界面热力学与晶界相图的研究进展

doi:10.11900/0412.1961.2021.00036

金属学报

2021, Vol. 57

Issue (9): 1199-1214 DOI: 10.11900/0412.1961.2021.00036

综述

本期目录 | 过刊浏览

界面热力学与晶界相图的研究进展

胡标¹, 张华清², 张金¹, 杨明军², 杜勇²(

), 赵冬冬³

^1.安徽理工大学材料科学与工程学院淮南 232001
^2.中南大学粉末冶金国家重点实验室长沙 410083
^3.天津大学材料科学与工程学院天津 300350

Progress in Interfacial Thermodynamics and Grain Boundary Complexion Diagram

HU Biao¹, ZHANG Huaqing², ZHANG Jin¹, YANG Mingjun², DU Yong²(

), ZHAO Dongdong³

^1.School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
^2.State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China
^3.School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China

引用本文:

胡标, 张华清, 张金, 杨明军, 杜勇, 赵冬冬. 界面热力学与晶界相图的研究进展[J]. 金属学报, 2021, 57(9): 1199-1214.
Biao HU, Huaqing ZHANG, Jin ZHANG, Mingjun YANG, Yong DU, Dongdong ZHAO. Progress in Interfacial Thermodynamics and Grain Boundary Complexion Diagram[J]. Acta Metall Sin, 2021, 57(9): 1199-1214.

全文: PDF(4420 KB) HTML

摘要:

晶界作为微观结构的重要组成部分，对材料的性能起着关键性的影响。晶界相变是准确阐述众多材料现象的重要信息。然而，由于晶界结构复杂、晶界相变观测困难等原因，迄今为止仍缺乏对这些材料现象的直接证据和机理解释。随着先进表征设备特别是球差校正透射电镜的发展，再加上功能强大的计算机模拟，建立界面热力学模型并构建不同类型的晶界相图，为晶界结构及晶界相变的研究提供了广阔的前景。本文从晶界与晶界相变的分类、表征、界面热力学模型、晶界相图的构建等方面，综述了界面热力学与晶界相图的研究进展，展望了该研究领域未来发展的重点及趋势。

关键词 ：晶界, 晶界相变, 界面热力学模型, 晶界相图

Abstract：

Grain boundaries (GBs), a crucial component of microstructures, have a significant influence on the properties of materials. The GB complexion (GBC) transitions are essential information to accurately explain numerous material phenomena. However, owing to the complexity of GB structures and the difficulty in observation of GBC transitions, there is still no direct evidence and mechanism explanation for these material phenomena. With the advancement of characterization equipment, especially spherical aberration-correction transmission electron microscopy, coupled with powerful computer simulation, the establishment of interfacial thermodynamic models to construct different types of GBC diagrams, which provide a broad prospect for the study of GB structures and GBC transitions, is essential. In this paper, the progress of interface thermodynamics and GBC diagrams from the aspects of the classification and characterization of GBs and GBC transitions, interface thermodynamic models, and the construction of GBC diagrams were reviewed. The paper also looks forward to the future development of interface thermodynamics and GBC diagrams.

Key words： grain boundary grain boundary complexion transition interface thermodynamic model grain boundary complexion diagram

收稿日期: 2021-01-21

ZTFLH:

TB113.14

基金资助:国家自然科学基金项目(52071002);安徽省自然科学基金项目(2008085QE200)

作者简介: 胡标，男，1985年生，教授，博士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00036 或 https://www.ams.org.cn/CN/Y2021/V57/I9/1199

图1 在未掺杂和掺杂的Al2O3中发现的6种Dillon-Harmer晶界相[26]，在金属材料中观察到的类似晶界相[12,27,37~39]，以及晶界相示意图[37]

图2 润湿转变示意图[37](a) the typical solid, liquid, and vapor three-phase wetting geometry (γsl, γsv, and γlv are the interfacial energies of solid-liquid, solid-vapor, and liquid-vapor, respectively. θ is contact angle)(b) the liquid phase completely wetting the solid phase(c) the β phase partially wetting the α-β grain boundary(d) the β phase completely wetting the α-β grain boundary

图3 bcc结构W中Σ5 (310)[001]晶界以及2种晶界相的共存和相转变行为[53]

图4 掺杂和未掺杂Al2O3晶界迁移率随温度的变化关系[26]

Type	Definition mode	Terminology	Meaning
Complexion	Defined by	Congruent	Grain boundary characters (R and n) remain invariant, atomic structure
transitions	geometry	transition	and composition of the grain boundary core change
category		Non-congruent	Grain boundary characters (R and/or n) change
		transition
		Structural	Bulk thermodynamic parameters (T, P, μ, etc.) change, interfacial
		transition	thermodynamic parameters (R, n, etc.) remain invariant
		Faceting	A single complexion decomposes into two complexions, the grain
		transition	boundary plane normal n decomposes into n₁ and n₂
		Dissociation	A single complexion decomposes into two complexions, a single grain
		transition	boundary dissociates into two new interfaces with the misorientation
			relationship of R→ R₁+ R₂
	Defined by	Premelting	A disordered, liquid-like film at a grain boundary forms below the
	structure and/or	transition	melting temperature (or solidus) of the bulk phase
	composition	Prewetting	A nanolayer complexion with fixed equilibrium thickness forms at the
		transition	interface near the temperature or composition of the wetting transition
		Adsorption	A dramatic change in the composition of an interface in which the
		transition	relative amount of solute increases or decreases significantly
Complexion	Defined by	Intrinsic	The complexion exists in pure systems, its composition is identical to
category	composition	complexion	the bulk composition
		Extrinsic	The complexion exists in a non-pure system, its composition is in
		complexion	general not equal to the bulk composition
	Dillon-Harmer	Clean	A complexion is structurally abrupt, solute segregation is not
	complexion	complexion	necessarily entirely absent, but is minimal or is not observed at all,
			which does not lead to an increase in thickness of the grain boundary
			core
		Monolayer	The majority of the adsorbed solute is confined to a thickness of a
		complexion	single atomic layer
		Bilayer	The most of the adsorbed solute occupies a thickness of two atomic
		complexion	layers
		Trilayer	The most of the adsorbed solute occupies a thickness of three atomic
		complexion	layers
		Nanolayer	The adsorbed solute occupies a thickness larger than three atomic
		complexion	layers, but which is still finite, fixed and governed by equilibrium
			thermodynamics, equivalent to intergranular film (IGF)
		Wetting	The bulk wetting film (solid or liquid) at a grain boundary, it has two
		complexion	complexions on each side of the wetting film
	Defined by	Dry	A complexion with no adsorbed solute or very little adsorption,
	thickness and	complexion	corresponds to the monolayer Dillon-Harmer complexion
	composition	Moist	A complexion with multilayer solute adsorption, corresponds to the
		complexion	bilayer, trilayer and nanolayer Dillon-Harmer complexions
		Wet	Refers to the bulk wetting film at a boundary, corresponds to the
		complexion	wetting Dillon-Harmer complexion

表1 晶界相变和晶界相的相关术语[37]

图5 Al-Zn-Mg-Cu合金120℃时效0.5 h的APT结果[42]

图6 亚固相准液相晶间膜示意图[92]

图7 一个对称平整的晶界示意图[94]

图8 构筑W-Ni-Fe三元系1673 K等温晶界λ相图示意图[35]及HRTEM像[10]

图9 300 K下Pt-Au体系的密度基Gibbs自由能[94]

图10 Pt-Au体系的块体相图(ρ = 1)和晶界相图(ρGB = 0.75)[94]

图11 Pt-Au体系700 K偏析等温线[94]

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