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Acta Metall Sin  2019, Vol. 55 Issue (10): 1291-1301    DOI: 10.11900/0412.1961.2019.00080
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Composition Rule of High Hardness and Electrical Conductivity Cu-Ni-Si Alloys
LI Dongmei1,2,JIANG Beibei1,LI Xiaona1,WANG Qing1,DONG Chuang1()
1. Key Lab 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. School of Mechanical Engineering, Inner Mongolia University For Nationalities, Tongliao 028000, China
Cite this article: 

LI Dongmei, JIANG Beibei, LI Xiaona, WANG Qing, DONG Chuang. Composition Rule of High Hardness and Electrical Conductivity Cu-Ni-Si Alloys. Acta Metall Sin, 2019, 55(10): 1291-1301.

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Abstract  

Cu-Ni-Si alloys are among the most widely used electrical conductive (>30%IACS) alloys with quite high strength level (>500 MPa), so they are especially suitable for lead frames and connector joints. However, these two properties are quite composition sensitive, apart from their tight connection with processing. Moreover, their compositions fall within quite broad ranges that poses difficulties for the industries. For instance, typical C7025 alloy has a specified composition (mass fraction, %) range of Ni 2.2~4.2, Si 0.25~1.2, Mg 0.05~0.3, plus less than 0.5 of other impurity elements. Obviously the composition ranges of the elements are far from even their absolute contents. The present work focuses on understanding the composition rule of Cu-Ni-Si via a new structural tool, the cluster-plus-glue-atom model. In this model, any solid solution is described by a nearest neighbor coordination polyhedron plus a one-to-six glue atoms. Specifically for Cu-based alloys, the cluster is cubooctahedron. The composition formula for solute-rich Cu-Ni-Si alloys and pure Cu are established, respectively [(Ni2/3Si1/3)-Cu12]Cu1~6 and [Cu-Cu12]Cu3. A series of Cu-Ni-Si alloys were designed on the basis of the cluster-plus-glue-atom model. In the concentrated solute region with Cu content less than 95%, the alloys were designed using the single cluster model [(Ni2/3Si1/3)-Cu12]Cu1~6. In the dilute solute region where Cu content is larger than or equal to 95%, the alloys were designed using the double cluster model {[(Ni2/3Si1/3)-Cu12]Cu3}A+{[Cu-Cu12]Cu3}B. The alloys were arc-melted into ingots under Ar atmosphere and were subjected to a solution treatment at 950 ℃ for 1 h plus water quenching, and then to an ageing at 450 ℃ for 4 h plus water quenching. The microstructure and properties of the alloys were characterized and tested by XRD, OM, TEM, Vickers hardness tester and digital metal conductivity instrument. The composition rule of the designed Cu-Ni-Si alloy was obtained by experiments.The results shown a special range of Cu content in 95.0%~95.8% as a composition sensitive region, in which, in addition to ageing precipitation strengthening, the alloys also have amplitude modulated decomposition strengthening, resulting in a sudden increase in Vickers hardness and a decrease in electrical conductivity. Vickers hardness and electrical conductivity change with composition variations in an irregular manner. In the concentrated and dilute solute region before and after the composition sensitive region, Vickers hardness (H) is linearly related to the Cu content (CCu) by H=-12.6CCu+1362.7 and H=-26.2CCu+2777.3, and the corresponding electrical conductivity (σ) is also linearly related to the CCu by σ=0.2CCu+28.6 and σ=5.2CCu-466.

Key words:  Cu-Ni-Si alloy      composition rule      hardness      electrical conductivity      composition sensitive region     
Received:  25 March 2019     
ZTFLH:  TG146.1  

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2019.00080     OR     https://www.ams.org.cn/EN/Y2019/V55/I10/1291

Commercial-grade alloy

Composition, mass fraction / %

(atomic fraction / %)

Ni/Si

(atomic ratio)

Electrical conductivity / %IACS

Vickers hardness

HV

CAC65[21]

Cu-3.2Ni-0.68Si-0.5Sn-1.0Zn

2.2

48

200

(Cu93.81Ni3.43Si1.53Sn0.27Zn0.96)

KLF-125[19]

Cu-3.2Ni-0.75Si-1.25Sn-0.3Zn

2.0

35

200

(Cu93.92Ni3.44Si1.69Sn0.66Zn0.29)

KLFA85[20]

Cu-3.2Ni-0.7Si-1.1Zn

2.2

40

260

(Cu93.95Ni3.42Si1.57Zn1.06)

HCL305[23]

Cu-2.5Ni-0.5Si-1.7Zn-0.03P

2.3

43

180

(Cu94.49Ni2.69Si1.12Zn1.64P0.06)

KLF-1[18]

Cu-3.2Ni-0.75Si-0.32Zn

2.0

55

180

(Cu94.59Ni3.42Si1.68Zn0.31)

MAX375[24]

Cu-2.85Ni-0.7Si-0.5Sn-0.5Zn

1.9

40

230

(Cu94.62Ni3.06Si1.57Sn0.27Zn0.48)

QSi0.7[19]

