ISSN 0031918X, The Physics of Metals and Metallography, 2011, Vol. 111, No. 1, pp. 45–52.

© Pleiades Publishing, Ltd., 2011.

Original Russian Text © T.F. Grigor’eva, S.A. Kovaleva, A.P. Barinova, P.A. Vityaz’, N.Z. Lyakhov, 2011, published in Fizika Metallov i Metallovedenie, 2011, Vol. 111, No. 1,
pp. 47–53.

STRUCTURE, PHASE TRANSFORMATIONS,

AND DIFFUSION

Study of the Interaction of Mechanochemically Produced

Cu–In Solid Solutions with Liquid Gallium and of the Structure
of Metallic Cements on Their Basis
T. F. Grigor’evaa, S. A. Kovalevab, A. P. Barinovaa, P. A. Vityaz’b, and N. Z. Lyakhova
a
Institute of SolidState Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences,
ul. Kutateladze 18, Novosibirsk, 630128 Russia
bJoint Institute of Mechanical Engineering, National Academy of Sciences of Belarus, Minsk, Belarus’

Received March 16, 2010;

in final form, June 15, 2010

Abstract—Methods of atomicforce and scanning electron microscopy and Xray diffraction and electron
microprobe analysis were used to study metallic cements formed upon the interaction of Cu–In mechano
composites with different contents of indium. It has been established that an increase in the amount of indium
in the mechanocomposite, which represents mainly a solid solution of indium in copper, leads to a decrease
in the sizes of particles of the basic intermetallic compound CuGa2 in the material obtained. After a certain
induction period, indium forms a solid solution with gallium in the form of separate crystallites and nanodi
mensional films on the faces of CuGa2 crystals.

Keywords: metallic cements, mechanocomposites, microstructure of alloys

DOI: 10.1134/S0031918X11010042

INTRODUCTION Cu–In powders by mechanical alloying in an AGO2

The previously performed investigations of the
chemical interaction of mechanocomposites of the
Cu–Bi system with liquid gallium showed that the use
of the mechanically obtained composites decreases
the time of diffusion processes and accelerates the for
mation of the alloys. In this case, since in this reaction
there interact only Cu and Ga, whereas bismuth does
not interact and is dissolved in none of the compo
nents, the intermetallic compound CuGa2 and the bis
muthcontaining phase are formed simultaneously.
The application of mechanochemically obtained Cu–
In powders as the solid phase in the reactions with liq
uid gallium increases the number of interacting sys
tems. Therewith, indium is dissolved quite well in gal
lium, and the formation of solid phases in this case can
occur not simultaneously. Thus, the final structure of
the alloy will be formed under conditions of compet
ing processes of different interactions.
This work is aimed at an analysis of the microstruc
ture of the material obtained upon the interaction of
the mechanosynthesized metallic compounds of the
Cu–In system with gallium melts.
EXPERIMENTAL
For the investigation, we used a PMS1 copper
powder (Russian State Standard GOST 4960–75) and
indium (GOST 10297–94), from which we obtained
highenergy watercooled ball planetary mill in an
argon atmosphere (volume of the drum, 250 cm3;
diameter of balls, 5 mm; speed of rotation of drums
about the common axis, ~1000 rev/min). Subse
quently, the powders were mixed with molten gallium
at a temperature of 40°C and after the end of the inter
action were cooled to room temperature.
The studies of the morphological characteristics
and topography of the surface of powders on the basis
of copper and its alloys were carried out using an
NT206 atomicforce microscope (Microtestma
chines, Gomel’) with standard commercial Vlike
probes (NSC11, Mikromasch) in the contact regime.
In the atomicforce microscopy (AFM), there were
recorded pointbypoint variations of the forces of
interaction (normal and lateral) of a cantilever needle
with the surface to be investigated [2], thereby obtain
ing images of the topographic contrast (topography)
and the distribution of lateral forces (torsion). The
identification of phases in the AFM images was per
formed on the basis of Xray diffraction (XRD) and
electronmicroprobe analysis (EMA) data.
For the analysis of the structure of the samples
obtained, we used a MIRA\TESCAN highresolution
scanning electron microscope (SEM) with an attach
ment for electron microprobe analysis (EMA). The
diameter of the electronic microprobe was 5.2 nm; the

