316L表面激光熔覆NiTi合金涂层的组织结构及元素占位

丰玉强; 胡正飞

doi:10.13801/j.cnki.fhclxb.20230614.003

316L表面激光熔覆NiTi合金涂层的组织结构及元素占位

doi: 10.13801/j.cnki.fhclxb.20230614.003

丰玉强^{1, 2},
胡正飞^{1, 2, ,}

1.
同济大学　材料科学与工程学院，上海 201804
2.
上海市金属功能材料开发应用重点实验室，上海 201804

基金项目: 国家自然科学基金(51971163)

详细信息

通讯作者:
胡正飞，博士，教授，博士生导师，研究方向为高强度轻量化金属材料和复合材料　E-mail: huzhengf@tongji.edu.cn

中图分类号: TG111；TB331
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- 被引次数: 0
出版历程
- 收稿日期: 2023-04-26
- 修回日期: 2023-05-24
- 录用日期: 2023-05-26
- 网络出版日期: 2023-06-14
- 刊出日期: 2024-02-01

Research on microstructure and site preference of NiTi alloy coating on 316L by laser cladding

FENG Yuqiang^{1, 2},
HU Zhengfei^{1, 2
, ,}

1.
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
2.
Shanghai Key Laboratory for R&D and Application of Metallic Functional Materials, Shanghai 201804, China

Funds: National Natural Science Foundation of China (51971163)

摘要

摘要: 60 NiTi (60wt%Ni-40wt%Ti)合金具有高硬度、高弹性模量及优异的耐磨和耐腐蚀性能，在许多领域有潜在的应用价值。本文对激光熔覆方法在316L不锈钢表面制备NiTi涂层的微观组织结构和物相组成进行了分析。结果表明：基材中主要成分Fe和Cr扩散到熔覆涂层中并显著地影响了镍钛涂层的组织结构和性能。熔覆涂层主要组成相为NiTi和Ni₃Ti，提高Ni含量可抑制NiTi₂析出。第一性原理计算结果显示，Fe和Cr元素易于固溶在B2结构的NiTi相中，并且都倾向于置换晶胞中的Ni原子。Ni₃Ti晶胞结构中的Ni和Ti原子各有2个不同的晶位，Fe原子倾向于置换晶胞中Ni-1晶位的Ni原子，而Cr原子倾向于置换晶胞中Ni-2晶位的Ni原子。根据涂层的成分分析结合模拟可知，镍钛合金涂层中NiTi和Ni₃Ti相的化学式分别为Ni₅Ti₈Fe₂Cr和Ni₉Ti₄Fe₂Cr。
- 激光熔覆 /
- 镍钛合金 /
- 第一性原理 /
- 合金元素掺杂 /
- 择优占位 /
- 表面改性
Abstract: 60 NiTi (60wt%Ni-40wt%Ti) alloy presents higher hardness, high elastic modulus, good abrasion performance and excellent corrosion resistance, making it suitable for various applications in different fields. This paper investigated the microstructure and phase composition of NiTi alloy coating on 316L stainless steel prepared by laser cladding. It shows that the main alloying elements Fe and Cr in the substrate are significantly doped into the cladding coating, which obviously affect the microstructure and properties of Ni-Ti coating. The main phases in the coating are NiTi and Ni₃Ti phases. Increase the content of Ni can inhibit the precipitation of NiTi₂. First-principles calculation based on density functional theory was used to study the phase preference and site preference occupations of the alloying elements Fe and Cr from substrate in NiTi and Ni₃Ti phases. The microstructure and phase composition of the coatings were investigated as well. The results show that, NiTi and Ni₃Ti are the major phases in the coating. Both Fe and Cr atoms prefer to substitute Ni atom in the NiTi (B2) crystal structure. However, in the Ni₃Ti crystal structure, each Ni and Ti atom has two different crystal positions, Fe atom prefers to substitute position Ni-1 and Cr atom prefers to substitute position Ni-2 instead. Combined the experiment and calculation results, the major phases in the coatings after element doping are supposed to be Ni₅Ti₈Fe₂Cr and Ni₉Ti₄Fe₂Cr.
- laser cladding /
- NiTi alloy /
- first-principles calculation /
- alloy doping /
- site preference /
- surface modification