Cu-3.2Ni-0.7Si-0.3Zn

2.2

56

220

(Cu94.72Ni3.42Si1.57Zn0.29)

C7025[22]

Cu-3.0Ni-0.65Si-0.15Mg

2.5

40

200

(Cu94.96Ni3.2Si1.45Mg0.39)

EFTEC-23Z[22]

Cu-2.5Ni-0.65Si-0.5Zn-0.03Ag

1.8

53

200

(Cu95.37Ni2.67Si1.46Zn0.48Ag0.02)

MAX251[24]

Cu-2Ni-0.5Si-0.5Sn-1Zn

1.9

48

178

(Cu95.49Ni2.15Si1.13Sn0.27Zn0.96)

MAX251C[24]

Cu-2Ni-0.5Si-0.5Sn-1Zn

1.9

37

195

(Cu95.49Ni2.15Si1.13Sn0.27Zn0.96)

C7035[21]

Cu-1.5Ni-0.6Si-1.1Co

2.1

55

260

(Cu95.87Ni1.61Si1.35Co1.17)

CW111C[21]

Cu-2.05Ni-0.6Si

1.6

40

150

(Cu96.46Ni2.2Si1.34)

C7026[25]

Cu-2Ni-0.45Si

2.1

40

200

(Cu96.84Ni2.15Si1.01)

C19010[26]

Cu-1.6Ni-0.3Si

2.5

60

150

(Cu97.6Ni1.72Si0.68)

QSi0.25[20]

Cu-1.0Ni-0.25Si-0.1Zn

1.9

61

160

(Cu98.26Ni1.08Si0.56Zn0.1)
Table1  Composition, Ni/Si, electrical conductivity and Vickers hardness of commercial-grade Cu-Ni-Si alloy[18,19,20,21,22,23,24,25,26]
Fig.1  Two-dimensional projection diagram of Ni-Si cluster structural units dispersed in Cu matrix

No.

Cluster formula

Composition, mass fraction / %

(atomic fraction / %)

Electrical conductivity

%IACS

Vickers hardness HV

FWHM

(°)

1

[(Ni2/3Si1/3)1.106-Cu12]Cu0.894

93.9Cu-4.95Ni-1.19Si

49

201

0.322

(Cu92.1Ni5.3Si2.6)

2

[(Ni2/3Si1/3)1.05-Cu12]Cu0.95

94.2Cu-4.7Ni-1.1Si

51

195

0.326

(Cu92.5Ni5Si2.5)

3

[(Ni2/3Si1/3)-Cu12]Cu1

94.4Cu-4.5Ni-1.1Si

51

193

0.329

(Cu92.8Ni4.8Si2.4)

4

[(Ni2/3Si1/3)-Cu12]Cu2

94.8Cu-4.2Ni-1Si

51

187

0.318

(Cu93.3Ni4.4Si2.2)

5

[(Ni2/3Si1/3)-Cu12]Cu3

95.1Cu-4Ni-0.9Si

52

183

0.25

(Cu93.7Ni4.2Si2.1)

6

[(Ni2/3Si1/3)-Cu12]Cu4

95.5Cu-3.6Ni-0.9Si

51

176

0.277

(Cu94.1Ni3.9Si2)

7

[(Ni2/3Si1/3)-Cu12]Cu6

95.9Cu-3.3Ni-0.8Si

50

169

0.314

(Cu94.7Ni3.5Si1.8)

8

{[(Ni2/3Si1/3)-Cu12]Cu3}4+

{[Cu-Cu12]Cu3}1

96.1Cu-3.1Ni-0.8Si

51

161

0.266

(Cu95Ni3.3Si1.7)

9

{[(Ni2/3Si1/3)-Cu12]Cu3}2+

{[Cu-Cu12]Cu3}1

96.8Cu-2.62Ni-0.63Si

39

216

0.348

(Cu95.8Ni2.8Si1.4)

10

{[(Ni2/3Si1/3)1.0602-Cu12]Cu3}0.996 +{[Cu-Cu12]Cu3}197.4Cu-2.1Ni-0.5Si

40

191

-

(Cu96.7Ni2.2Si1.1)

11

{[(Ni2/3Si1/3)-Cu12]Cu3}2+

{[Cu-Cu12]Cu3}3

98.1Cu-1.5Ni-0.4Si

48

172

0.278

(Cu97.5Ni1.7Si0.8)
Table 2  The cluster formula, composition, electrical conductivity, Vickers hardness and full-width half-maximum (FWHM) of the design Cu-Ni-Si alloys
Fig.2  XRD spectra of the Cu-Ni-Si alloys after ageing at 450 ℃ for 4 h
Fig.3  OM images of Cu-Ni-Si alloys after ageing at 450 ℃ for 4 h
Fig.4  Bright-field TEM images (a, c) and corresponding SAED parrerns (b, d) of No.9 (a, b) and No.10 (c, d) alloys after ageing at 450 ℃ for 4 h
Fig.5  The variations of Vickers hardness (a) and electrical conductivity (b) with atomic fraction of Cu (CCu) of Cu-Ni-Si alloys after ageing at 450 ℃ for 4 h
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