45
46 GRIGOR’EVA et al.
region of excitation, 100 nm. For the investigation of
the distribution of chemical elements over the surface
and for the detection of the compositional inhomoge
neity of the surface, images in secondary and in back
scattered electrons were obtained; in the latter case,
the brightness distribution was determined by the aver
age atomic number Z of the substance in each
microregion.
The study of the phase composition of the powders
after mechanoactivation and of the dynamics of the
formation of the products of their interaction with liq
uid gallium were performed using Xray diffraction.
The Xray diffraction analysis and the semiquanti
tative estimation of the products of interaction was
carried out on a D8 Advance Bruker (Germany) dif
fractometer by the powder method in the θ–2θ config
uration in the stepbystep mode with a step of 0.1°.
The identification of phases was performed based on a
diffraction pattern recorded in CuКα1 radiation (λ =
1.54051 Å). The refinement of the crystallattice
parameters was carried out by the Rietveld method
using a TOPAS code. The approximation of the pro
files of the peaks was achieved using the pseudoVoigt
function.
RESULTS AND DISCUSSION
For studying the interaction of solid and liquid
metals in the multiphase system, we used, as the initial
solidphase component, the mechanochemically syn
thesized powders obtained in the Cu + 12% In and
Cu + 20% In (hereinafter, wt %) systems.
According to the phase diagram of the Cu–In sys
tem, indium has a limited solidstate solubility in cop
per even at high temperatures. It is equal to 10.85 at %
at the temperature of the eutectoid decomposition
(574°C) and only 1.15 at % at the temperature of
250°С [3]. In this system, there exist also several inter
metallic phases.
The Xray diffraction analysis of the products of
mechanical alloying (Fig. 1) showed that upon the
mechanoactivation of a copper powder with 12%
indium there is formed a solid solution of indium in
copper. In this case, the lattice parameter of copper
increases to a = 3.665(9) Å (ast = 3.6150 Å). As the con
centration of the alloying component increases to
20%, the mechanoactivation leads to an even larger
increase in the lattice parameter of copper (to a =
3.728(7) Å), which indicates an increase in the indium
concentration in the copper lattice. An increase in the
content of indium leads to a decrease in the size of
crystallites of the copperbased solid solution from
30 to 12 nm.
The morphology of particles changes depending on
the content of indium in the solid solution. It was
shown by the AFM method that the mechanical acti
THE PHYSICS OF METALS AND METALLOGRAPHY
vation of Cu + 12% In system leads to the formation of
small particles of the solid solution of indium in cop
per (150–230 nm). The recrystallization of the solid
solution of copper and the formation of grains of more
than 15 μm in size are also possible. Upon the
mechanical activation of the Cu + 20% In composi
tion, the particle size decreases to 100–150 nm; the size
spread decreases as well; the particles can form scaly
aggregates with dimensions on the order of 1–1.5 μm.
When studying powders of Cu–In solid solutions,
the simultaneously obtained torsion and deflection
images allowed us to observe specific topographic fea
tures of the surface of “large” crystals of the Cu(In)
solid solution. Thus, on the faces of Cubased solid
solution crystals there are revealed local radially ori
ented regions, which supposedly were formed as a
result of the local melting of indium particles upon the
mechanoactivation and due to the collisions of molten
indium droplets with the faces (Fig. 2). Such struc
tures could not be revealed by other methods because
of the low height of the objects (on the order of 22 nm
in the center and 0.5–1.7 nm at the edges). These
images can serve as a confirmation for the fact that in
the process of mechanical activation there occurs a
local increase in temperature, such that it leads to the
melting of indium (Tm = 156°C) and, therefore, to a
chemical interaction of copper with liquid indium.
As is known, the decrease in the size of the particles
of the precursor powder ensures a large contact surface
between the components of the solid and liquid phases
and, therefore, shorter diffusion lengths during their
subsequent interactions with the metallic melts. Since
both copper and indium are soluble in liquid gallium,
it can be expected that the rate of dissolution of the
mechanosynthesized solid solutions of the Cu–In sys
tem will be significant. But an increase in the indium
concentration in the Cu(In) solid solution leads to an
increase in the rate of saturation of the melt by indium.
Therefore, as copper is spent for the formation of the
intermetallic compound CuGa2, the crystallization
rate of the new phase of indium must increase.
In the Ga–In system, according to the phase dia
gram [3], the solubility of In in solid Ga is less than
0.3 at %, and the solubility of Ga in In is 3.1 at %. The
eutectic point corresponds to 14.2 at % In and a tem
perature of 15.3°C. At a temperature of 60°C, indium
can be dissolved in liquid gallium to 48 wt %.
The in situ Xray diffraction study of the interaction
of solidsolution–intermetalliccompound mechano
composites in the Cu–In system with liquid gallium
showed that first, immediately after mixing at room
temperature, there is formed an intermetallic com
pound CuGa2 without the formation of any intermedi
ate solidsolution states. The crystallization of the
indiumcontaining phase begins after a certain induc
tion period. We believe that as copper and gallium are
Vol. 111 No. 1 2011
 STUDY OF THE INTERACTION 47

