NanoStrucmred Materials, Vol. 12, pp.

139-142, 1999
Elsevier Science Ltd
Pergamon 8 1999 Acta Metallurgica Inc.
Printed in the USA. All rights reserved
096%9773/99/$-see front matter
PI1 s0965-9773(99)00083-5

FORMATION OF IRON-NICKEL NANOCRYSTALLINE ALLOY BY

MECHANICAL ALLOYING

V.V. Tcherdyntsevl, S.D. Kaloshkinl, LA. Tomilinl, E.V. Shelekhovl, Yu.V. Baldokhin*
‘Department of Physical Chemistry, Moscow Steel and Alloys Institute, Leninsky prosp.,
4, Moscow, 117936, Russia, vvch@phch.misa.ac.ru
2Institute of Chemical Physics Academy of Science, Kosygina str., 4, Moscow 117334,
Russia

Abstract - Fe,.,Ni, alloys were prepared by mechanical alloying of elemental

powders in high-energy planetary ball mill in a wide concentration range of components (10
sx -40). The structure was studied by X-ray diffractometry. It is shown that concentration
ranges of single-phase solid solution of MA samples are markedly wider than that of
thermodynamically stable alloys. Character of X-ray peaks indicates that there is a high
density of crystalline lattice defects including stacking faults. Block sizes, calculated without
considering stacking faults presence, was found to be 8 - 15 nm, and calculated with
considering of stacking faults 30 - 80 nm. The results were discussedon the basis of
thermodynamic model of MA. 01999 Acta Metallurgica inc.

INTRODUCTION

Possibility of production of nonequilibrium phases and very defective structures

induce especial interest to the processes which occur during MA. It is possible to prepare
amorphous phases, supersaturated solid solutions, and other nonequilibrium structures by
MA. Unusual distribution of structure defects comparing to those in the alloys prepared
by traditional methods is typical for the MA alloys.
Iron-nickel alloys are of great interest due to their magnetic and mechanical
properties. There are some studies, where structure and properties of MA iron-nickel
alloys were investigated. Unfortunately, investigation of MA Fe-Ni alloys in a wide
concentration range was reported only in few studies [l - 31. Concentration ranges of b.c.c.
and f.c.c. phases existing in MA Fe-Ni alloys depend on milling intensity: an increase of
intensity leads to extending of the concentration range of existing of f.c.c phase and to
narrowing of that of b.c.c phase [1 ,3]. This phenomena may be associated with an increase
of the temperature in the mill [1] or with a dependence of the density of structure defects
on milling intensity [3].

139
140 FOURTH INTERNATIONAL CONFERENCE ON NAN~STRUCTURED MATERIALS

The aim of the present work is to study structure of MA Fe-Ni alloys in a wide
concentration range. A study of magnetic hyperfine interaction in this system, which is
also of interest, will be published separately [4].

EXPERIMENTAL PROCEDURE

Pure carbonyl Fe (powder, purity 99.95 %) and electrolytic Ni (powder, purity

99,5 %) were used as starting materials. The following compositions were studied: FeimxNix
9where x = 10, 20,22,24,26, 28,30,32,34, 36, 38,40, 50,60,65,70, 75, 80, 85, and 90 at.
%. MA was carried out in a AGO-2U planetary ball mill in air atmosphere. About 15 g of
material and 150 g of steel balls 8 mm in diameter were loaded into steel hermetic vials
(160 cm3). All the samples were milled for 1 hour. A specific power of the process was
estimated to be about 1O-20 Wig depending on the method of determination. Annealing of
samples was carried out for 0.5 hours at 350 and 65OoC in argon atmosphere.
A DRON-3 diffractometer with Co K, and Cu IS, radiations was used to study
the phase composition and crystalline structure of the samples. Structure parameters were
computer-determined. An original method [5] was used to determine stacking faults
concentration.

