ISSN 0036-0295, Russian Metallurgy (Metally), Vol. 2008, No. 6, pp. 475–479. © Pleiades Publishing, Ltd., 2008.

Original Russian Text © A.I. Ancharov, T.F. Grigoryeva, A.P. Barinova, V.V. Boldyrev, 2008, published in Metally, 2008, No. 6, pp. 33–38.

Interaction between Copper and Gallium

A. I. Ancharova, b, T. F. Grigoryevaa, A. P. Barinovaa, and V. V. Boldyreva, b
aInstitute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences,
ul. Kutateladze 18, Novosibirsk, 630128 Russia
e-mail: grig@solid.nsc.ru
bNovosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia

Received March 17, 2008

Abstract—The interaction between solid copper and liquid gallium is considered, which is the main process
during the setting of diffusion-solidifying solders. The dependences of the process rate and the size character-
istics on the phase composition of the initial mixture are found. The intermetallic compound CuGa2 is shown
to be the product of the interaction in all cases.
PACS number: 74.72.-h
DOI: 10.1134/S0036029508060049

INTRODUCTION
The interaction of metals with liquid gallium is the
basis of setting of metallic cements and diffusion-solid-
ifying solders. The main problems with these materials
are the process rate and the grain size of the forming
products, which determine their mechanical properties.
For metallic cements setting at room temperature, cop-
per and its alloys are used the most extensively. The
main product of interaction of copper with gallium is
the intermetallic compound CuGa2. The interaction is a
diffusion process, and interdiffusion is likely to occur
through the product layer. At temperatures near 20°C,
the process takes more than two days [1, 2]. Clearly, the
chemical-reaction rate depends substantially on the
grain size of the solid-phase component and its phase
composition.
The aim of this work is to study how the size char-
acteristics of the primary copper-bearing solid-phase
component and its phase composition affect the kinet-
ics of the interaction with liquid gallium and the crys-
tallite sizes of the forming products.
EXPERIMENTAL
As the solid-phase components, we used a PMS-1
copper powder and intermetallic copper–gallium com-
pounds (Cu + 20% Ga solid solution and Cu9Ga4) pre-
pared mechanochemically from the corresponding mix-
tures of copper and gallium (State Standard GOST
12797-77) in an AGO-2 high-energy water-cooled plan-
etary ball mill in an argon atmosphere. The cylinder vol-
ume was 250 cm3, the ball diameter was 5 mm, the
charge weight was 200 g, the sample weight was 10 g,
and the rate of cylinder rotation about the total axis was
~1000 min–1.
The solid-phase components were mixed with liquid
gallium in proportions approximately corresponding to
the stoichiometry of the main reaction of copper with
gallium at a small copper excess. Before mixing, gal-
lium was melted at a temperature of ~37°C. All opera-
tions (installation of a sample in a diffractometer, hold-
ing to the end of the reaction, measurements) were then
performed at a temperature of ~20°C. The end of inter-
action was indicated by termination of the change in the
reflection intensities of CuGa2.
The in situ diffraction studies were carried out on a
station at the fourth beamline of the VEPP–3 SR stor-
age ring of the Siberian Synchrotron Radiation Center
at the Nuclear Physics Institute, Siberian Branch, Rus-
sian Academy of Sciences [3]. We used a method in
which a thin 0.4 × 0.4-mm monochromatic radiation
beam (λ = 0.3686 Å) passed through a thin layer in a
sample and yielded a diffraction pattern recorded by a
flat two-dimensional detector. The diffracted radiation
was recorded using a detector system based on a
MAR345 (Marresearch) storage screen.
Precise diffraction measurements were performed
on a station of the second SR beamline using parallel
beam recording. A high degree of monochromatization
was achieved with a double silicon monochromator,
which cut off fluorescence radiation in the diffracted
beam and played the role of a narrow slit with an angu-
lar resolution that was equal to the rocking curve width
of the crystal (~0.001 deg). The studies performed on
the station at the second SR beamline ensured high
accuracy of the data on the unit-cell parameters of the
phases.

475
476 ANCHAROV et al.

Cu

Cu

Cu

0
0 x

Fig. 1. X-ray diffraction patterns of the product of the reaction of a copper powder with liquid gallium two days after mixing of the
components: (right) general view, (upper left) fragment in an enlarged two-dimensional representation, and (lower left) three-
dimensional representation of this fragment. All reflections belong to the forming intermetallic compound CuGa2.