1400

1300

1200

1100

1000

900
Intensity, rel. units

800

700

600

500

400

300 (b)

200
In

Cu

In
Cu
In

In

(a)
In

100 Cu

Cu
0
30 40 50 60 70 80 90 100
2θ, deg

Fig. 1. Xray diffraction pattern of Cu–In powders after mechanical activation (20 min) in argon: (a) Cu + 12% In and (b) Cu +
20% In powder mixtures.

Z, nm
30

25

20

15

10

5
3 μm 1 μm
0

Fig. 2. 3D topography of a particle of the Cu–12% In solidsolution powder after mechanical activation with local regions of mol
ten indium.

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 111 No. 1 2011

48 GRIGOR’EVA et al.

3000

2500

2000
Intensity, rel. units

1500

1000
(b)

500

(a)

30 40 50 60 70 80 90
2θ, deg

Fig. 3. Xray diffraction patterns of (a) Cu + 12% In + Ga and (b) Cu + 20% In + Ga alloys: (×) CuGa2; ( ) In; and ( ) Cu.

spent for the formation of the intermetallic compound
CuGa2, indium is freed and is dissolved in the gallium
melt, being accumulated in it. The crystallization of
the indiumbased phase occurs after a certain concen
tration limit is exceeded. Thus, the induction period
prior to the beginning of the crystallization of indium
upon the mechanoactivation of the Cu + 20% In pow
der was 210 min [4], after which there was observed a
rapid growth of the In(Ga) phase and the complete
solidification of the alloy.
The Xray diffraction analysis of the end products
of the interaction of the Cu–In mechanocomposites
with gallium showed the presence of three phases: the
intermetallic compound CuGa2, indium, and unre
acted Cu(In) solid solution (Fig. 3). With an increase
of the indium concentration in the Cu(In) solid solu
tion, the size of the indium crystallites increases from
30 to 130 nm. In the case of the indium concentration
in the initial powder equal to 12%, there is observed a
decrease in the parameter c of the indium unit cell in
the arising alloy to с = 4.930(6) Å (сst = 4.9459 Å) and,
therefore, of the unitcell volume to V = 52.19 Å3 (Vst =
52.30 Å3). At the indium concentration of 20%, these
parameters increase insignificantly (to с = 4.949(5) Å
(V = 52.32 Å3)). The size of the crystallites of the cop
perbased solid solution in both alloys is identical and
is approximately 7 nm. Insignificant changes in the
volume of the unit cell of indium can be connected
with the formation of the solid solution of gallium in
indium.
On the polished sections of the alloys obtained
upon the interaction of the mechanocomposites of the
Cu–In system with liquid gallium (Fig. 4), regions of
the unreacted solid solution of indium in copper are
noted.
In the process of interaction, indium is dissolved in
the molten gallium and concentrated and crystallized
at the solid–liquid interfaces. With an increase in the
indium concentration and with a decrease in the size
of particles of the Cu(In) solid solution, the size of
macropores decreases from 100 to 25 μm. The con
centration of defects at the boundaries of macropores
also decreases. The formation of the indium phase
occurs in the matrix of the intermetallic compound.
The studies of the surface topography of the alloys
by the SEM and AFM methods showed that the alloys
are characterized by a large spread in the sizes of par
ticles of the intermetallic compound CuGa2 (from 0.5
to 10 μm). With an increase in the indium concentra
tion to 20%, there is observed a decrease in the number
of large faceted crystals of CuGa2; the average size of
crystals of the intermetallic compound is approxi
mately 4 μm.

