Phase-composition design of high-hardness and high-electric-conductivity Cu-Ni-Si Alloy

Li Dong-Mei; Han Jing-Yu; Dong Chuang

doi:10.7498/aps.68.20190593

Abstract

Cu-Ni-Si alloy has good electrical conductivity, thermal conductivity, high strength, and high hardness, and is widely used in electronic components and other fields. When the compositions of the Cu-Ni-Si alloy are designed, the determination of the phase component is critical. In this work, the composition of Cu-Ni-Si alloy is designed according to the "precipitation phase" by cluster-plus-glum-atom model. Following the cluster selection criteria, the δ-Ni₂Si, γ-Ni₅Si₂ and β-Ni₃Si phase clusters are determined, respectively, and the corresponding cluster formulas are [Ni-Ni₈Si₅]Ni,[Si-Ni₁₀]Si₃, and [Si-Ni₁₂]Si₃. the compositions of a series of Cu-Ni-Si alloys are designed according to the different precipitated phases of δ-Ni₂Si, γ-Ni₅Si₂, and β-Ni₃Si each with Cu atom content being 93.75%, 95%, 95.8%, 96.7% and 97.5%, respectively. The alloy raw material is melted into alloy ingot in an argon-filled vacuum arc furnace. The ingots undergoes solid-solution at 950 ° C for 1 hour and water quenching then aging treatment at 450 ° C for 4 hour and water quenching. The conductivity and Vickers hardness of the alloy are tested by conductivity meter and hardness meter, respectively. The microstructure of the alloy is characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). In general, the electrical conductivity of Cu-Ni-Si is the main consideration in the design of alloy composition, the content values of matrix Cu atoms are in the ranges of 90%-95.63% and 95.63%-97.5% respectively, the precipitated phases are designed according to δ-Ni₂Si and γ-Ni₅Si₂ respectively; the content of matrix Cu atoms is over 97.5%, it can be designed according to any phase of δ-Ni₂Si, γ-Ni₅Si₂ and β-Ni₃Si, with no difference in electrical conductivity among them. If the strength of the alloy is the main factor in the composition design, the content values of Cu atoms in the matrix are in the ranges of 90% — 93.93%, 93.93% — 94.34%, 94.34%— 95.63%, and 95.63%—96.12% respectively, according to the composition intervals the precipitated phases are designed as δ-Ni₂Si, γ-Ni₅Si₂, β-Ni₃Si, and γ-Ni₅Si₂, respectively. Once the content of Cu in the matrix is greater than 96.12%, the precipitated phase can be designed according to any of the phases of δ-Ni₂Si, γ-Ni₅Si₂ and β-Ni₃Si.

Keywords:

Cu–Ni–Si alloy /
cluster plus glue atom /
precipitation phase composition design /
high hardness /
electrical conductivity

Authors and contacts

1.
Key Laboratory of Materials Modification by Laser, Iron, and Electron Beams (Ministry of Education), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
2.
Inner Mongolia University For Nationalities, Tongliao 028000, China

Corresponding author: Dong Chuang, dong@dlut.edu.cn

Funds: Project supported by The National Natural Science Foundation of China (Grant No. 11674045)

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Cited By

图 1 基体Cu中立方八面体团簇

Figure 1. Cubooctahedral cluster in Cu matrix.

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图 2 δ-Ni₂Si团簇的三种构型

Figure 2. Three configurations of δ-Ni₂Si cluster

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图 3 δ-Ni₂Si相中分别以Ni¹, Ni², Si¹为心部原子的团簇径向原子密度

Figure 3. Radial atomic density around 3 different sites Ni¹, Ni² and Si¹ in the δ-Ni₂Si phase.