RESULTS

Fig. 1 shows concentration ranges of phase existence in as-milled and annealed

samples according to X-ray data and according to the equilibrium phase diagram [6]. One
can see that in MA alloy concentration ranges of existence of single-phase solid solutions
are markedly extended. In contrast to the stable diagram, FeNi compound was not
observed in MA alloys. Annealing of MA alloys at 350 OCdoes not lead to any change of

0 24 40 cm 80 lcm m IO 46 66 8B 100
l t%Ni a,. % Ni

Fig. 1. Concentration ranges of phase existing in as-milled (a), annealed at

65OOC(b), and thermodynamically stable [6] (c) alloys; Diagrams of Gibbs energy for
Fe-Ni system at 300 K (d) and 600 K (e). 1 - liquid alloys; 2 - b.c.c. structure; 3 -
h.c.p. structure; 4 - f.c.c. structure.
 FOURTH INTERNATIONAL CONFERENCE ON NAN~STRUCTURED MATERIALS 141

crystalline structure, but annealing at 65O’JC leads to the b.c.c.+f.c.c. + f.c.c. phase
transformation in alloys with x = 22 - 28 at. % and to the b.c.c. + b.c.c.+f.c.c.
transformation in alloys with x = 10 and 20 at. % (see. Fig. lb). This transformation,
which is far from equilibrium (Fig. lc), becomes possible, because equilibrium state in Fe-
Ni system may be reached only by very slow cooling.
The X-ray diffraction patterns of MA samples are characterised by significant
peak broadening. Crystallite sizes and microstrains, which are calculated from the
experimental data, were found to be within the ranges 8 - 15 nm and 0.5 - 0.8 %
respectively. Fig. 2 shows lattice parameters of f.c.c. alloys vs. alloy composition. Lattice
parameters of these phases for equilibrium alloy [7] are also presented on Fig. 2. It is easily
seen that equilibrium alloys lattice parameters are smaller than those of MA alloys. The
same effect was found in our previous work for Fe-Mn alloys [9].
It is known that ball milling of materials can lead to the formation of structures
with high concentration of stacking faults. Concentration of stacking faults in all MA
alloys with the f.c.c. structure was determined from the X-ray diffraction data. Fig. 3a
shows a dependence of stacking fault probability CLon the MA alloy composition. True
crystallite sizes proved to be almost an order of magnitude larger than corresponding
apparent values, which were determined ignoring the presence stacking faults in crystalline
lattice. The typical values of true crystallite sizes fall in the range 20 - 80 nm. Stacking
fault concentration decreases with increasing Ni content.
0.362
l
a,
a, nm
0.360

30 mm
0.356 *,"a ox I.,1
f 0 l 6c

0.356 5 2500 b
< 2
1500
1
500
5 i
-500 I
60 30 40 50 60 70 80 60 100
at. % Ni at. % NI

Fig. 2. Lattice parameter of f.c.c. phase: l- Fig. 3. Dependence of stacking faults

this study; 2- for termodynamically concentration CL (a) and difference
equilibrium alloys [7]; 3- For mechanically between Gibbs energy of h.c.p. and
alloyed alloys [3]. 4- For electrodeposited f.c.c.phases (b) on alloy content. I- for
alloys [8]. 300K, 2- for 600 K.
142 FOURTHINTERNATIONAL C~NFEREWE ON NANOSTRUCTURED MATERIALS

DISCUSSION

This above-mentioned results may be discussed on the base of thermodynamical

model of MA [lo]. Figure 1 shows Gibbs energy diagram for Fe-Ni system at 300K (d)
and 600K (e), calculated on the base of data [1 11. It is known, that MA process tend to
form single-phase alloys, because decreasing of Gibbs energy by wide double-phase region
formation is impossible due to the processes of compulsory levelling of the chemical
composition during MA. It is rearkable that experimental ranges of phase existing in our
case are in the better agreement with Gibbs energy diagram for 600, than for 300 K. The
same result was observed for Fe-Mn system [9], which is associate with effect of
temperature increasing in the vial during MA. On the base of Gibbs enerdy diagramms, a
question about a reason of dependence of ranges of phase existence on milling intensity in
Fe-Ni alloys [I, 31 may be explane. Really, it is easy to see from Fig. 1 that the
concentration range of existing of f.c.c phase expands, and that of b.c.c. phase narrows
down with increasing temperature, i.e. above-mentioned phenomena depend on the
temperature in the vial, as it was proposed in [3].
As was proposed in [12], stacking faults concentration depend on difference
between free energy of h.c.p. and f.c.c. phase. This difference for 300K (a) and 600K (b),
which was calculated on the base of Fig. 1, is shown on Fig. 3b. Indeed, stacking faults
concentration increase with decreasing of the difference beween Gibbs energy ob theese
two phases.
On the base of discussion, we can conclude that thermodynamyc model is very
useful for explanation of the structure of MA alloys.
This study was supported by RFBR grant no. 97-03-33630a

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