Zr-X(X=Li, Na, K, Sc, Hf)体系的二元相图理论研究

doi:10.7503/cjcu20150345

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 1939.doi: 10.7503/cjcu20150345

Zr-X(X=Li, Na, K, Sc, Hf)体系的二元相图理论研究

胡标^1,², 周鹏², 潘成岭¹(), 杜勇²(), 刘树红², 李一为², 韩江军¹

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

收稿日期:2015-04-29 出版日期:2015-10-10 发布日期:2015-09-18
作者简介:联系人简介: 潘成岭, 男, 博士, 教授, 主要从事复合材料性能研究. E-mail:chengling_pan@126.com;杜勇, 男, 博士, 教授, 主要从事相图热力学动力学研究等. E-mail:yong-du@csu.edu.cn
基金资助:
国家重大基础研究发展计划(批准号: 2011CB610401)、国家自然科学基金(批准号: 21201006, 51501002)和安徽理工大学引进人才科研启动基金(批准号: ZX979)资助

Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems^†

HU Biao^1,², ZHOU Peng², PAN Chengling^1,^*(), DU Yong^2,^*(), LIU Shuhong², LI Yiwei², HAN Jiangjun¹

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

Received:2015-04-29 Online:2015-10-10 Published:2015-09-18
Contact: PAN Chengling,DU Yong E-mail:chengling_pan@126.com;yong-du@csu.edu.cn
Supported by:
† Supported by the National Basic Research Program of China(No.2011CB610401), the National Natural Science Foundation of China(Nos.21201006, 51501002) and the Scientific Research Starting Foundation for the Introduced Talents of Anhui University of Science and Technology Project, China(No;ZX979)

摘要/Abstract

摘要：

采用相图计算(CALPHAD: Calculation of phase diagrams) 方法对Zr-X(X=Li, Na, K, Sc, Hf)5个二元体系进行了相图热力学研究. 基于实验数据, 通过热力学优化计算获得了一套描述液相及(αZr), (βZr), (Li), (Na), (K), (αSc), (βSc), (αHf)和(βHf)相的热力学参数. Zr-Li, Zr-Na和Zr-K体系中的气相视为理想气体. 与实验相图数据对比发现, 本文获得的热力学参数能够准确地描述实验相平衡数据.

关键词: Zr-X(X=Li, Na, K, Sc, Hf)体系, 二元相图, 热力学模型, 相图计算方法

Abstract:

The Zr-X(X=Li, Na, K, Sc, Hf) systems were studied with the calculation of phase diagrams(CALPHAD) approach. A set of the thermodynamic parameters of the liquid, (αZr), (βZr), (Li), (Na), (K), (αSc), (βSc), (αHf) and (βHf) phases was obtained based on the critical review of the available experimental data. The gas phase for the three binary systems, i.e. Zr-Li, Zr-Na and Zr-K, was treated with the ideal gas model. Comparisons between the calculated and measured phase diagrams show that the experimental phase equilibria information is satisfactorily accounted for by the present thermodynamic description.

Key words: Zr-X(X=Li, Na, K, Sc, Hf) system, Binary phase diagram, Thermodynamic modeling, Calculation of phase diagrams approach

中图分类号:

O642
O614.4

TrendMD:

胡标, 周鹏, 潘成岭, 杜勇, 刘树红, 李一为, 韩江军. Zr-X(X=Li, Na, K, Sc, Hf)体系的二元相图理论研究. 高等学校化学学报, 2015, 36(10): 1939.

HU Biao, ZHOU Peng, PAN Chengling, DU Yong, LIU Shuhong, LI Yiwei, HAN Jiangjun. Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems^†. Chem. J. Chinese Universities, 2015, 36(10): 1939.

图/表 7

Table 1 Summary of the thermodynamic parameters in the Zr-X(X=Li, Na, K, Sc, Hf) systems

System	Phase	Model	Thermodynamic parameter/(J·mol^-1)
Zr-Li	Liquid	(Li, Zr)₁	⁰ $L Li, Zr Liquid$ =92517
	(Li, βZr)	(Li, Zr)₁Va₃	⁰ $L Li, Zr : Va (Li, βZr)$ =108305
	(αZr)	(Li, Zr)₁Va_0.5	⁰ $L Li, Zr : Va (αZr)$ =89754
	Gas	(Li, Li₂, Zr, Zr₂)₁	⁰ $G Li Gas$ =RTln(P)+GASLI(T)
			⁰ $G L i 2 Gas$ =RTln(P)+GASLI2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-Na	Liquid	(Na, Zr)₁	⁰ $L Na, Zr Liquid$ =59106.339
	(Na,βZr)	(Na, Zr)₁Va₃	⁰ $L Na, Zr : Va (Na, βZr)$ =74883.736
	(αZr)	(Na, Zr)₁Va_0.5	⁰ $L Na, Zr : Na (αZr)$ =181544.538
	Gas	(Na, Na₂, Zr, Zr₂)₂	⁰ $G Na Gas$ =RTln(P)+GASNA(T)
			⁰ $G N a 2 Gas$ =RTln(P)+GASNA2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-K	Liquid	(K, Zr)₁	⁰ $L K, Zr Liquid$ =52775.945
	(K,βZr)	(K, Zr)₁Va₃	⁰ $L K, Zr : Va (K, βZr)$ =65916.68
	(αZr)	(K, Zr)₁Va_0.5	⁰ $L K, Zr : Na (αZr)$ =125195.31
	Gas	(K, K₂, Zr, Zr₂)₁	⁰ $G K Gas$ =RTln(P)+GASK(T)
			⁰ $G K 2 Gas$ =RTln(P)+GASK2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-Sc	(βZr, βSc)	(Sc,Zr)₁Va₃	⁰ $L Sc, Zr : Va (βZr, βSc)$ =-6048.834+4.4931T
	(αZr, αSc)	(Sc,Zr)₁Va_0.5	⁰ $L Sc, Zr : Na (αZr, αSc)$ =-10689.553+5.8839T
Zr-Hf	Liquid	(Hf,Zr)₁	⁰ $L Hf, Zr Liquid$ =-1467.872
			¹ $L Hf, Zr Liquid$ =-558.748
	(αZr, αHf)	(Hf,Zr)₁Va_0.5	⁰ $L Hf, Zr : Na (αZr, αHf)$ =832.587
			¹ $L Hf, Zr : Na (αZr, αHf)$ =104.255

