钽合金表面渗碳层中碳化物析出及其性能的第一性原理研究

doi:10.11900/0412.1961.2024.00096

金属学报

2025, Vol. 61

Issue (5): 797-808 DOI: 10.11900/0412.1961.2024.00096

研究论文

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钽合金表面渗碳层中碳化物析出及其性能的第一性原理研究

孟祥龙¹, 刘瑞良¹(

), Li D. Y.²(

)

1 哈尔滨工程大学材料科学与化学工程学院超轻材料与表面技术教育部重点实验室哈尔滨 150001
2 Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 1H9

First Principles Study on the Precipitation and Properties of Carbides in the Surface Carburized Layer of Tantalum Alloys

MENG Xianglong¹, LIU Ruiliang¹(

), Li D. Y.²(

)

1 Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
2 Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 1H9

引用本文:

孟祥龙, 刘瑞良, Li D. Y.. 钽合金表面渗碳层中碳化物析出及其性能的第一性原理研究[J]. 金属学报, 2025, 61(5): 797-808.
Xianglong MENG, Ruiliang LIU, D. Y. Li. First Principles Study on the Precipitation and Properties of Carbides in the Surface Carburized Layer of Tantalum Alloys[J]. Acta Metall Sin, 2025, 61(5): 797-808.

全文: PDF(1843 KB) HTML

摘要:

Ta及其合金具有熔点高和耐磨性好等特点，采用渗碳等表面改性技术可在Ta及其合金表面获得含碳化钽的改性层，显著提高其表面性能，但是不同钽合金表面析出碳化钽的结构和性能尚不清楚。本工作以Ta-Mo和Ta-W钽合金为研究对象，构建了含不同种类及含量合金元素的fcc和hcp结构复合碳化钽(Ta, M)C (M = Mo、W)模型，利用基于密度泛函理论的第一性原理方法对不同复合碳化钽结构的能量和力学性质进行计算，探索复合碳化钽的强韧化机制。计算结果表明，当Mo和W含量低于50%时，易于形成fcc结构的复合碳化钽，且Mo、W原子浓度越高，具有fcc结构的复合碳化钽的模量和硬度越低，韧性越好；当Mo和W含量高于50%时，易于形成hcp结构的Ta的碳化物，随着Mo、W原子浓度的提高，具有hcp结构的复合碳化钽的模量和硬度增加，韧性降低。

关键词 ：钽合金, 复合碳化钽, 第一性原理计算, 晶体结构, 稳定性, 力学性能

Abstract：

Tantalum and its alloys have high melting points and good wear resistance, which are primarily used in fields such as the aerospace and nuclear energy industry. Surface modification techniques such as carburization can be used to obtain a modified layer containing tantalum carbide on the surface of tantalum and its alloys, thereby significantly improving their surface properties. However, the structure and properties of tantalum carbide precipitated on the surface of different tantalum alloys remain unclear. This study focuses on Ta-Mo and Ta-W alloys, and constructs fcc and hcp complex tantalum carbide (Ta, M)C (M = Mo, W) models with different alloying elements and their contents. The energy and mechanical properties of different complex tantalum carbide structures were calculated using the first principles method based on the density functional theory to explore the strengthening and toughening mechanisms of complex tantalum carbides. Calculation results indicate that when the content of Mo and W is less than 50%, fcc structured complex tantalum carbide can be easily formed, and the higher the concentration of Mo and W atoms, the lower the modulus and hardness of the complex tantalum carbide with an fcc structure, and the better the toughness. When the content of Mo and W exceeds 50%, tantalum carbides with an hcp structure are easy to form. As the concentration of Mo and W atoms increases, the modulus and hardness of complex tantalum carbides with an hcp structure increase, whereas the toughness decreases.