The electron-microscopic studies were performed
on a JSM-T20 electron microscope and high-resolution
JEM-2010 and JEM-400 electron microscopes.
RESULTS AND DISCUSSION
We carried out an in situ X-ray diffraction study of the
interaction between a copper powder and the mecha-
nochemically prepared gallium solid solutions in copper
or the intermetallic compound Cu9Ga4 using synchrotron
radiation.
10 µm
Fig. 2. Micrograph of the reaction product of a copper pow-
der with liquid gallium two days after mixing of the compo-
nents.
Figure 1 shows the X-ray diffraction pattern
obtained for the reaction products of the copper powder
with liquid gallium two days after mixing of the com-
ponents. It is seen than the reaction product contains
only unreacted copper and the intermetallic compound
CuGa2. There are no other copper–gallium intermetal-
lic compounds.
The crystallite sizes in the sample can be estimated
from the X-ray diffraction pattern taken with a two-
coordinate X-ray detector. At a crystallite size larger
than 1 µm, the X-ray diffraction pattern is known to
consist of individual sections with an intensity exceed-
ing the background rather than of continuous rings. It
follows from the X-ray diffraction pattern in Fig. 1 that
the integrated intensities of the individual reflections of
the intermetallic compound CuGa2 are many times
higher than those of the reflections of the initial copper
powder, which almost yield a continuous ring. More-
over, the reflections forming another X-ray diffraction
ring exhibit a large scatter of the intensities of the dif-
fracted radiation. Hence, it may be assumed that the
crystallite size of the intermetallic compound CuGa2
should also be larger than 1 µm. To verify this assump-
tion, we performed electron-microscopic studies of the
interaction products (Fig. 2), and they showed that the
sample consisted mainly of 1- to 5-µm particles. Some
particles were 10 µm in size. In general, the particles
have irregular shapes and likely consist of several
mutually misoriented crystallites.

RUSSIAN METALLURGY (METALLY) Vol. 2008 No. 6

 INTERACTION BETWEEN COPPER AND GALLIUM 477

The mechanochemically prepared gallium solid

solution in copper (the coherent domain size is <16 nm)
has a lattice parameter of a = 0.3667 nm (pure copper
has a = 0.3615 nm) and a high concentration of stack-
ing faults (indicated by arrows in Fig. 3). The study of
the chemical interaction of the solid solution with liq-
uid gallium shows that it is completed within less than
one day.
Unlike the products of interaction of copper with
gallium, the reflections in the X-ray diffraction pattern
of the reaction products in this case are more uniform
in intensity (Fig. 4), although there are some peaks.
20 nm
The electron-microscopic studies also show finer
grain sizes of the intermetallic compound CuGa2 as
Fig. 3. High-resolution micrograph of the Cu + 20 at % Ga
compared to the product of interaction of the copper solid solution after activation for 20 min; the arrows show
powder with liquid gallium. However, the crystallite stacking faults in the solid solution.
size (>100 nm, see Fig. 5) is substantially larger than
the grain size of the initial solid solution (~16 nm).
adjustment on a goniometer take ~5 min. About 50% the
The mechanically synthesized intermetallic com- intermetallic compound forms in the sample preparation
pound Cu9Ga4 with a lattice parameter of a = 0.8731 nm time and exposure time.
contains 33 at % Ga. In this case, the grain size is 16–
18 nm. The interaction of Cu9Ga4 with liquid gallium As a result of the interaction, the intermetallic com-
occurs more intensely than that using the copper powder pound CuGa2 forms as well. The X-ray diffraction pat-
or the solid solution. The interaction of the copper pow- terns of the reaction products show that, unlike the reac-
der with gallium is completed within two days; the inter- tion products of copper or the gallium solid solution in
action of the gallium solid solution in copper with gal- copper with liquid gallium, the integrated intensities of the
lium is completed within one day; and the complete reflections of the intermetallic compound CuGa2 obtained
interaction of the intermetallic compound Cu9Ga4 with as a result of the Cu9Ga4 + Ga interaction decrease signif-
gallium occurs in less than 1 h. The mixing of the com- icantly (Fig. 6). This conclusion is confirmed by the elec-
ponents, the application of the paste on a holder, and its tron microscopy data (Fig. 7). The micrograph shows that

111Cu(Ga)

111Cu(Ga)
I
200Cu(Ga)

0
0 x

Fig. 4. X-ray diffraction pattern of the product of the reaction of a Cu(Ga) solid solution with liquid gallium: (right) general view,
(upper left) fragment in an enlarged two-dimensional representation, and (lower left) three-dimensional representation of this frag-
ment. All reflections belong to the intermetallic compound CuGa2.

