Metal Science and Heat Treatment Vol. 50, Nos.

5 – 6, 2008

CORRESPONDENCE
UDC 539.37:669-175.2

REPLY TO COMMENTS BY Yu. A. SKAKOV AND M. A. SHTREMEL’

ON THE ARTICLE “INDUCED DIFFUSION: THE MAIN MECHANISM
FOR THE PRODUCTION OF DRIVEN ALLOYS”

V. L. Gapontsev1

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 5, pp. 48 – 55, May, 2008.

The paper considers the basic physical hypotheses used in constructing models for activated alloy formation
by cold intensive plastic deformation. The basis for the model is a messenger mechanism of evolution for the
stress pattern in plastic deformation of a polycrystalline material. Allowance is made for the vacancy fluxes as
additional accommodation mode for the strain, which provides preservation of the continuity, and which en-
ables one to describe the alloy composition redistribution on strain. Experimental data are compared with con-
clusions from models for activated alloy formation: a model operated on a ballistic mechanism for atomic mi-
gration and an alternative new model considered in the paper.

INTRODUCTION and ones caused by external factors. The specific feature of

My paper was published in this journal recently that pro-
posed a new model for activated alloy formation during cold
intensive plastic strain (CIPS) [1]. It was written in response
to a discussion conducted in this journal in the main by
Yu. A. Skakov and M. A. Shtremel’.2 The discussion was
concerned with the mechanism of mechanoalloying, but in
fact concerned a different object: the scope for using me-
thods from the mechanics of continuous media with thermo-
dynamics (Skakov’s concept) or the need to abandon them
(Shtremel’s concept) in describing phenomena accompany-
ing CIPS in solids. The [1] model assigns the leading part to
diffusion induced by vacancy flows. The vacancy sources
and sinks are nonconservative dislocation reactions in ter-
nary junctions between grains containing partial disclina-
tions. That model agrees with Skakov’s viewpoint and is an
alternative ballistic model corresponding to Shtremel’s view-
point. To describe CIPS action in alloys, in 1981 Martin pro-
posed a new form of ballistic mechanism by analogy with the
ballistic mechanism in alloys that have been irradiated [2]. In
both cases, the atomic jumps are of two forms: thermal ones
1 of dislocations. In the original form, it examined the particu-
Russian State Professional Pedagogic University, Ekaterinburg,
Russia.
2 disclinations and the Burgers vectors of the dislocations were
See Metalloved. Term. Obrab. Met., No. 8 (2002) and No. 4
(2004).
CIPS is that the ballistic jumps are correlated and arise when
dislocations glide through crystallites. My paper [1] has
caused various criticisms by major participants in the discus-
sion [3, 4], to which I offer a reply here.
In his comments on [1], Skakov correctly points out that
it inadequately deals with the physical principles of the
model and for no good reason excludes atomic transfer by an
internodal mechanism. The first circumstance was related to
the need to demonstrate the scope for the model on a wide
range of systems. I seek to remedy this deficiency and give
the main physical hypotheses adopted in constructing the
model.
BASIC MODEL HYPOTHESES
1. CIPS messenger mechanism. This mechanism for
plastic strain was proposed to describe the late stages [5],
where experiment indicates that the main modes of strain are
grain-boundary sliding and grain rotation [6]. Plastic strain in
a polycrystalline material is considered as the evolution of a
three-dimensional network of disclinations exchanging flows
lar case where the orientation of the Frank vectors of the
matched in such a way that the strain occurred conserva-

