多元合金-碳化物粘结相对金刚石复合材料组织的影响

邱天旭; 张伟; 刘咏

doi:10.13801/j.cnki.fhclxb.20221014.006

多元合金-碳化物粘结相对金刚石复合材料组织的影响

doi: 10.13801/j.cnki.fhclxb.20221014.006

中南大学　粉末冶金国家重点实验室，长沙 410083

基金项目: 国家重点研发计划重点专项(2021 YFB3701800)；国家自然科学基金区域创新发展联合基金(U20 A20236)

详细信息

通讯作者:
刘咏，博士，教授，博士生导师，研究方向为硬质合金、高熵合金、金刚石超硬材料等设计与制备　E-mail: yonliu@csu.edu.cn

中图分类号: TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2022-07-14
- 修回日期: 2022-09-15
- 录用日期: 2022-10-02
- 网络出版日期: 2022-10-17
- 刊出日期: 2023-07-15

Effect of multi-element alloy-carbide bonding phase on the microstructure of diamond composites

State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China

Funds: National Key Research and Development Program of China (2021 YFB3701800); Regional Innovation and Development Joint Fund of National Natural Science of China (U20 A20236)

摘要

摘要: 金刚石复合材料在加工、钻探等领域应用广泛，提高材料中金刚石骨架的结合强度是重要研究方向。以Co₅₀Ni₄₀Fe₁₀多元合金-碳化物替代纯Co作为粘结相，在高温高压条件下制备了金刚石复合材料，结合热力学计算研究了多元合金和碳化物对材料组织的影响。结果表明：相比于Co，Co₅₀Ni₄₀Fe₁₀多元合金具有更强的促进C原子迁移和扩散的能力，能加快金刚石骨架的形成。高温高压条件下，WC中C含量轻微增加，对金刚石骨架的形成影响不大；TiC轻微失C，能在一定程度上促进金刚石骨架的形成；Cr₃C₂分解产生的C能促进金刚石骨架的形成。
- 多元合金 /
- 碳化物 /
- 热力学 /
- 聚晶金刚石 /
- 金刚石骨架
Abstract: Diamond composites are widely used in processing, drilling and other fields, and improving the bonding strength of the diamond skeleton is an important research direction. In this work, Co₅₀Ni₄₀Fe₁₀ multi-element alloy-carbide was used as the binder instead of Co to prepare diamond composites under high temperature and high pressure, and the influence of multi-element alloys and carbides on the microstructure of composites was studied by experiments and thermodynamic calculations. The results show that, compared with Co, Co₅₀Ni₄₀Fe₁₀ multi-element alloy has stronger ability to promote the migration and diffusion of C atoms, which can accelerate the formation of diamond skeleton. Under the condition of high temperature and high pressure, the carbon content in WC increased slightly, which has little effect on the formation of diamond skeleton; TiC lost C slightly, which can promote the formation of diamond skeleton to a certain extent; The C produced by Cr₃C₂ decomposition can promote the formation of diamond skeleton.
- multi-element alloy /
- carbide /
- thermodynamics /
- polycrystalline diamond /
- diamond skeleton

HTML全文

图 1 高温高压法制备金刚石复合材料示意图

Figure 1. Schematic of diamond composites manufactured by high temperature and high pressure method

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图 2 Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia.复合材料的微观组织和元素分布(MC代表碳化物)：((a)~(c)) WC-Comp.；((d)~(f)) Cr₃C₂-Comp.；((g)~(i)) TiC-Comp.

Figure 2. Microstructures and elemental distribution of Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia. composites (MC is carbide): ((a)-(c)) WC-Comp.; ((d)-(f)) Cr₃C₂-Comp.; ((g)-(i)) TiC-Comp.

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图 3 Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia.复合材料的XRD图谱(a)和拉曼光谱(b)

Figure 3. XRD patterns (a) and Raman spectra (b) of Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia. composites

FCC—Face centered cubic; HCP—Hexagonal close packed

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图 4 Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia.复合材料的力学性能：(a) 硬度(HRA)；(b) 横向断裂强度(TRS)

Figure 4. Mechanical properties of Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia. composites: (a) Hardness (HRA); (b) Transverse rupture strength (TRS)

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图 5 复合材料金刚石骨架的断口形貌：((a), (c)) CoNiFe-Comp.；((b), (d)) Co-Comp.

Figure 5. Fracture morphologies of diamond skeleton of composites: ((a), (c)) CoNiFe-Comp.; ((b), (d)) Co-Comp.