RUSSIAN METALLURGY (METALLY) Vol. 2008 No. 6

478 ANCHAROV et al.
10 µm
Fig. 5. Micrograph of the product of the reaction of the solid
solution of gallium in copper with liquid gallium two days
after mixing the components.
the sizes of most particles are 1–2 µm. Moreover, there are
also particles ~10 µm in size. However, since the particles
have an extremely irregular shape, these coarse particles
are assumed to consist of several crystallites.
It is important to note that the integrated intensities
of the reflections of the same X-ray diffraction line is
330Cu9Ca4
330Cu9Ca4
Fig. 6. Fragments of the X-ray diffraction pattern of the reaction product of the intermetallic compound Cu9Ga4 with liquid gallium
(a) within 15 min and (b) within 1 h after mixing the components. All reflections belong to the intermetallic compound CuGa2.
RUSSIAN METALLURGY (METALLY)
proportional to the number of atoms composing the
reflecting crystallites. An increase in the crystallite size
by a factor of 2 leads to an increase in the reflection
intensity by a factor of 8.
The reflection intensities of the intermetallic com-
pound CuGa2 are many times higher than the reflection
intensities of the initial reagents (copper powder, mech-
nochemically synthesized solid solution Cu(Ga), inter-
metallic compound Cu9Ga4). This may be sufficient to
assume that the intermetallic compound CuGa2 solidifies
from a liquid phase. Is most likely that the particles of the
initial solid phase dissolve in liquid gallium. The slower
the accumulation of copper in the solution, the larger the
CuGa2 crystallites. This is explained by the hypothesis
that the dissolution of a solid metal in a liquid metal
occurs by the diffusion of solvent atoms from the liquid
to the solid phase up to formation of solid solutions
(or intermetallic compounds), whose concentration per-
mits them to pass to the liquid via melting, in the near-
boundary layer [4, 5]. To test this assumption, we pre-
cisely measured the (400) Cu diffraction reflection for
the initial copper powder and the copper retained after
the interaction with liquid gallium. The unit-cell param-
eters obtained as a result of the processing of the X-ray
diffraction data for the initial copper powder and the cop-
(a)
0
0 x
(b)
0
0 x
Vol. 2008 No. 6
 INTERACTION BETWEEN COPPER AND GALLIUM
10 µm
Fig. 7. Micrograph of the product of the Cu9Ga4 + Ga reac-
tion taken within two days after mixing the components.
per retained after the interaction with liquid gallium are
a = 3.6152 ± 0.0004 and 3.6148 ± 0.0004 Å, respectively
(Fig. 8).
An analysis of the broadening of the X-ray diffrac-
tion line makes it possible to estimate the coherent
domain size (CDS) of the X-ray radiation. In this case,
we can assume that every particle is represented by one
CDS. The measured copper particle size is ~120 Å.
Assuming that the thickness of the near-boundary layer
in which solid solutions can form is three unit-cell
parameters, we find that this layer contains about half
the number of atoms composing a particle (45%).
When the solid solution of gallium in copper forms, the
unit-cell parameter should increase. Thus, we can state
that, when solid copper interacts with liquid gallium, no
near-boundary layer consisting of a solid solution
forms and the interaction in the Cu–Ga system occurs
according to another scheme.
CONCLUSIONS
(1) The intermetallic compound CuGa2 is the single
product of the interaction of copper or a number of its
intermetallic compounds with liquid gallium; i.e., the
interaction always yields CuGa2, which is an interme-
tallic compound with the highest content of the liquid-
phase component.
(2) For all the systems under study, the CuGa2 phase
forms as particles that are substantially larger than the
particles of the initial solid-phase component.
(3) The time it takes for the chemical reaction to fin-
ish depends not only on the particle size of the initial
solid-phase component (the sizes of the Cu(Ga) and
RUSSIAN METALLURGY (METALLY) Vol. 2008
479
216
162
108
400Cu
54
0
116.0 116.4 116.8 2θ, deg
Fig. 8. X-ray diffraction patterns of (solid line) the copper
powder and (dashed line) the product of the interaction of
copper with liquid gallium.
Cu9Ga4 particles are almost the same) but also on the
content of the low-melting-point component in the
intermetallic compound (the higher the gallium content
in the solid-phase component, the faster the reaction of
the CuGa2 formation).
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