Table 1 Summary of the thermodynamic parameters in the Zr-X(X=Li, Na, K, Sc, Hf) systems

System	Phase	Model	Thermodynamic parameter/(J·mol^-1)
Zr-Li	Liquid	(Li, Zr)₁	⁰ $L Li, Zr Liquid$ =92517
	(Li, βZr)	(Li, Zr)₁Va₃	⁰ $L Li, Zr : Va (Li, βZr)$ =108305
	(αZr)	(Li, Zr)₁Va_0.5	⁰ $L Li, Zr : Va (αZr)$ =89754
	Gas	(Li, Li₂, Zr, Zr₂)₁	⁰ $G Li Gas$ =RTln(P)+GASLI(T)
			⁰ $G L i 2 Gas$ =RTln(P)+GASLI2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-Na	Liquid	(Na, Zr)₁	⁰ $L Na, Zr Liquid$ =59106.339
	(Na,βZr)	(Na, Zr)₁Va₃	⁰ $L Na, Zr : Va (Na, βZr)$ =74883.736
	(αZr)	(Na, Zr)₁Va_0.5	⁰ $L Na, Zr : Na (αZr)$ =181544.538
	Gas	(Na, Na₂, Zr, Zr₂)₂	⁰ $G Na Gas$ =RTln(P)+GASNA(T)
			⁰ $G N a 2 Gas$ =RTln(P)+GASNA2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-K	Liquid	(K, Zr)₁	⁰ $L K, Zr Liquid$ =52775.945
	(K,βZr)	(K, Zr)₁Va₃	⁰ $L K, Zr : Va (K, βZr)$ =65916.68
	(αZr)	(K, Zr)₁Va_0.5	⁰ $L K, Zr : Na (αZr)$ =125195.31
	Gas	(K, K₂, Zr, Zr₂)₁	⁰ $G K Gas$ =RTln(P)+GASK(T)
			⁰ $G K 2 Gas$ =RTln(P)+GASK2(T)
			⁰ $G Zr Gas$ =RTln(P)+GASZR(T)
			⁰ $G Z r 2 Gas$ =RTln(P)+GASZR2(T)
Zr-Sc	(βZr, βSc)	(Sc,Zr)₁Va₃	⁰ $L Sc, Zr : Va (βZr, βSc)$ =-6048.834+4.4931T
	(αZr, αSc)	(Sc,Zr)₁Va_0.5	⁰ $L Sc, Zr : Na (αZr, αSc)$ =-10689.553+5.8839T
Zr-Hf	Liquid	(Hf,Zr)₁	⁰ $L Hf, Zr Liquid$ =-1467.872
			¹ $L Hf, Zr Liquid$ =-558.748
	(αZr, αHf)	(Hf,Zr)₁Va_0.5	⁰ $L Hf, Zr : Na (αZr, αHf)$ =832.587
			¹ $L Hf, Zr : Na (αZr, αHf)$ =104.255

Table 2 Calculated invariant equilibria in the Zr-X(X=Li, Na, K, Sc) systems compared with literature data

System	Invariant reaction	Temperature/℃	System	Invariant reaction	Temperature/℃
Zr-Li	Gas+Liquid#2=(βZr)	1854.1(1855^[4])	Zr-Na	Liquid#1+(αZr)=(Na)	97.7(98^[5])
	Gas+(βZr)=Liquid#1	1338.3(1342^[4])	Zr-K	Gas+Liquid#2=(βZr)	1853.8(1855^[6])
	Liquid#1+(βZr)=(αZr)	865.9(863^[4])		Gas+(βZr)=(αZr)	865.2(863^[6])
	Liquid#1+(αZr)=(Li)	180.6(180^[4])		Gas+(αZr)=Liquid#1	761.2(779^[6])
Zr-Na	Gas+Liquid#2=(βZr)	1854(1855^[5])		Liquid#1+(αZr)=(K)	63.7(64^[6])
	Gas+(βZr)=Liquid#1	885.4(882^[5])	Zr-Sc	(αZr, αSc)=(βZr, βSc)	1407.4(1410^[7])
	Liquid#1+(βZr)=(αZr)	865.3(863^[5] )

Fig.1 Calculated phase diagram of Zr-Li

Fig.2 Calculated phase diagram of Zr-Na

Fig.3 Calculated phase diagram of Zr-K

Fig.4 Calculated phase diagram of Zr-Sc and the experimental data

Fig.5 Calculated phase diagram of Zr-Hf and the experimental data

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Zr-X(X=Li, Na, K, Sc, Hf)体系的二元相图理论研究

Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems^†

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Zr-X(X=Li, Na, K, Sc, Hf)体系的二元相图理论研究

Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems†

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Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems^†