructure of aluminium alloys. A lot of researches have been carried out to uncover the grain refining mechanisms as well as to show the microstructure formation under the effect of grain refiner. These researches demonstrated that the grain refining efficiency is closely related to the number density of TiB₂ particles as well as the solute Ti concentration in the melt. However, there exist still problems to be resolved, such as the limited grain refinement potency of Al-5Ti-1B master alloy. Recently, the addition of trace La to the melt has attracted much attention to control the microstructure of aluminium alloys. The Al-Cu alloys are widely applied to the automobile and aerospace fields due to their high strength, good ductility and high temperature properties. It has been reported that Cu can segregate to Al/TiB₂ interface in the Al-Cu melt inoculated with Al-5Ti-1B master alloy. But the effect of Cu segregation on the grain refinement result is not clear yet. Meanwhile, whether the grain refinement effect of Al-5Ti-1B master alloy on Al-Cu alloy can be improved by the addition of trace La has not been reported.Solidification experiments are carried out for Al-2Cu alloy with the addition of Al-5Ti-1B master alloy+ trace La. The synergistic effect of trace La and Al-5Ti-1B on the solidification microstructure of Al-2Cu alloy is investigated. It is found that trace La can effectively enhance the refinement result of Al-2Cu alloy and further diminish the nucleation undercooling. Experimental and calculated results demonstrate that solute Cu segregates to the Al/TiB₂ interface and thus increases the interatomic spacing mismatch between Ti (0001) plane of the TiB₂ particles and the interfacial monolayer, while La segregation reduces the interatomic spacing mismatch. The trace La addition reduces the interfacial energy between α-Al and TiB₂ particles, improves the potency of TiB₂ particles to nucleate α-Al, and thus enhances the grain refinement result of Al-5Ti-1B master alloy.

Keywords:

作者及机构信息

1.
中国科学院金属研究所, 师昌绪先进材料创新中心, 沈阳　110016

2.
中国科学技术大学材料科学与工程学院, 沈阳　110016

通信作者: 张丽丽, llzhang@imr.ac.cn ; 赵九洲, jzzhao@imr.ac.cn

基金项目: 国家重点研发计划(批准号: 2021YFA0716303)、中国载人航天工程和国家自然科学基金(批准号: 51901231, 51971227)资助的课题.

Authors and contacts

1.
Shi-changxu Innovation Centre for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

2.
School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

Corresponding author: Zhang Li-Li, llzhang@imr.ac.cn ; Zhao Jiu-Zhou, jzzhao@imr.ac.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2021YFA0716303), the China Manned Space Station Project, and the National Natural Science Foundation of China (Grant Nos. 51901231, 51971227).