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 STUDY OF THE INTERACTION 49

Cu(In)
CuGa2
In(Ga)
In(Ga)
Cu(In) Cu(In)
CuGa2

(a) 50 μm (b) 50 μm

Fig. 4. Microstructure of the alloy surface after polishing: (a) Cu + 12% In + Ga; and (b) Cu + 20% In + Ga.

sol. solution (In)

CuGa2

(a) 1 μm (b) 1 μm

Fig. 5. AFM images of the surface of unpolished samples of the Cu + 12% In + Ga: (a) topography and (b) torsion image.

The study of the morphology of the arising structures
by the AFM method and simultaneously obtaining dis
tributions of images of the normal (topography) and lat
eral (torsion) forces made it possible to reveal specific
features of the structure of the phase of the solid solu
tion of gallium in indium (Fig. 5). Its distinctive feature
is the presence of streaks in the crystals of the solid solu
tion of gallium in indium, which are connected appar
ently with the phase separation of the solid solution into
regions with greater and smaller concentrations of the
components; this is seen well in the torsion image
(Fig. 5b). The size of separate grains of the solid solu
tion of gallium in indium exceeds 10 μm.
For studying the surface microstructure of the
alloys, scanning electron microscopy was used; the
images of the surface of the alloy Cu + 20% In + Ga
were also obtained in secondary (Fig. 6a) and back
scattered (Fig. 6b) electrons. The application of the
EBSD method makes it possible to investigate the
composition inhomogeneity of the surface (the bright
ness distribution in the image depends on the atomic
number of an element). It is seen from Fig. 6b that in
the EBSD images the contrast is determined by the
topographic features of the surface and that the bright
ness distribution is uniform. The electronmicroprobe
analysis at different points of the surface and on the
faces of particles of the intermetallic compound
CuGa2 showed the presence of indium in concentra
tions from 0.1 to 8.08 wt % (Figs. 6a, 7a).
One additional characteristic feature of the surface
of samples obtained upon the interaction of Cu–In
mechanocomposites with liquid gallium is the pres
ence of fine formations on the surface of crystals and
CuGa2 grains, which are seen more clearly in the
AFM images (Fig. 7b) and are noted in the SEM
images (Fig. 7a). The formation of such structures on
the surface of intermetalliccompound particles can
be connected with the crystallization of indium on the
surface of growing crystals. This makes it possible to
suggest the presence of indium on the surface of crys
tals of the intermetallic compound CuGa2 in the form
of thin films and dispersed formations. According to
the AFM data, the thickness of films can reach 20 nm
(Fig. 8b).

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50 GRIGOR’EVA et al.

Cu Ga In
Spectrum 1 16.20 32.10 50.90
Spectrum 2 28.21 66.32 4.48
Spectrum 3 29.99 66.08 3.93
Spectrum 4 26.49 57.29 16.22
Spectrum 5
Spectrum 6
7.30 42.22
9.87 37.20
50.48
52.93 Spectrum 1 Spectrum 3
Spectrum 7 30.03 63.00 1.98
Spectrum 8 30.89 68.43 0.68

Spectrum 7

Spectrum 8 Spectrum 2

Spectrum 4

Spectrum 5

(a) Spectrum 6 2 μm (b) 2 μm

Fig. 6. SEM image of the Cu + 20% In + Ga taken in (a) forward and (b) backscattered electrons. In the upper lefthand part of
Fig. 1a, the table of data of the electronmicroprobe analysis carried out at the points indicated in the figure is given.

