MA TE RI A L S CH A R A CT ER IZ A TI O N 59 ( 20 0 8 ) 5 4 2–5 4 6

Microscopic bonding mechanism of welding interface with

molten Cu–4Zn deposited on solid-state steel

Hengzhi Wang a,b , Kehong Wang a , Rongkun Zheng b , K. Satya Prasad b,c , Simon P. Ringer b,⁎
a
Department of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, PR China
b
Australian Key Centre for Microscopy & Microanalysis, The University of Sydney, NSW 2006, Australia
c
Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad, 500 058, India

AR TIC LE D ATA ABSTR ACT

Article history: An initial characterization was carried out on the heat affected zone between a 30CrMnSi
Received 1 November 2006 steel and a Cu–4Zn (wt.%) alloy formed from a novel welding technique involving induction
Received in revised form melting of a Cu alloy over a steel substrate at 1100 °C. A very thin (∼ 20 nm) reaction interface
26 March 2007 between the steel substrate and the Cu alloy is shown to play a key role in effecting these
Accepted 5 April 2007 joints. This reaction interface is an Fe–Cu rich discrete phase with a FCC structure and
substantial coherence to both the steel substrate and the Cu alloy layer. This reaction
interface is expected to form under highly non-equilibrium conditions and provides a
Keywords: bridging effect for the join. This is proposed as the major reason for the strength and
Welding mechanical integrity of the weld.
Cu–4Zn alloy © 2007 Elsevier Inc. All rights reserved.
Steel substrate
Interface
Bonding

1. Introduction where [1,6] a Cu alloy was melted at 1100 °C and solidified on

In order to improve electrical or thermal conductivity or
corrosion resistance, or to modify hardness on the surface of
steel substrate, a layer of copper alloy either coated or welded
to the steel substrate is known to be effective [1]. The
thickness of this copper alloy layer may vary from microns
to several millimeters [2,3]. However, normal arc-welding
techniques usually fail in achieving a strong bond due to
incomplete fusion of the steel substrate [1,2,4,5].
There has been much interest in aeronautical and military
applications for the development of welding technology that
can fuse fine thin layers of Cu alloy to solid-state steel
substrates. A novel welding technique termed Induction-Heat
Deposition of Molten-Copper (IHDMC) [1,6,7], has been devel-
oped recently to meet such these requirements and is shown
schematically in Fig. 1(a). In this technique, described else-
the solid-state steel substrate. The temperature of the molten
Cu–4Zn alloy is measured by optical pyrometry and is
controlled by the input power to the induction coil or by the
speed of movement of the Cu–4Zn and steel. Wang et al. [1,6]
have used this IHDMC technique to produce the weldments
that exhibit excellent mechanical properties (e.g. micro-
hardness near the interface, shear strength, twist strength
and tensile strength) of the weld joint. In Fig. 1(b), most of the
shear strength values of the weld joint are actually higher than
that of the base copper alloy (170 MPa). However, the
preliminary examination of these weldments was unable to
reveal any details of the fusion zone of the join [1,2,6].
The aim of this paper is to characterize the interface
between steel and Cu–4Zn alloy produced by IHDMC techni-
que using electron microscopy so as to investigate the likely
origins of the fusion.

⁎ Corresponding author. Tel.: +61 2 9351 2351; fax: +61 2 9351 7682.
E-mail address: simon.ringer@emu.usyd.edu.au (S.P. Ringer).