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图 1 IPG YLS-10000激光熔覆设备：(a) 设备全貌；(b) 激光熔覆过程示意图

Figure 1. IPG YLS-10000 laser equipment: (a) Overview of the equipment; (b) Schematic diagram of the laser cladding process

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图 2 熔覆涂层表面形貌及截面金相图：(a) 55 NiTi涂层；(b) 60 NiTi涂层

Figure 2. Surface morphology and cross-section metallography of the coatings: (a) 55 NiTi coating; (b) 60 NiTi coating

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图 3 60 NiTi和55 NiTi两种熔覆涂层的XRD图谱

Figure 3. XRD patterns of the 60 NiTi and 55 NiTi coating

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图 4 熔覆涂层中部微观形貌图：(a) 55 NiTi涂层；(b) 60 NiTi涂层

Figure 4. Microstructure of the coating middle area: (a) 55 NiTi coating; (b) 60 NiTi coating

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图 5 铁镍钛三元合金系在1000℃的等温截面图

Figure 5. Isothermal section of the Fe-Ni-Ti ternary system phase diagram at 1000℃

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图 6 55 NiTi和60 NiTi熔覆层里NiTi相和Ni₃Ti相中Ni、Ti、Fe和Cr原子占比

Figure 6. Atomic proportion of Ni, Ti, Fe and Cr in NiTi phase and Ni₃Ti phase of 55 NiTi coating and 60 NiTi coating

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图 7 晶胞结构示意图：(a) NiTi体心立方结构；(b) Ni₃Ti密排六方晶体结构

Figure 7. Schematic diagram of the crystal structure: (a) NiTi crystal with bcc structure; (b) Ni₃Ti crystal with close-packed hexagonal structure

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图 8 NiTi晶胞结构示意图：(a)置换前；(b)置换后

Figure 8. Schematic diagram of NiTi crystal structure: (a) Before substitution; (b) After substitution

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图 9 Ni₃Ti晶胞中原子位置示意图：(a) 三维透视图；(b) 俯视图

Figure 9. Atom position in the Ni₃Ti crystal structure: (a) 3D perspective view; (b) Vertical view

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图 10 单个Fe和Cr原子置换Ni₃Ti中的Ni和Ti原子后形成能

Figure 10. Formation energy after substitution of single Fe and Cr atom to replace Ni and Ti atom in the Ni₃Ti crystal

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图 11 置换后晶胞示意图：(a) Ni₅Ti₈Fe₂Cr；(b) Ni₉Ti₄Fe₂Cr

Figure 11. Schematic diagram of crystal structure after substitution: (a) Ni₅Ti₈Fe₂Cr; (b) Ni₉Ti₄Fe₂Cr

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表 1 基体材料316L不锈钢的化学成分

Table 1. Chemical composition of 316L stainless steel substrate

Element	Fe	Cr	Ni	Mo	Mn	Si	P	C	S
Mass fraction/wt%	Balance	16.320	10.120	2.040	0.920	0.340	0.026	0.016	0.015

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表 2 Ni粉末和55 NiTi合金粉末的化学成分

Table 2. Chemical composition of Ni and 55 NiTi powders

Element	Ni	Ti	Fe	Nb	Co	C	Si	O
Mass fraction of Ni powder/wt%	Balance	—	0.003	—	0.020	0.020	0.003	0.006
Mass fraction of 55 NiTi powder/wt%	56.460	Balance	0.005	0.010	0.005	0.005	—	0.037

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表 3 激光熔覆工艺参数

Table 3. Process parameters for laser cladding

Parameter	Value
Laser power/kW	2.0
Scan speed/(mm·s^–1)	2.0
Laser beam spot diameter/mm	7.2
Working distance/mm	10
Overlap ratio/%	55
Powder feed rate/(r·min^–1)	50
Carrier gas flow rate/(L·min^–1)	8
Shielding gas flow rate/(L·min^–1)	5