(a)
Spectrum 4
Spectrum 1
Spectrum 5
Spectrum 7

Spectrum 2
Spectrum 6

Spectrum 8

Spectrum 3

Cu Ga In
Spectrum 1 31.22 66.58 2.20
Spectrum 2 29.94 49.47 26.59
Spectrum 3 30.11 68.08 1.21
Spectrum 4 31.80 66.15 2.05 1 μm 0.5 μm
Spectrum 5
Spectrum 6
31.61 65.76
28.94 52.99
2.53
8.08
(b)
Spectrum 7 31.48 60.12 0.40
Spectrum 8 30.33 59.33 0.24

Fig. 7. (a) SEM and (b) AFM images of the faces of particles of the intermetallic compound CuGa2 obtained upon the interaction
of the Cu–20% In alloy with Ga.

Thus, on the basis of the obtained EMA data and
the AFM and SEM results, it can be assumed that
indium crystallizes not only in the form of large crys
tals of the phase of the solid solution of gallium in
indium, but also on the faces of intermetalliccom
pound particles, forming in this case nanosized films
of indium with a thickness of about 20 nm and den
dritic structures (see Fig. 7b) caused by the constitu
tional supercooling of the indium melt because of the
consumption of gallium for the formation of СuGa2.

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 111 No. 1 2011

 STUDY OF THE INTERACTION 51

1
2

1 μm
(a) (b)

−15
CSTopography, nm

−22

−29

−36

−43
0 1 2
Length, um
CSTopography
Absolute values: [a] x = 214.2 nm; z(1) = 11.3 nm; [b] x = 562.4 nm; z(1) = 30.9 nm;
Difference between markers: dx = 348.41 nm; dz(1) = 19.6 nm;
Difference between first two lines: x[a] = 214.2 nm; dz(a) = 0 nm; x[b] = 562.4 nm; dz(b) = 0 nm.

Fig. 8. AFM image of the face of an intermetalliccompound particle and the profile of its transverse section.

CONCLUSIONS On the basis of the data of electronmicroprobe

As a result of the investigations of the structure of
alloys obtained by the interaction of mechanically
synthesized solid solutions of the Cu–In system with
molten gallium, it has been established that the first to
be formed are crystals of the intermetallic compound
CuGa2. The crystallization of the phase of the solid
solution of gallium in indium is characterized by an
induction period, which is connected with the accu
mulation of indium to a state corresponding to the
constitutional supercooling in the molten gallium.
The AFM and SEM data showed that the size and the
morphology of crystals depend on the indium concen
tration in the initial composite. With an increase in the
content of indium from 12 to 20%, the average size of
particles of the basic intermetallic compound CuGa2
decreases from approximately 8 to 4 μm.
analysis and the results of the AFM and SEM studies,
it can be supposed that indium crystallizes not only in
the form of crystals of the solid solution of gallium in
indium, but also in the form of nanosized films of
indium or solid solution of gallium in indium on the
faces of intermetalliccompound particles.
ACKNOWLEDGMENTS
This work is carried out within the framework of the
integrated project of the Belarusian Republican Foun
dation for Fundamental Research, no. 09SO014, and
of the Siberian Branch, Russian Academy of Sciences,
no. 138, “The Creation of the Fundamentals of the
Effect of Force Activation on the Control of the Pro
cesses of Interaction of Solid Metals and Their Com

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52 GRIGOR’EVA et al.

pounds with Metallic Melts for the Purpose of Cre
ation of Functional Materials with Assigned Structure
and Properties.”
REFERENCES
1. T. F. Grigor’eva, A. P. Barinova, and N. Z. Lyakhov,
Mechanochemical Synthesis in Metal Systems (Novosi
birsk, 2008) [in Russian].
2. V. L. Mironov, Principles of Scanning Probe Microscopy
(Nizhnii Novgorod, 2004) [in Russian].
3. Phase Diagrams of Binary Metal Systems: A Handbook,
Ed. by N. P. Lyakishev (Mashinostroenie, Moscow,
1997), Vol. 2, pp. 636–637 [in Russian].
4. A. I. Ancharov, T. F. Grigorieva, S. V. Tsybulya, and
V. V. Boldyrev “Chemical Interaction of Cu–In, Cu–
Sn, and Cu–Bi Solid Solutions with Liquid Ga–In and
Ga–Sn Eutectics,” Neorg. Mater. 42 (10), 1164–1170
(2006) [Inorg. Mater. 42 (10), 1058–1064 (2006)].

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