1044-5803/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2007.04.002
 M A TE RI A L S CH A RACT ER IZ A TI O N 59 ( 20 0 8 ) 5 4 2 –5 4 6
2. Experimental Procedure
In the present work, a block of Cu–4Zn/Steel weldment was
available from an industrial scale IHDMC process [1,6] as
shown in Fig. 1(a). The nominal chemical composition (wt.%)
of the steel substrate was Fe, 0.3C, 0.75Cr, 0.9Mn, 0.9Si and
b0.025 (S and P) and that of the copper alloy is Cu–4Zn.
Scanning electron microscopy (SEM) studies were made on the
transverse section of the weld joint following preparation
using standard metallographic polishing procedures. The as-
polished specimens were etched with 3 vol.% HNO3 in
methanol to reveal the steel microstructure. The etched
specimens were observed using a Philips XL30 analytical
SEM attached with an EDAX energy dispersive X-ray spectro-
meter (EDXS). Elemental mapping of different elements was
carried out with a collection time of about 7 h. All micro-
structural observations were made normal to the weld
interface.
For transmission electron microscopy (TEM) examination,
0.4 mm thick specimens were cut normal to the Cu–4Zn/Steel
interface using a low speed diamond saw. Discs of 3 mm dia
were punched to include a minimum portion of steel so as to
minimize the magnetic field for TEM studies. These discs were
thinned mechanically to ∼ 50 μm by tripod polishing followed
by ion milling using a Gatan 691 precision ion polishing
Fig. 1 – (a) Schematic diagram of IHDMC welding process, and (b) the shear strength of weldment.
543
system under a beam energy of 3.5 kV and a beam current of 8–
10 μA. In the present study, all the TEM/HRTEM work was
carried out on a JEOL 3000F TEM operating at 300 kV, which is
equipped with an EDXS (INCA, Oxford). Digital Micrograph was
used for Fast Fourier Transformation (FFT) to obtain the
diffraction patterns from the high resolution lattice images.
3. Results and Discussion
Fig. 2(a) provides a SEM micrograph of the weld joint between
the steel and Cu–4Zn alloy. It was observed that the interface
is very sharp and without un-welded regions and welding
cracks. Well delineated prior austenite grain boundaries
(marked by arrows) were observed in the steel annotated in
Fig. 2(b) and EDXS elemental mapping of Fe–Kα and Cu–Kα
results are presented in Fig. 2(c) and (d), respectively. The
degree of inter-diffusion of either Fe or Cu was observed to be
quite limited at this level of magnification, because the
transitional composition thickness was well within 1 μm for
iron or copper element. Considering the microstructure on
either side of the Cu–4Zn/steel interface and the limited
elemental diffusion indicated in Fig. 2(c) and (d), it was
suggested that the mechanism underpinning the IHDMC
technique is completely different from the traditional droplet
welding [8], die welding [9] and flow welding [10]. The apparent
544 MA TE RI A L S CH A R A CT ER IZ A TI O N 59 ( 20 0 8 ) 5 4 2–5 4 6
Fig. 2 – (a) and (b) SEM micrographs of etched surface of the weld joint at low and high magnifications respectively. (c) and (d) are
the X-ray elemental maps of Fe and Cu respectively.
Fig. 3 – TEM micrographs of (a) dark field and (b) bright field
images showing the reaction interface at the Cu–4Zn/stell
weld joint.
novelty of this welding technique required further investiga-
tion of the interface at higher resolution.
Fig. 3 shows the dark field and bright field TEM images of
the steel/Cu–4Zn alloy. A single-phase microstructure was
observed on the Cu–4Zn side, whereas a ferrite and eutectoid
ferrite + pearlite microstructure was observed. The interface
was found to be continuous along the weld joint, however, a
few discontinuities were also observed. This reaction interface
is considered a particularly significant observation, the
thickness of this band was between 5 and 30 nm. This reaction
interface region seems to have formed due to the partial
melting and/or fusion of the steel substrate and the Cu–4Zn
alloy.
Fig. 4 provides a HRTEM image of the reaction interface
region indicating that the reaction interface phase has a
polycrystalline structure and was well bonded with both the
steel and the Cu alloy. Moreover, the reaction interface
consisted of very small grains. During observation of the
HRTEM micrograph, to identify the crystal structure of the
nanosized grains, FFT operation was employed to several
small regions, including the marked positions (A, B, and C) in
Fig. 4. Corresponding to the position-A, FFT result showed that
the substrate steel was oriented with the b111N zone axis of
BCC structure parallel to the electron beam. However, very
close to the reaction interface on the steel (position-B), the FFT
image also provided the b111N zone axis containing 1/3 and 2/3
g{110} additional reflections. This modified pattern indicated
that the original BCC phase had transformed into a new
structure due to the limited diffusion of Cu into the solid-state
steel and the heat effect during IHDMC processing. Based on
the acquired FFT pattern, it was suggested that a BCC-to-9R
phase transformation [11,12] could take place in position-B
 M A TE RI A L S CH A RACT ER IZ A TI O N 59 ( 20 0 8 ) 5 4 2 –5 4 6 545