文章全文 : translate this paragraph

参考文献

[1]	张丽丽 2017 博士学位论文 (沈阳: 中国科学院大学) Zhang L L 2017 Ph. D. Dissertation (Shenyang: University of Chinese Academy of Sciences) (in Chinese)
[2]	Greer A L, Bunn A M, Tronche A, Evans P V, Bristow D J 2000 Acta Mater. 48 2823 Google Scholar
[3]	Quested T E, Greer A L 2004 Acta Mater. 52 3859 Google Scholar
[4]	Quested T E, Greer A L 2005 Acta Mater. 53 4643 Google Scholar
[5]	Easton M A, StJohn D H 2001 Acta Mater. 49 1867 Google Scholar
[6]	Easton M A, StJohn D H 2005 Metall. Mater. Trans. A 36 1911 Google Scholar
[7]	Easton M A, StJohn D H 2008 Mater. Sci. Eng. A 486 8 Google Scholar
[8]	Fan Z, Wang Y, Zhang Y, Qin T, Zhou X R, Thompson G E, Pennycook T, Hashimoto T 2015 Acta Mater. 84 292 Google Scholar
[9]	Cibula A 1951 J. Inst. Met. 80 1
[10]	Crossley F A, Mondolfo L F 1951 JOM. 3 1143 Google Scholar
[11]	Jones G P, Jones H 1987 Solidification Processing (Sheffield: University of Sheffield) p496
[12]	Mohanty P S, Gruzleski J E 1995 Acta Metall. Mater. 43 2001 Google Scholar
[13]	Fan Z Y 2013 Metall. Mater. Trans. A 44 1409 Google Scholar
[14]	Maxwell I, Hellawell A 1975 Acta Metall. 23 229 Google Scholar
[15]	Zhang L L, Zheng Q J, Jiang H X, Zhao J Z 2019 Scr. Mater. 160 25 Google Scholar
[16]	Li J H, Hage F S, Ramasse Q M, Schumacher P 2021 Acta Mater. 206 116652 Google Scholar
[17]	吴俊子, 贾锦玉, 姜佳鑫 2018 稀土信息 2 30 Wu J Z, Jia J Y, Jiang J X 2018 Rare Earth Inform. 2 30
[18]	韩延峰 2007 博士学位论文 (上海: 上海交通大学) Han Y F 2007 Ph. D. Dissertation (Shanghai: Shanghai Jiao Tong University) (in Chinese)
[19]	Zhang Z, Bian X, Wang Y, Liu, X 2003 Mater. Sci. Eng. A 352 8 Google Scholar
[20]	李克, 饶磊, 闫洪, 王俊, 孙宝德 2006 铸造 9 894 Li K, Rao L, Yan H, Wang J, Sun B D 2006 Foundry 9 894
[21]	董天顺, 崔春翔, 刘双进, 刘福才 2008 稀有金属材料与工程 1 29 Dong T S, Cui C X, Liu S J, Liu F C 2008 Rare Metal Mater. Eng. 1 29
[22]	Wang Z J, Si N C 2015 Rare Metal Mater. Eng. 44 2970 Google Scholar
[23]	Ma T F, Chen Z Y, Nie Z R, Huang H 2013 J. Rare Earths 31 622 Google Scholar
[24]	Wang K, Cui C X, Wang Q, Liu S, Gu C 2012 Mater. Lett. 85 153 Google Scholar
[25]	Wang K, Cui C X, Wang Q, Zhao L, Hu Y 2013 J. Rare Earths 31 313 Google Scholar
[26]	Zhang L L, Song Y, Yang L J, Zhao J Z, He J, Jiang H X 2022 Materials 15 600 Google Scholar
[27]	Zhang M X, Kelly P M, Easton M A, Taylor J A 2005 Acta Mater. 53 1427 Google Scholar
[28]	Wang Y, Fang C M, Zhou L, Hashimoto T, Fan Z 2018 Acta Mater. 164 428 Google Scholar
[29]	Iida T, Guthrie R I L 1993 The Physical Properties of Liquid Metals (Oxford: Clarendon Press) p71
[30]	Fan T X, Yang G, Zhang D 2005 Metall. Mater. Trans. A 36 225 Google Scholar
[31]	Dinsdale A T 1991 Calphad. 15 317 Google Scholar
[32]	李淑波, 杜文博, 王旭东, 刘轲, 王朝辉 2018 金属学报 54 911 Google Scholar Li S B, Du W B, Wang X D, Liu K, Wang C H 2018 Acta Metall. Sin. 54 911 Google Scholar
[33]	Zhang L L, Jiang H X, He J, Zhao J Z 2020 Scr. Mater. 179 99 Google Scholar
[34]	Okamoto H 2013 J. Phase Equilib. Diffus. 34 493 Google Scholar
[35]	Elliott R P, Shunk F A 1981 Bull. Alloy Phase Diagrams 2 219 Google Scholar

施引文献

图 1 Al-2Cu和不同La添加量下经0.4% Al-5Ti-1B中间合金细化处理的Al-2Cu合金晶粒平均尺寸和微观组织的OM像

Fig. 1. Average size of α-Al grains and OM images of the Al-2Cu alloys without addition of inoculant, inoculated with 0.4% Al-5Ti-1B and inoculated with 0.4% Al-5Ti-1B + 0.08% La.