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图 4 γ-Ni₅Si₂团簇的十三种构型

Figure 4. Thirteen configurations of γ-Ni₅Si₂ cluster

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图 5 γ-Ni₅Si₂晶体相中分别以Ni¹, Ni², Si¹, Ni³, Ni⁴, Si², Si³, Si⁴, Si⁵, Ni⁵, Ni⁶, Ni⁷, Ni⁸为心的团簇径向原子分布

Figure 5. Radial atomic density around 13 different sites Ni¹, Ni², Si¹, Ni³, Ni⁴, Si², Si³, Si⁴, Si⁵, Ni⁵, Ni⁶, Ni⁷, Ni⁸ and Ni⁸ in the γ-Ni₅Si₂ phase.

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图 6 β-Ni₃Si团簇的两种构型

Figure 6. Two configurations of β-Ni₃Si cluster

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图 7 Ni/Si(at.%)分别为 (a) 2, (b) 2.5和(c) 3在C_Cu分别为 93.75%, 95%, 95.83%, 96.7%和97.5% 每一成分点处的合金XRD谱图

Figure 7. XRD patterns of the alloys when C_Cu is 93.75%, 95%, 95.83%, 96.7% and 97.5%, and the Ni/Si (at.%) is (a) 2, (b) 2.5 and (c) 3 in each composition point, respectively.

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图 8 合金的微观形貌. C_Cu为 93.75% 时Ni/Si 分别为(a) 2, (b) 2.5和(c) 3及C_Cu为96.7% 时Ni/Si 分别为(d) 2, (e) 2.5或(f) 3

Figure 8. The microstructure of the alloys. The Ni/Si is (a) 2, (b) 2.5 and (c) 3 when C_Cu is 93.75% and Ni/Si is (a) 2, (b) 2.5 and (c) 3 when C_Cu is 96.7%, respectively.

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图 9 Cu_96.7Ni_2.36Si_0.94 样品的(a)明场像和(b)选区衍射图***图(b)(123)中，2上面也有横杠***

Figure 9. (a) Bright-field micrographs and (b) selected area diffraction patterns of the Cu_96.7Ni_2.36Si_0.94 sample.

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图 10 (a) Ni/Si分别为2, 2.5, 3时, 维氏硬度和导电性随C_Cu的变化; 三元相图中 (b) 导电性和(c)维氏硬度随Cu, Ni和Si元素的原子分数的变化***图(a)和(b)中均应为%IACS***

Figure 10. (a) Ni/Si is 2, 2.5 and 3 respectively, the variation of vickers hardness and electrical conductivity as increase C_Cu; the variation of (b) electrical conductivity and (c) vickers hardness as atomic percent of Cu,Ni and Si in ternary phase diagram.

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表 1 δ-Ni₂Si相中以3种占位原子为心的径向原子分布

Table 1. Radial atomic distributions around 3 different sites in the δ-Ni₂Si phase.

心部原子	壳层原子数目	壳层原子种类	壳层原子与心部原子的距离r/nm	径向原子密度ρ/nm^-3	团簇	团簇构型
Ni¹	1	Si¹	0.20823	52.909	Ni₉Si₄	图2(a)
	2	Si¹	0.22614	82.615
	1	Si¹	0.23232	95.245
	2	Ni²	0.25359	102.526
	1	Ni²	0.26231	105.871
	1	Ni²	0.26268	118.602
	2	Ni¹	0.27021	133.174
	2	Ni²	0.27132	155.464
	1	Si¹	0.29611	128.795
Ni²	2	Si¹	0.24629	47.964	Ni₉Si₅	图2(b)
	2	Si¹	0.24872	77.619
	1	Si¹	0.24972	92.092
	2	Ni¹	0.25359	117.172
	2	Ni²	0.25818	138.792
	1	Ni¹	0.26231	145.573
	1	Ni¹	0.26268	158.136
	2	Ni¹	0.27132	167.423
	1	Si¹	0.32162	107.695
	2	Ni²	0.34426	93.668
Si¹	1	Ni¹	0.20823	52.909	SiNi₉	图2(c)
	2	Ni¹	0.22614	82.615
	1	Ni¹	0.23232	95.245
	2	Ni²	0.24629	111.915
	2	Ni²	0.24872	139.715
	1	Ni²	0.24972	153.381
	1	Ni¹	0.29611	101.196
	2	Si¹	0.31484	99.496
	1	Ni²	0.32162	100.515
	2	Si¹	0.34056	96.754

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表 2 γ-Ni₅Si₂ 相中以13种占位原子为心的径向原子分布

Table 2. Radial atomic distributions around 13 different sites in the γ-Ni₅Si₂ phase.