Key words： tantalum alloy complex tantalum carbide first-principles calculation crystal structure stability mechanical property

收稿日期: 2024-03-27

ZTFLH:

TG146.4

基金资助:国家自然科学基金项目(52371060);黑龙江省自然科学基金项目(LH2023E060);中央高校基本科研业务费项目(3072023WD010)

通讯作者: 刘瑞良，liuruiliang@hrbeu.edu.cn，主要从事金属材料强韧化及其表面改性研究；
D. Y. Li，dongyang.li@ualberta.ca，主要从事材料表/界面以及计算材料学研究

Corresponding author: LIU Ruiliang, professor, Tel: (0451)82518731, E-mail: liuruiliang@hrbeu.edu.cn;
D. Y. Li, Tel: (0451)82518731, E-mail: dongyang.li@ualberta.ca

作者简介: 孟祥龙，男，1999年生，硕士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2024.00096 或 https://www.ams.org.cn/CN/Y2025/V61/I5/797

图1 不同结构复合碳化钽的特殊准随机结构(SQS)超胞模型

Crystal structure	Carbide	Lattice constant nm	Angle (°)	Volume nm³	E_f eV·atom^-1	E_c eV·atom^-1
fcc	TaC, this work	$a ¯$ = 0.44781	α = β = γ = 90.00	0.71839	-0.5962	-8.5998
	TaC^[34]	a = 0.447			-0.59
	Ta_0.75Mo_0.25C	$a ¯$ = 0.44554	α = 90.04, β = γ = 90.00	0.70753	-0.4089	-8.1705
	Ta_0.5Mo_0.5C	$a ¯$ = 0.44320	α = β =89.78, γ = 90.22	0.69645	-0.2246	-7.7442
	Ta_0.25Mo_0.75C	$a ¯$ = 0.44061	α = 89.79, β = γ = 90.00	0.68428	-0.0432	-7.6155
	MoC	$a ¯$ = 0.43699	α = β = γ = 90.00	0.66756	0.1400	-6.8956
hcp	Ta₂C	a = b = 0.31249, c = 0.49593	α = β = 90.00, γ = 120.00	0.33551	-0.6163	-8.6566
	(P $3 ¯$ m1, this work)	a = b = 0.31249, c = 0.49593	α = β = 90.00, γ = 120.00
	Ta₂C (P $3 ¯$ m1)^[34]	a = b = 0.311, c = 0.495	γ = 120.00		-0.60
		a = b = 0.311, c = 0.495	γ = 120.00
	Ta_0.75Mo_0.25C	a = 0.45271, b = 0.45256, c = 0.43049	α = 90.05, β = 89.96, γ = 120.01	0.68590	-0.1681	-7.9208


	Ta_0.5Mo_0.5C	a = 0.44703, b = 0.44702, c = 0.42883	α = 90.07, β = 89.98, γ = 120.01	0.59361	-0.1616	-7.6633


	Ta_0.25Mo_0.75C	a = 0.44261, b = 0.44227, c = 0.42681	α = 89.99, β = 90.01, γ = 120.02	0.57870	-0.1610	-7.4476


	MoC	a = b = 0.43761, c = 0.42422	α = β = 90.00, γ = 120.00	0.56283	-0.1519	-7.1876
		a = b = 0.43761, c = 0.42422	α = β = 90.00, γ = 120.00

表1 含Mo复合碳化钽结构的晶体参数、形成能(Ef)和内聚能(Ec)

图2 不同结构含Mo复合碳化钽的Ec和Ef

Crystal structure	Carbide	Lattice constant nm	Angle (°)	Volume nm³	E_f eV·atom^-1	E_c eV·atom^-1
fcc	TaC, this work	$a ¯$ =0.44781	α = β = γ = 90.00	0.71839	-0.5962	-8.5998
	TaC^[34]	a = 0.447			-0.59
	Ta_0.75W_0.25C	$a ¯$ = 0.44543	α = 90.00, β = 89.99, γ = 90.00	0.70699	-0.3759	-8.6364


	Ta_0.5W_0.5C	$a ¯$ = 0.44339	α = 89.79, β = 90.19, γ = 90.06	0.69731	-0.1566	-8.2123


	Ta_0.25W_0.75C	$a ¯$ = 0.44096	α = β = 90.00, γ = 90.06	0.68590	0.0565	-8.3138
			α = β = 90.00, γ = 90.06
	WC	$a ¯$ = 0.43821	α = β = γ = 90.00	0.67320	0.2909	-7.8169
hcp	Ta₂C	a = b = 0.31249, c = 0.49593	α = β = 90.00, γ = 120.00	0.33551	-0.6163	-8.6566
	(P $3 ¯$ m1, this work)	a = b = 0.31249, c = 0.49593	α = β = 90.00, γ = 120.00
	Ta₂C (P $3 ¯$ m1)^[34]	a = b = 0.311, c = 0.495	γ = 120		-0.60
		a = b = 0.311, c = 0.495
	Ta_0.75W_0.25C	a = 0.45263, b = 0.45262, c = 0.43127	α = 89.94, β =90.08, γ = 120.00	0.61212	-0.1640	-8.1946


