Transactions of The Indian Institute of Metals
Effect of Zn concentration on diffusion induced grain boundary
migration in Cu –Zn system
A.K. Pradhan, S.P. Gupta and K. Mondal
Department of Materials and Metallurgical Engineering, Indian Institute of Technology, Kanpur-208 016, UP, India.
E-mail: kallol@iitk.ac.in
Received 19 January 2009
Revised 24 April 2009
Accepted 29 May 2009
Online at www.springerlink.com
© 2009 TIIM, India
Abstract
Cu-Zn alloy system with three different compositions has been chosen to study the time, temperature and composition dependence of the
Diffusion Induced Grain boundary Migration (DIGM) in the temperature range of 277-427
o
C. The grain boundary migration follows parabolic
rate law as a function of time. The diffusivity, D
b
α, was calculated from concentration-distance profile using growth rate, v. The activation
energy for diffusion is found to be 101kJ/mol which is nearly half of the activation energy required for volume diffusion indicating that
preferential grain boundary diffusion is more favorable than volume diffusion leading to grain boundary migration in Cu-Zn system.
1. Introduction
Diffusion Induced Grain boundary Migration (DIGM) is
a part of the more general Chemically Induced Interface
Migration (CIIM), which includes Liquid Film Migration
(LFM) and simple Interface Migration (IM) between two
different phases
1
. CIIM plays an important role during many
different practical processes like welding, preferential
oxidation, sintering, and isothermal heat treatment of systems
involving two phases which are not in equilibrium with each
other [1]. The preferential diffusion of solute atom into the
grain boundary than that into the grain is the basis for
DIGM. When a poly-crystalline material is exposed to any
solute vapor at low temperature where volume diffusion is
negligible, the solute diffusion will be more through the grain
boundary because of its open structure compared to that of
the packed structure of the grain, which leads to a
concentration gradient between the grain boundary and
adjacent grain interior and this causes the grain boundary to
migrate leaving behind the solute atoms in order to maintain
homogeneity [1].
Rhines and Montgomery [2] first discovered DIGM in
Cu-Zn system. However, composition change was not
observed. After that many researchers have shown that at
low temperature the composition change due to DIGM is
much faster than due to the volume diffusion process [3-5].
Diffusion coefficient of solute in DIGM has been observed
to be 8-10 orders of magnitude higher than that in volume
diffusion process. Though many theories have been
proposed for the occurrence of DIGM such as coherency
strain energy theory [6], chemical free energy theory [7],
grain boundary energy theory [8] etc, it is still not clear what
guides the grain boundary movement. Recently, Sivaiah
et al. [4] have shown the DIGM in Cu-Zn system using Cu-
38wt% Zn alloy as source and they have concluded
coherency strain energy to be the driving force for DIGM. In
Keywords:
diffusion induced grain boundary migration; SEM EDAX; activation
energy; diffusivity; optical metallography
the present case, Cu-Zn system with three different
compositions has been chosen to study the composition
dependence of DIGM in the temperature range of 277-427
o
C.
It has been shown that the preferential grain boundary
diffusion of solute atom is the main reason for DIGM.
2. Experimental
High purity Cu in rod form and Zn in small pieces of
99.9% purity was used. The Cu rod of 9mm diameter was first
swaged into 5mm diameter. The swaged Cu rod was then
rolled into 0.9mm thickness plate and then cut into pieces
with approximately 7.62 cm (3 inch) length each. These pieces
were polished by using 4/0 emery paper and then
ultrasonically cleaned first using methanol for 10 minutes
and then using water for 10 minutes. The water cleaning was
done to remove methanol completely and this would avoid
the formation of dark spots on the samples during heat
treatment.
Cu pieces were vacuum-encapsulated in quartz tube at a
pressure less than 10
-5
mbar and annealed at 900
o
C for 24
hours to relieve any internal stress present in sample and to
obtain large grains. This helps to study DIGM under optical
microscope easily. Internal stress may alter the result since
coherency strain produced by diffused solute atoms is
supposed to be the driving force for DIGM. After annealing
the Cu sheets were cut into pieces with 6mm width using a
slow speed diamond cutter and thus avoid any stress
generation during cutting. The final dimension of the sample
remains approximately 9mm x 6mm x 0.8mm (L x W x T).
Alloy with desired compositions (33 wt% Zn, 20 wt% Zn
and 10 wt% Zn) were prepared by encapsulating the Cu
sheet and Zn pieces in required amount inside quartz tube
under vacuum. The alloy compositions are so chosen as per
binary phase diagram of Cu-Zn system
9
in order to avoid the