下载: 全尺寸图片幻灯片

图 2 添加1% Al-5Ti-1B的Al-2Cu合金的TEM像及元素分布图　(a) 低倍TEM像; (b)—(e) 元素Al (b), Cu (c), Ti (d), B (e)分布图; (f) TiB₂粒子的高倍TEM像, 其中插图为元素Al, Cu和Ti在蓝框内的平均电子能量损失谱线

Fig. 2. TEM image and elemental maps in the Al-2Cu alloy inoculated by 1% Al-5Ti-1B: (a) TEM image at low magnification; (b)–(e) elemental maps of Al (b), Cu (c), Ti (d), B (e); (f) TEM image at high magnification of TiB₂ particles, where inset shows the electron energy loss spectroscopy line profiles of elements Al, Cu and Ti averaged over the area indicated in Fig. (f) by blue box

下载: 全尺寸图片幻灯片

图 3 (a) 添加1% Al-5Ti-1B + 0.08% La的Al-2Cu合金的高倍TEM像; (b)—(e) 元素Al (b), Cu (c), Ti (d), La (e)的X射线能量散谱图; (f) Al, Cu, Ti和La元素的电子能量损失谱线

Fig. 3. (a) TEM image at high magnification in Al-2Cu alloy inoculated by 1% Al-5Ti-1B + 0.08% La; (b)–(e) energy dispersive X-ray spectroscopy maps of Al (b), Cu (c), Ti (d), La (e); (f) electron energy loss spectroscopy line profiles of elements Al, Cu, Ti and La averaged over the area indicated in (a) by pink box of TiB₂ particles.

下载: 全尺寸图片幻灯片

图 4 添加1% Al-5Ti-1B + 0% La (a)和1% Al-5Ti-1B +0.08% La (b)的Al-2Cu合金HRTEM像; (c) TiB₂粒子中Ti (0001)面与界面单原子层间界面示意图

Fig. 4. HRTEM images showing the basal plane (0001) of TiB₂ in Al-2Cu alloy inoculated with 1% Al-5Ti-1B + 0% La (a) and 1% Al-5Ti-1B +0.08%La (b), respectively; (c) schematic illustration of interface between the Ti (0001) plane of TiB₂ surface and the monolayer

下载: 全尺寸图片幻灯片

图 5 经0.4% Al-5Ti-1B细化处理的Al-2Cu合金的DTA升温(虚线)和冷却(实线)曲线, 其中T_m 和T_n分别为合金的熔点和开始形核温度, T_m = 926.2K; 插图为α-Al的形核过冷度ΔT_Heter

Fig. 5. DTA heating (dashed line) and cooling (solid line) curves for the Al-2Cu alloys with the addition of 0.4% Al-5Ti-1B master alloy. T_n and T_m = 926.2K are respectively the nucleation temperature of α-Al and the melting point temperature of Al. Inset shows the undercooling ΔT_Heter.

下载: 全尺寸图片幻灯片

图 6 微量La添加量对经0.4%Al-5Ti-1B细化处理的Al-2Cu合金生长限制因子的影响

Fig. 6. Effect of trace La addition on the growth restriction factor of Al-2Cu alloy inoculated with 0.4% Al-5Ti-1B master alloy.

下载: 全尺寸图片幻灯片

表 1 (13)式中涉及的参数

Table 1. Parameters used in Eq. (13).

i k_i m_i/(K·%^–1) $ {c'_{{\text{S}}i}}/\% $ $ {c'_{{\text{L}}i}}/\% $ Reference

Ti 7.8 33.3 — — [12]
Cu 0.17 –3.4 5.69 32.5 [34]
La 0.004 –1.71 0.05 11.7 [35]