心部原子	壳层原子数目	壳层原子种类	壳层原子与心部原子的距离r/nm	径向原子密度ρ/nm^–3	团簇	团簇构型
Ni¹	3	Si⁵	0.23282	113.557	Ni₇Si₅	图4(a)
	6	Ni⁸	0.25853	138.229
	2	Si¹	0.26156	160.177
	6	Ni⁷	0.32954	120.138
	6	Ni⁴	0.39376	93.896
	6	Ni⁶	0.42716	91.935
	3	Si⁵	0.43428	96.236
	6	Ni⁸	0.45646	97.946
	6	Si²	0.47401	100.921
	2	Ni²	0.49734	91.258
Ni²	1	Ni²	0.23332	37.61	Ni₈Si₄	图4(b)
	1	Si¹	0.23578	54.668
	3	Si⁴	0.2421	100.995
	3	Ni⁶	0.24757	141.671
	3	Ni⁵	0.25331	176.342
	3	Ni⁵	0.34555	86.834
	3	Ni⁷	0.34582	103.957
	3	Ni³	0.38621	87.072
	3	Si³	0.4174	78.829
	3	Ni⁶	0.41824	88.149
	3	Ni⁵	0.42043	96.421
	3	Ni³	0.43617	94.99
Ni³	3	Si⁴	0.24409	65.696	Ni₁₀Si₄	图4(c)
	1	Si²	0.24965	76.755
	3	Ni⁵	0.25453	115.879
	3	Ni⁶	0.26112	147.572
	3	Ni⁵	0.26706	175.563
	1	Si³	0.36558	73.329
	3	Ni⁷	0.37339	82.588
	3	Ni²	0.38621	87.072
	3	Ni⁶	0.41335	81.169
	3	Ni⁵	0.42222	85.68
Ni⁴	3	Si⁵	0.23225	76.265	Ni₁₀Si₄	图4(d)
	1	Si³	0.25456	72.399
	3	Ni⁸	0.25532	114.807
	3	Ni⁷	0.25574	157.083
	3	Ni⁸	0.27402	162.522
	1	Si²	0.35821	77.949
	3	Ni⁶	0.37974	78.514
	3	Ni¹	0.39376	82.159
	3	Ni⁷	0.39797	90.948
	3	Ni⁸	0.41739	88.689
Ni⁵	1	Si⁴	0.23142	38.544	Ni₈Si₃	图4(e)
	1	Si³	0.23246	57.044
	1	Si⁴	0.24177	67.606
	1	Ni⁶	0.25071	75.786
	1	Ni⁶	0.25316	88.328
	1	Ni²	0.25331	102.866
	1	Ni⁵	0.25375	116.951
	1	Ni³	0.26706	137.942
	1	Ni⁶	0.28031	130.136
	2	Ni⁵	0.29349	132.276
Ni⁶	1	Si²	0.22997	39.278	Ni₉Si₄	图4(f)
	1	Si¹	0.23889	52.56
	1	Si⁴	0.2445	65.366
	1	Ni²	0.24757	78.706
	1	Si³	0.24916	92.651
	1	Ni⁵	0.25071	103.499
	1	Ni⁵	0.25316	117.77
	1	Ni⁸	0.25429	130.733
	1	Ni⁷	0.25495	144.134
	1	Ni⁷	0.26059	148.474
	1	Ni³	0.26112	160.988
	1	Ni⁷	0.26728	162.621
Ni⁷	1	Si³	0.22567	41.566	Ni₉Si₄	图4(g)
	1	Si¹	0.22958	59.218
	1	Si⁵	0.23849	70.434
	1	Si²	0.24038	85.982