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图 6 Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia.复合材料金刚石骨架的断口形貌：((a), (d)) WC-Comp.；((b), (e)) Cr₃C₂-Comp.；((c), (f)) TiC-Comp.

Figure 6. Fracture morphologies of diamond skeleton of Co₅₀Ni₄₀Fe₁₀-5vol%MC-75vol%Dia. composites: ((a), (d)) WC-Comp.; ((b), (e)) Cr₃C₂-Comp.; ((c), (f)) TiC-Comp.

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图 7 碳化物分解反应的吉布斯自由能ΔG：(a) WC = W + Dia.和TiC = Ti + Dia.；(b) Cr₃C₂ + Liquid₁ = 2Dia. + Liquid₂

Figure 7. Gibbs free energy ΔG for the reaction of carbide decomposition: (a) WC = W + Dia. and TiC = Ti + Dia.; (b) Cr₃C₂ + Liquid₁ = 2Dia. + Liquid₂

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表 1 金刚石复合材料的命名及成分组成

Table 1. Nomenclature and compositions of diamond composites

Name	Composition
WC-Comp.	(Co₅₀Ni₄₀Fe₁₀)-5vol%WC-75vol%Dia.
Cr₃C₂-Comp.	(Co₅₀Ni₄₀Fe₁₀)-5vol%Cr₃C₂-75vol%Dia.
TiC-Comp.	(Co₅₀Ni₄₀Fe₁₀)-5vol%TiC-75vol%Dia.
CoNiFe-Comp.	(Co₅₀Ni₄₀Fe₁₀)-75vol%Dia.
Co-Comp.	Co-75vol%Dia.
Notes: Comp.—Composites; Dia.—Diamond.

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表 2 图2中不同物相的成分分析结果

Table 2. Elements analysis of different phases in Fig.2 at%

Spot	Phase	Co	Ni	Fe	W/Cr/Ti	C
1	Diamond	—	—	—	—	100.00
2	Alloy in WC-Comp.	46.30±1.62	36.04±1.39	9.47±0.74	0.96±0.76(W)	7.23±2.27
3	WC	3.63±0.77	3.17±0.85	1.26±0.47	38.68±3.79(W)	53.25±7.74
4	Cr-rich phase	29.95±2.05	9.05±1.97	6.92±1.06	35.31±1.75(Cr)	18.77±2.97
5	Ni-rich phase	42.10±4.68	38.72±3.87	8.14±1.46	4.30±0.67(Cr)	6.64±1.65
6	TiC	1.00±1.46	0.78±1.12	0.33±0.59	62.13±4.58(Ti)	35.78±6.99
7	Alloy in TiC-Comp.	44.38±7.55	32.39±4.24	9.22±1.48	0.65±0.44(Ti)	13.35±10.32

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表 3 式(3)、(4)和(10)中涉及物质的物理性质参数

Table 3. Physical parameters of the substances involved in the reaction (3), (4) and (10)

Substance	Volume expansion coefficient γ/K⁻¹	$ {B}_{0} $/GPa	${B'}_{0}$
Diamond^[27]	−2.013×10⁻⁶+2.4×10⁻⁸T−9.219×10⁻¹²T²+ 1.237×10⁻¹⁵T³	443.0	4.0
W^[28-29]	(1+4.40×10⁻⁶)³−1	309.2	6.6
WC^[30-31]	(1+6.25×10⁻⁶)³−1	389.6	4.3
Cr	(1+6.20×10⁻⁶)³−1	161.5	4.26
Cr₃C₂^[32]	(1+10.3×10⁻⁶)³−1	329.0	4.0
Ti	(1+10.1×10⁻⁶)³−1	96.5	3.65
TiC^[28]	(1+7.7×10⁻⁶)³−1	253.0	4.1
Notes: B₀—Bulk modulus; $ {B'}_{0} $—Derivative of B₀; $ {B}_{0} $ and $ {B'}_{0} $ of Cr and Ti are obtained by the author through first-principles calculations.

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表 4 Akira Takeuchi和Akihisa Inoue计算的组元i和j的二元混合焓($ {\Delta H}_{i,j}^{\mathrm{m}\mathrm{i}\mathrm{x}} $)的值^[34]

Table 4. Values of binary mixing enthalpy of components i, j ($ {\Delta H}_{i,j}^{\mathrm{m}\mathrm{i}\mathrm{x}} $) calculated by Akira Takeuchi and Akihisa Inoue^[34]

$ {\Delta H}_{i,j}^{\mathrm{m}\mathrm{i}\mathrm{x}} $/(kJ·mol)	Ni	Fe	Cr
Co	0	−1	−4
Ni	—	−2	−7
Fe	—	—	−1

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