Effects of Ni addition on the microstructure and properties of nanostructured copper–germanium alloys

doi:10.1016/j.intermet.2013.02.015

Intermetallics

Volume 38, July 2013, Pages 80-87

https://doi.org/10.1016/j.intermet.2013.02.015 Get rights and content

Abstract

The effects of Ni addition on the structure and various phase transitions of nanocrystalline Cu–Ge alloys were investigated for the first time. Cu₈₄Ge_16−xNi_x (x = 0,1,3 and 5 wt.%) alloys were mechanically alloyed at room temperature and evaluated by means of X-ray diffraction, differential thermal analysis, thermal gravimetry, and scanning and transmission electron microscopy observations. Nanocrystalline α−Cu(Ge) solid solution was observed to form during the early stages of mechanical alloying. After prolonged milling times, it was partially transformed into the ζ−Cu₅Ge intermetallic compound with an hcp structure. Increased quantities of Ni in the alloys not only delayed the formation of the intermetallic phase upon mechanical alloying and the nanocrystallization transition during annealing but also decreased the crystallite and particle size, which gave rise to nanocrystalline alloys with a high thermal stability at temperatures near their melting points. The mechanism leading to the high stability achieved was also investigated and described.

Graphical abstract

Highlights

► The effects of Ni on the structural evolution of nanocrystalline Cu–Ge alloys were investigated. ► Ni addition resulted in diminishing the crystallite and particle sizes during mechanical alloying. ► Ni addition resulted in postponing the nanocrystallization transition during heat treatment. ► Excellent thermal stability was demonstrated at high temperatures. The mechanism was proposed.

Introduction

Over the past two decades, copper–germanium alloys have received a great deal of attention on account of their outstanding semiconducting properties, which is an indispensable property required for electrical and electronic applications. Recently, it has become increasingly important to develop novel semiconducting and dielectric materials with enhanced performance [1], [2], [3], [4], [5], [6], [7], [8], [9]. The most facile and practicable method for developing the new alloys of interest is adding alloying elements to the binary Cu–Ge alloys. Depending principally on the desired properties and functionalities, a variety of alloying elements have been utilized in the ternary Cu–Ge-X alloys including Sn [10], Mn [10], [11], [12], Fe [12], [13], [14], Co [12], Ni [12], [15], [16], [17], [18], Ag [19], [20], [21], Al [22], Te [23], Se [24], Si [25], [26], Tl [27], Ga [28], Tm [29], Au [30] and Ce [31]. Among these elements, transition metals like Ni are significant mainly due to their properties such as compatibility, relatively low cost, and availability.

Ternary Cu–Ge–Ni alloys were first investigated by Bochvar et al. [16] and Burkhardt and Schubert [17] on a partial isothermal section at 500 °C. Cockayne and Raynor [12] assessed the effect of Ni addition on the lattice constants of the ζ−Cu₅Ge phase. Recently, Cornish and Watson reviewed all previous studies on this ternary system [15]. However, no further systematic study is reported in the literature on Cu–Ge–Ni alloys, especially on the effects of adding Ni to nanocrystalline Cu–Ge alloys. As an attempt to establish a promising direction for further developments in the field, the present research work was designed to explore the effects of Ni on the microstructure and various properties of nanostructured copper–germanium alloys.

Section snippets

Materials processing

High purity elemental powders of Cu, Ni, and Ge with average particle sizes of 10, 10 and 5–20 μm, respectively, were subjected to high energy ball milling in a Fritsch P6 planetary ball mill using 10 mm WC balls and vial to form the Cu₈₄Ge_16−xNi_x (x = 0, 1, 3 and 5 wt.%) compositions. We will refer to the four alloys by their nominal Ni addition throughout the current article, as presented in Table 1. A ball to powder ratio (BPR) of 10:1 was maintained and milling speed was kept at 300 rpm for

XRD studies

The XRD patterns of the four study alloys after different MA times are presented in Fig. 1 (a–d) in which the diffraction peaks of the initial materials can be clearly seen. According to this Figure, the diffraction peaks weakened and broadened gradually with milling time. However, as shown in all the XRD patterns, the intensity of Ni and Ge elements diminished more rapidly than those of Cu, which can be attributed to the negligible solubility of Ni in Ge structure, whereas Ge can be highly

Conclusion

In this study, adding Ni to binary Cu–Ge alloys by means of MA, and the subsequent annealing were investigated. It was found that increasing Ni content in the alloys leads to such consequences as suppressing the formation of the intemetallic phase during MA, reducing the driving force for nanocrystallization during subsequent annealing, and decreasing the crystallite size of the alloys; hence, the high thermal stability of the Ni containing Cu–Ge nanostructured alloys prepared. Furthermore, it

Acknowledgement

ARK would like to thank Asma Rezaei for her valuable contribution to this project.

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¹: Present address. School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran.

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Effects of Ni addition on the microstructure and properties of nanostructured copper–germanium alloys

Abstract

Graphical abstract

Highlights

Introduction

Section snippets

Materials processing

XRD studies

Conclusion

Acknowledgement

J Alloys Compd

J Less-Common Met

Acta Metall

J Alloys Compd

Acta Metall

CALPHAD

Acta Metall

Acta Mater

Acta Mater

Polymer

J Supercrit Floids

Intermetallics

Mater Sci Eng A

Scr Metall Mater

Scr Metall Mater

Scr Metall Mater

Scr Metall Mater

Acta Mater

Nanostruct Mater

Acta Mater

Mater Sci Eng A

Nanostruct Mater

J Cryst Growth

Acta Mater

Scr Metall

Acta Metall

Acta Metall

Self-assembled three-dimensional Cu–Ge nanoweb composite

Nanotechnology

Morphological instability of bilayers of copper germanide films and amorphous germanium

Appl Phys Lett

Cu–Ge core shell nanowire arrays as three dimensional electrodes for high-rate capability lithium-ion batteries

J Mater Chem

Compositional study of copper–germanium ohmic contact to n-GaN

J Electron Mater

Effect of phase transitions in copper-germanium thin-film alloys on their electrical resistivity

J Mater Sci

High density germanium nanowire growth directly from copper foil by self-induced solid seeding

Chem Mater

Atomic scale alignment of copper–germanide contacts for Ge nanowire metal oxide field effect transistors

Nano Lett