	Ta_0.5W_0.5C	a = 0.44731, b = 0.44718, c = 0.43034	α = 89.93, β = 89.98, γ = 120.00	0.59638	-0.1561	-8.2137


	Ta_0.25W_0.75C	a = 0.44306, b = 0.44305, c = 0.42889	α = 90.00, β = 89.99, γ = 119.99	0.58335	-0.1573	-8.2381


	WC	a = b =0.43868, c = 0.42730	α = β = 90.00, γ = 120.00	0.56968	-0.1543	-8.2621
		a = b =0.43868, c = 0.42730	α = β = 90.00, γ = 120.00

表2 含W复合碳化钽结构的晶体参数、Ef和Ec

图3 不同结构含W复合碳化钽的Ec和Ef

Carbide (fcc)	C₁₁ ( $C ¯$ ₁₁) GPa	C₁₂ ( $C ¯$ ₁₂) GPa	C₄₄ ( $C ¯$ ₄₄) GPa	G GPa	B GPa	E GPa	H_V GPa	G / B	$ν$
TaC, this work	720	134	154	200	330	500	21.8	0.607	0.25
TaC^[34]	737	141	175	216.90	339.67		24.53
Ta_0.75Mo_0.25C	668	138	152	167	302	423	20.9	0.605	0.25
Ta_0.5Mo_0.5C	576	165	146	151	310	389	17.0	0.554	0.27
Ta_0.25Mo_0.75C	581	174	123	122	339	327	13.2	0.486	0.29
MoC	684	166	70	200	331	499	7.0	0.360	0.34
Ta_0.75W_0.25C	715	139	156	179	310	450	21.5	0.603	0.25
Ta_0.5W_0.5C	630	150	147	156	341	407	18.8	0.577	0.26
Ta_0.25W_0.75C	611	207	132	129	370	346	12.4	0.458	0.30
WC	769	170	67	200	330	500	7.0	0.348	0.34

表3 fcc结构复合碳化钽的弹性常数和力学性质

Carbide (hcp)	C₁₁	C₁₂	C₁₃	C₃₃	C₄₄
Ta₂C (P $3 ¯$ m1, this work)	480	143	138	498	120
Ta₂C (P $3 ¯$ m1)^[34]	479	164	149	504	133
Ta_0.75Mo_0.25C	511	194	138	764	120
Ta_0.5Mo_0.5C	532	203	151	783	157
Ta_0.25Mo_0.75C	568	206	159	811	203
MoC	618	213	159	854	263
Ta_0.75W_0.25C	537	197	138	787	130
Ta_0.5W_0.5C	581	209	154	823	181
Ta_0.25W_0.75C	621	224	164	878	235
WC	699	232	167	953	302

表4 hcp结构复合碳化钽的弹性常数 (GPa)

Carbide (hcp)	G GPa	B GPa	E GPa	H_v GPa	G / B GPa	$ν$
Ta₂C (P $3 ¯$ m1, this work)	149	255	374	16.9	0.583	0.26
Ta₂C (P $3 ¯$ m1)^[34]	148.08	264.66		15.87
Ta_0.75Mo_0.25C	160	300	407	15.6	0.532	0.27
Ta_0.5Mo_0.5C	180	315	454	18.8	0.573	0.26
Ta_0.25Mo_0.75C	209	330	517	23.6	0.632	0.24
MoC	246	348	597	30.3	0.706	0.21
Ta_0.75W_0.25C	171	310	433	17.2	0.552	0.27
Ta_0.5W_0.5C	203	333	507	22.1	0.609	0.25
Ta_0.25W_0.75C	234	356	576	26.8	0.658	0.23
WC	282	385	681	34.7	0.732	0.21

表5 hcp结构复合碳化钽的力学性质

图4 不同结构含Mo复合碳化钽的力学性质

图5 不同结构含W复合碳化钽的力学性质

图6 不同结构复合碳化钽的总态密度和投影态密度

图7 不同结构复合碳化钽的金属丰度(fm)

表6 不同结构复合碳化钽中各原子的平均Bader电荷

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