	1	Ni⁸	0.24588	96.408
	1	Ni⁸	0.25044	106.443
	1	Ni⁶	0.25495	115.307
	1	Ni⁴	0.25574	128.522
	1	Ni⁵	0.26021	135.569
	1	Ni⁶	0.26059	148.474
	1	Ni⁶	0.26728	150.111
	1	Ni⁸	0.27224	153.893
Ni⁸	1	Si⁵	0.23059	38.962	Ni₉Si₄	图4(h)
	1	Si⁵	0.24054	51.486
	1	Ni⁸	0.2457	64.413
	1	Ni⁷	0.24588	80.34
	1	Si²	0.24656	95.613
	1	Ni⁷	0.25044	106.443
	1	Ni⁶	0.25429	116.207
	1	Ni⁴	0.25531	129.173
	1	Ni¹	0.25853	138.229
Ni⁸	1	Si¹	0.27197	130.605	Ni₉Si₄	图4(h)
	1	Ni⁷	0.27224	142.055
	1	Ni⁴	0.27402	150.913
Si¹	3	Ni⁷	0.22958	78.957	SiNi₁₁	图4(i)
	1	Ni²	0.23578	91.113
	3	Ni⁶	0.23889	140.161
	1	Ni¹	0.26156	120.132
	3	Ni⁸	0.27197	142.479
	3	Ni⁵	0.34489	87.334
	3	Si⁵	0.35017	100.131
	3	Si²	0.38543	87.602
	3	Si³	0.39237	94.898
	3	Si⁴	0.41136	92.647
Si²	3	Ni⁶	0.22997	78.556	SiNi₁₀	图4(j)
	3	Ni⁷	0.24038	120.375
	3	Ni⁸	0.24656	159.354
	1	Ni³	0.24965	168.861
	3	Ni⁵	0.33462	89.249
	3	Si⁵	0.35153	93.475
	1	Ni⁴	0.35821	93.539
	3	Si¹	0.38543	87.602
	3	Si³	0.38982	96.772
	3	Si⁴	0.40727	95.466
Si³	3	Ni⁷	0.22567	83.132	SiNi₁₀	图4(k)
	3	Ni⁵	0.23246	133.102
	3	Ni⁶	0.24916	154.418
	1	Ni⁴	0.25456	159.277
	3	Ni⁸	0.33473	89.161
	3	Si⁴	0.35895	87.797
	1	Ni³	0.36558	87.995
	3	Si²	0.38982	84.676
	3	Si¹	0.39237	94.898
	3	Si⁵	0.40056	100.344
Si⁴	2	Ni⁵	0.23142	57.816	SiNi₁₀	图4(l)
	2	Ni⁵	0.24177	84.507
	2	Ni²	0.2421	117.827
	2	Ni³	0.24409	147.817
	2	Ni⁶	0.2445	179.758
	2	Ni⁵	0.29512	120.803
	2	Si³	0.35895	77.468
	2	Si⁴	0.36743	81.857
	4	Si⁴	0.39431	81.816
	2	Si²	0.40727	81.323
Si⁵	2	Ni⁸	0.23059	58.364	SiNi₉	图4(m)
	2	Ni⁴	0.23225	95.331
	1	Ni¹	0.23282	113.559
	2	Ni⁷	0.23849	140.868
	2	Ni⁸	0.24054	171.621
	2	Ni⁸	0.28808	119.887
	2	Si¹	0.35017	77.879
	2	Si²	0.35153	76.979
	4	Si⁵	0.37643	80.603
	2	Si³	0.40056	74.329