region, because the reported 9R-structure exhibited the same Table 1 – EDXS chemical composition (at.%) obtained from
b111N FFT pattern and very close chemical compositions (1.63 different regions of the weld joint
at.% Cu ). In thermally-aged Fe-1.23 wt.% Cu alloy, Othen et al. Region Fe Cu Cr Zn Mn Si
[11,12] showed that the initially coherent nanoscale Cu
Reaction interface 48.02 51.22 0.75
precipitates could martensitically transform into a twinned
Steel-side 95.83 1.63 1.7 0.49 0.88
9R structure upon annealing at 550 °C. An ideal 9R structure Cu–4Zn-side 35.4 62.19 2.1
has an orthorhombic unit cell with a = 0.43 nm, b = 0.25 nm,
and c = 1.84 nm [12], and the name of “9R” came from the
stacking sequence along [001] direction or c-axis. In terms of the various crystal interfaces generated during
Within the reaction interface region shown in Fig. 4, it was this weld, it was observed that most of the α-Fe lattice
noted that the whole interfacial area was composed of matched very closely with the reaction interface lattice.
nanosized polycrystalline grains, and different crystallo- Accordingly, it was proposed that the strong bond between
graphic orientations were displayed in the crystal lattice
the α-Fe and reaction interface established by metallic
image. In order to identify the crystal structure of the reaction
bonding. In the case of Cu–4Zn/reaction interface joining
interface, FFT operations were carried out on several specific
region lattice match was observed all along. Considering the
crystal lattices. It was interesting to find that some FFT matching state of the two crystal lattices, the Cu–Zn/reaction
patterns could be indexed as a FCC phase with b112N (to interface, excellent lattice matching was observed. This
position-C), b110N, and b111N zone axes, respectively. The matching is likely due to the solidification of the Cu–4Zn
calculated lattice parameter from the FFT images was alloy on the reaction interface phase providing an effective
approximately 0.85 nm. At present, however, further experi- bridging effect.
mental work is required to provide more detailed information
on the crystal structure of these nanoscale polycrystalline
grains in the reaction interface.
4. Conclusions
Electron microanalysis using EDXS experiments were
carried out using a low background holder to investigate the
The present investigation of the microscopic bonding
chemical composition of the reaction interface and also on the
mechanism and elemental diffusion across a Cu–4Zn/steel
either side close to reaction interface. The semi-quantitative
welding interface are arising from the IHDMC process. The
chemical analysis obtained from all the three regions are
results indicate that there exists a very thin layer of reaction
listed in Table 1. The reaction interface phase contains
interface (∼ 20 nm in thickness) between the Cu–4Zn alloy and
approximately equal fractions of both Cu and Fe. From the
steel substrate, which formed during IHDMC processing. The
composition table, it is interesting to note that the diffusion of
reaction interface possesses a FCC structure. The chemical
Fe into Cu–4Zn side is much more (35.4 at.%) compared to the
composition of the reaction interface was found to contain
Cu into the steel (only 1.63 at.%). This could be due to the fact
approximately equal fractions of Fe and Cu. The reaction
that the Cu alloy is in the molten state and the diffusion rate is
interface covered most (N90%) of the welding interface.
high. These results indicate that the reaction interface region
Accordingly, the weld strength is attributed to the structural
could be a mushy zone on the steel substrate during the
bridging associated with this reaction interface region.
welding. The diffraction results and microanalysis suggest
that the reaction interface is a compound that has formed
under non-equilibrium conditions.
Acknowledgements

The first author (HZW) gratefully acknowledges Prof. Xu YL

and Prof. Wang JP for their contributions to the Cu–4Zn/Steel
weldment by IHDMC technique. HZW would like to acknowl-
edge the Department of Science and Technology (Nanjing
University of Science and Technology, China) for their
financial support through the NJUST Development Founda-
tion (2002). Satya Prasad is grateful for the DMRL, Hyderabad,
India for leave to take up a visiting scientist position at The
University of Sydney. The authors are grateful for scientific
and technical input and support from the NANO-MNRF node
at The Electron Microscope Unit at The University of Sydney,
particularly from Dr. Kyle Ratinac.

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