下载: 导出CSV

[1]	张丽丽 2017 博士学位论文 (沈阳: 中国科学院大学) Zhang L L 2017 Ph. D. Dissertation (Shenyang: University of Chinese Academy of Sciences) (in Chinese)
[2]	Greer A L, Bunn A M, Tronche A, Evans P V, Bristow D J 2000 Acta Mater. 48 2823 Google Scholar
[3]	Quested T E, Greer A L 2004 Acta Mater. 52 3859 Google Scholar
[4]	Quested T E, Greer A L 2005 Acta Mater. 53 4643 Google Scholar
[5]	Easton M A, StJohn D H 2001 Acta Mater. 49 1867 Google Scholar
[6]	Easton M A, StJohn D H 2005 Metall. Mater. Trans. A 36 1911 Google Scholar
[7]	Easton M A, StJohn D H 2008 Mater. Sci. Eng. A 486 8 Google Scholar
[8]	Fan Z, Wang Y, Zhang Y, Qin T, Zhou X R, Thompson G E, Pennycook T, Hashimoto T 2015 Acta Mater. 84 292 Google Scholar
[9]	Cibula A 1951 J. Inst. Met. 80 1
[10]	Crossley F A, Mondolfo L F 1951 JOM. 3 1143 Google Scholar
[11]	Jones G P, Jones H 1987 Solidification Processing (Sheffield: University of Sheffield) p496
[12]	Mohanty P S, Gruzleski J E 1995 Acta Metall. Mater. 43 2001 Google Scholar
[13]	Fan Z Y 2013 Metall. Mater. Trans. A 44 1409 Google Scholar
[14]	Maxwell I, Hellawell A 1975 Acta Metall. 23 229 Google Scholar
[15]	Zhang L L, Zheng Q J, Jiang H X, Zhao J Z 2019 Scr. Mater. 160 25 Google Scholar
[16]	Li J H, Hage F S, Ramasse Q M, Schumacher P 2021 Acta Mater. 206 116652 Google Scholar
[17]	吴俊子, 贾锦玉, 姜佳鑫 2018 稀土信息 2 30 Wu J Z, Jia J Y, Jiang J X 2018 Rare Earth Inform. 2 30
[18]	韩延峰 2007 博士学位论文 (上海: 上海交通大学) Han Y F 2007 Ph. D. Dissertation (Shanghai: Shanghai Jiao Tong University) (in Chinese)
[19]	Zhang Z, Bian X, Wang Y, Liu, X 2003 Mater. Sci. Eng. A 352 8 Google Scholar
[20]	李克, 饶磊, 闫洪, 王俊, 孙宝德 2006 铸造 9 894 Li K, Rao L, Yan H, Wang J, Sun B D 2006 Foundry 9 894
[21]	董天顺, 崔春翔, 刘双进, 刘福才 2008 稀有金属材料与工程 1 29 Dong T S, Cui C X, Liu S J, Liu F C 2008 Rare Metal Mater. Eng. 1 29
[22]	Wang Z J, Si N C 2015 Rare Metal Mater. Eng. 44 2970 Google Scholar
[23]	Ma T F, Chen Z Y, Nie Z R, Huang H 2013 J. Rare Earths 31 622 Google Scholar
[24]	Wang K, Cui C X, Wang Q, Liu S, Gu C 2012 Mater. Lett. 85 153 Google Scholar
[25]	Wang K, Cui C X, Wang Q, Zhao L, Hu Y 2013 J. Rare Earths 31 313 Google Scholar
[26]	Zhang L L, Song Y, Yang L J, Zhao J Z, He J, Jiang H X 2022 Materials 15 600 Google Scholar
[27]	Zhang M X, Kelly P M, Easton M A, Taylor J A 2005 Acta Mater. 53 1427 Google Scholar
[28]	Wang Y, Fang C M, Zhou L, Hashimoto T, Fan Z 2018 Acta Mater. 164 428 Google Scholar
[29]	Iida T, Guthrie R I L 1993 The Physical Properties of Liquid Metals (Oxford: Clarendon Press) p71
[30]	Fan T X, Yang G, Zhang D 2005 Metall. Mater. Trans. A 36 225 Google Scholar
[31]	Dinsdale A T 1991 Calphad. 15 317 Google Scholar
[32]	李淑波, 杜文博, 王旭东, 刘轲, 王朝辉 2018 金属学报 54 911 Google Scholar Li S B, Du W B, Wang X D, Liu K, Wang C H 2018 Acta Metall. Sin. 54 911 Google Scholar
[33]	Zhang L L, Jiang H X, He J, Zhao J Z 2020 Scr. Mater. 179 99 Google Scholar
[34]	Okamoto H 2013 J. Phase Equilib. Diffus. 34 493 Google Scholar
[35]	Elliott R P, Shunk F A 1981 Bull. Alloy Phase Diagrams 2 219 Google Scholar

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微量元素La和Al-5Ti-1B复合细化Al-Cu机理