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表 4 图4中标出点位的EDS扫描结果

Table 4. EDS scanning results for positions marked in Fig.4

Coating	Position	Ni/at%	Ti/at%	Fe/at%	Cr/at%	Major phase
55 NiTi	1	35.34	41.28	15.63	7.75	NiTi
	2	59.59	25.74	10.32	4.35	Ni₃Ti
	3	45.10	34.77	14.52	5.61	Ni₃Ti + NiTi
60 NiTi	4	38.48	42.89	13.42	5.21	NiTi
	5	61.63	23.27	9.26	5.84	Ni₃Ti
	6	50.08	30.34	16.33	3.25	Ni₃Ti + NiTi

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表 5 NiTi相和Ni₃Ti相的晶胞结构和原子位置

Table 5. Crystal structure and atom position of the NiTi and Ni₃Ti phase

Compound	Lattice category	Lattice parameter	Atom	Position
NiTi	SP No.221	a=b=c=0.3005 nm	Ni	1a
NiTi	SP No.221	α=β=γ=90°	Ti	1b
Ni₃Ti	SP No.194	a=b=0.5096 nm	Ni-1	6g
		c=0.8304 nm	Ni-2	6h
		α=β=90°	Ti-1	2a
		γ=120°	Ti-2	2c

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表 6 Ni、Ti、Fe和Cr的原子半径及其电负性

Table 6. Atom radius and its electronegativity of Ni, Ti, Fe and Cr atom

Element	Atomic radius/nm	Atomic electronegativity/eV
Ni	0.125	1.91
Ti	0.145	1.54
Fe	0.124	1.83
Cr	0.125	1.66

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表 7 Ni₃Ti相晶胞中原子坐标

Table 7. Atom coordinates in Ni₃Ti crystal structure

Compound	Atom	x	y	z
Ni₃Ti	Ni-1	0.5	0	0
	Ni-2	0.8333	0.6667	0.25
	Ti-1	0	0	0
	Ti-2	0.3333	0.6667	0.25

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表 8 Fe和Cr原子置换后Ni₃Ti晶胞的晶格常数

Table 8. Lattice parameters of Ni₃Ti crystal after substitution of Fe and Cr atom

Atom	Replaced position	Composition	a/nm	b/nm	c/nm
Fe	Ni-1	Ni₁₁Ti₄Fe	0.5118	0.4418	0.8316
	Ni-2	Ni₁₁Ti₄Fe	0.5116	0.4419	0.8317
	Ti-1	Ni₁₂Ti₃Fe	0.5068	0.4388	0.8286
	Ti-2	Ni₁₂Ti₃Fe	0.5060	0.4385	0.8281
Cr	Ni-1	Ni₁₁Ti₄Cr	0.5122	0.4434	0.8357
	Ni-2	Ni₁₁Ti₄Cr	0.5129	0.4443	0.8377
	Ti-1	Ni₁₂Ti₃Cr	0.5088	0.4407	0.8293
	Ti-2	Ni₁₂Ti₃Cr	0.5085	0.4404	0.8293

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表 9 Fe和Cr原子在NiTi和Ni₃Ti结构中的原子占比

Table 9. Atomic proportion of Fe and Cr atom in NiTi and Ni₃Ti crystal structure after substitution

Phase	Composition after substitution	Ni/at%	Ti/at%	Fe/at%	Cr/at%
NiTi (B2)	Ni₅Ti₈Fe₂Cr	31.25	50.00	12.50	6.25
Ni₃Ti	Ni₉Ti₄Fe₂Cr	56.25	25.00	12.50	6.25

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表 10 Fe和Cr原子置换后的形成能及晶格常数

Table 10. Formation energy and lattice parameters after substitution of Fe and Cr atoms

Crystal	Composition	Formation energy/eV	a/nm	b/nm	c/nm
NiTi (B2)	Ni₅Ti₈Fe₂Cr	−0.3286	0.5962	0.5962	0.6007
Ni₃Ti	Ni₉Ti₄Fe₂Cr	−0.3050	0.5128	0.4432	0.8362

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