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表 3 β-Ni₃Si相中以不同原子为心的径向原子分布

Table 3. Radial atomic distributions around 2 different sites in the β-Ni₃Si phase.

心部原子	壳层原子数	壳层原子种类	壳层原子与心部原子的距离r/nm	径向原子密度ρ/ nm⁻³	团簇	团簇构型
Ni¹	4	Si¹	0.24791	203.795	Ni₉Si₄	图6(a)
Ni¹	8	Ni¹	0.24791	203.795	Ni₉Si₄	图6(a)
Si¹	12	Ni¹	0.24791	203.795	SiNi₁₂	图6(b)

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表 4 Cu-Ni-Si-M (M = Fe or null)系列合金的Ni/Si(原子比)、团簇成分式、成分(原子分数)、维氏硬度(kgf/mm²)和导电率(%IACS)

Table 4. Ni/Si(at.%), Cluster formula, Composition(at.%), Vickers Hardness (kgf/mm²) and Electrical conductivity(%IACS) of Cu-Ni-Si-M (M = Fe or null) alloys.

Ni/Si (at.%)	cluster formulas	composition wt.% /at.%	Vickers Hardness kgf·mm^–2	Electrical Conductivity /%IACS
2	[(Fe_1/15Ni_9/15Si_5/15)Cu₁₂]Cu₃	95.18Cu3.52Ni0.93Si0.37Fe (Cu_93.75Ni_3.75Si_2.08Fe_0.42)	258	35
	([(Ni_10/15Si_5/15)Cu₁₂]Cu₃)₄+([CuCu₁₂]Cu₃)	96.14Cu3.11Ni0.75Si (Cu₉₅Ni_3.33Si_1.67)	161	51
	([(Ni_10/15Si_5/15)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)	96.79Cu2.59Ni0.62Si (Cu_95.83Ni_2.78Si_1.39)	189	35
	{[(Ni_10/15Si_5/15)_1.0602Cu₁₂]Cu₃}_0.996 +{[CuCu₁₂]Cu₃}	97.4Cu2.1Ni0.5Si (Cu_96.7Ni_2.2Si_1.1)	191	40
	([(Ni_10/15Si_5/15)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)₃	98.08Cu1.55Ni0.37Si (Cu_97.5Ni_1.67Si_0.83)	172	48
2.5	[(Fe_1/14Ni_9/14Si_4/14)Cu₁₂]Cu₃	95.04Cu3.75Ni0.8Si0.41Fe (Cu_93.75Ni_4.01Si_1.79Fe_0.45)	262	32.5
	([(Ni_10/14Si_4/14)Cu₁₂]Cu₃)₄+([CuCu₁₂]Cu₃)	96.03Cu3.33Ni0.64Si (Cu₉₅Ni_3.57Si_1.43)	201	41
	([(Ni_10/14Si_4/14)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)	96.69Cu2.78Ni0.53Si (Cu_95.83Ni_2.98Si_1.19)	201	38
	{([(Ni_10/14Si_4/14) _1.0602Cu₁₂]Cu₃)}_{0.996 +}([CuCu₁₂]Cu₃)	97.39Cu2.2Ni0.41Si (Cu_96.7Ni_2.36Si_0.94)	168	41
	([Ni_10/14Si_4/14)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)₃	98.02Cu1.66Ni0.32Si (Cu_97.5Ni_1.79Si_0.71)	176	48
3	([(Fe_1/16Ni_11/16Si_4/16)Cu₁₂]Cu₃)	94.93Cu4.02Ni0.7Si0.35Fe (Cu_93.75Ni_4.3Si_1.56Fe_0.39)	241	30
	([(Ni_12/16Si_4/16)Cu₁₂]Cu₃)₄+([CuCu₁₂]Cu₃)	95.94Cu3.5Ni0.56Si (Cu₉₅Ni_3.75Si_1.25)	225	33
	([(Ni_12/16Si_4/16)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)	96.63Cu2.91Ni0.46Si (Cu_95.83Ni_3.13Si_1.04)	191	36
	{([(Ni_12/16Si_4/16)_1.0602Cu₁₂]Cu₃)}_0.996 + ([CuCu₁₂]Cu₃)	97.33Cu2.31Ni0.36Si (Cu_96.7Ni_2.47Si_0.83)	160	39
	([(Ni_12/16Si_4/16)Cu₁₂]Cu₃)₂+([CuCu₁₂]Cu₃)₃	97.98Cu1.74Ni0.28Si (Cu_97.5Ni_1.87Si_0.63)	171	47

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Vol. 68, Issue 19 - 2019-10-05

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