252
0026-0673/08/0506-0252 © 2008 Springer Science + Business Media, Inc.
Reply to Comments by Yu. A. Skakov and M. A. Shtremel’
tively (with volume retention). In general, continuity reten-
tion requires the introduction of vacancy fluxes between the
poles of adjacent disclinations differing in sign. The vacancy
concentration is
æ UV + VV Sp sij ö in [1] I spoke of the impossibility of direct use of the second
CV = exp çç - ÷,
÷ (1)
è kT ø
where UV is the vacancy formation energy, VV the vacancy
volume, and sij the stress tensor. Vacancies are generated in
stressing areas and are absorbed in compression ones. Calcu-
lations have been performed with the electron density func-
tional [7], which showed that the following condition is
obeyed in a metal in which the CIPS near stress concentra-
tors, where the local relative tensile strains attain the value 1.2:
UV + VV Spsij = 0
and the value of the vacancy concentration attains unity, i.e.,
micropores are formed. The stress concentrators are triple
junctions between grains, points of localization for partial
disclination poles. The conclusion on vacancy generation
and absorption in the region of partial dislocation poles is of
thermodynamic character, but the detailed features of these
processes are dependent on the complicated picture of
nonconservative dislocation reactions at grain boundaries
and at ternary junctions. It is difficult to determine the partic-
ular form of the boundary conditions for the vacancy diffu-
sion equation.
2. Local alloy equilibrium far from vacancy sources
and sinks. Numerical and analytical studies have been made
on the solutions to the equation systems for diffusion of mat-
ter and vacancies, which have shown that the steady-state
composition distributions between vacancy sources and
sinks are not dependent on the details of the boundary condi-
tions if during the strain one provides a value for the relative
instantaneous vacancy supersaturation CVm /CVe > 100, in
which CVm is the maximal value of the vacancy concentration
in a source, and CVe is the vacancy concentration in a sink
[8]. This is a key point in the construction of the model be-
cause it allows one to separate the comparatively simple
one-dimensional diffusion treatment from the complicated
task of describing the plastic strain and the vacancy genera-
tion at triple grain junctions. The volume of the polycrys-
talline material is split into two regions: 1 ) the vacancy
sources and sinks with fractions of about 0.0001 of the total
volume; and 2 ) the rest of the volume, where vacancies and
matter diffuse. In the first region, one cannot introduce ther-
modynamic potentials as functions of the state parameters
and no thermodynamic description is possible. That includes
the impossibility of any use of the second law of thermody-
namics. In the second region, the diffusion processes are de-
scribed by means of Gurov’s nonequilibrium hole gas model.
In [8] it has been shown that this model agrees with linear
253
nonequilibrium thermodynamics. All conditions imposed by
the second law of thermodynamics on the Onsager kinetic
coefficient matrix are obeyed. This involves the assumption
that in CIPS, in much of the polycrystalline volume the state
of the material is locally in equilibrium. It is in that sense that
law of thermodynamics in describing processes accompany-
ing CIPS. An alloy acted on by CIPS does not tend to equi-
librium but instead departs from it. Indirectly, the second law
of thermodynamics is applied to the entire volume, excluding
narrow regions around the vacancy sources and sinks. Then
there is no doubt that the second law of thermodynamics ap-
plies where it should.
We note that a literal translation is used for the term
“driven alloy,” which exactly reproduces the meaning that
during the external treatment (CIPS or irradiation), the alloy
is driven from the equilibrium state: immiscible components
(2)
are mixed, while a homogeneous solid solution with unre-
stricted solubility splits up. The ballistic mechanism cannot
provide the second effect and therefore is not a universal
mechanism for the formation of driven alloy. One can give a
quantitative description of the deviation from equilibrium if
the entropy is a function of the local straight parameters,
which in our case is so far from vacancy sources and sinks.
Translation of “driven alloy” as “activated alloy” corre-
sponds to the traditional use in the Russian literature of the
terms “mechanoactivated” for the systems produced by CIPS
and “activated state” for systems subject to CIPS [9].
3. Quasistatic state of material between disclination
poles. The material transport between disclination poles is
described by expressions for the diffusion fluxes (1) and (2)
(see paper [1]). They lack convective terms on the assump-
tion that the material is immobile. This is possible only if
there is complete balancing between the diffusional transport
in the opposite direction to the flow of material as trans-
ported by dislocations. If this crude assumption is violated,
the continuity of the medium at the triple junctions is main-
tained if one takes account of the additional material migra-
tion mechanisms: grain-boundary diffusion and the diffusion
of interstitial atoms generated as are vacancies in the region
of disclination poles. Skakov correctly places emphasis on
the latter transport mechanism. However, the role of that
transport mechanism in bulky solid solution formation is not
evident. The compositions approximate to equiatomic, and
the formation of such solid solutions is difficult to explain by
recombination of interstitial atoms and vacancies in the bulk.
Interstitial atoms on account of their substantially greater
mobility flow rapidly to the grain boundaries. They partici-
pate in setting up nonequilibrium segregations, but not in the
formation of bulky solid solutions. It is possible that the ori-
gins of bulk solutions involving vacancies and interstitial at-
oms can be explained on a dumbbell mechanism of joint dif-
fusion. This complicates the model so much that an analysis
becomes virtually impossible. The main body of experimen-
tal data can be explained qualitatively, by rejecting grain-
254
boundary diffusion in a first approximation, together with the
diffusion of interstitial atoms, the dumbbell diffusion mecha-
nism, and the influence of ballistic effects on the atomic mi-
gration.
4. Effects of local stresses on structure defects as va-
cancy sources and sinks. We consider cold plastic strain
when equilibrium is not established along the grain bound-
aries. Then the interaction between the grain boundaries and
the intensive vacancy flux should be considered locally, as
for the interaction of other structure defects. During CIPS,
the structure defects in lattice stretching areas are vacancy
sources, while in compression areas they are sinks. Structure
defects localized in regions where stresses are absent are in
dynamic equilibrium with the field of vacancies set up by the
main sources and sinks, which are related to stress concentra-
tors. That hypothesis in a certain sense conflicts with the one
on local vacancy equilibrium. The latter involves the as-
sumption that the stresses everywhere are small and that all
the sources and sinks have the same capacity, apart from the
grain boundaries, which instantaneously relax the excess vo-
lume.
ASSUMPTION USE IN ALLOY DESCRIPTION
It is necessary to adopt a system of assumptions in de-
scribing CIPS for alloys. Those assumptions should not con-
flict with existing experimental data. A ballistic model also
involves such assumptions, but they are adopted by default,
i.e., without discussion. Even in the simpler situation in the
absence of external action on the alloys, Gurov in setting up
a microscopic theory of diffusion was forced to use the ap-
proximation of local (quasiequilibrium) vacancy situations.
That approximation is not confirmed vigorously either by ex-
periment or theory, and there are only heuristic arguments in
favor of it. An experimental test requires the establishment of
local correlations between the concentration fields of vacan-
cies and matter, which falls outside the scope of current tech-
niques. A rigorous theoretical basis requires allowance for
the sources and sinks within a logical microscopic theory
such as the ABv model [10]. There are rigorous constraints
in constructing strict models for metal systems, both analyti-
cal and numerical from first principles. One of them is the
fixed amount and types of lattice nodes, which means that
one cannot include the vacancy sources and sinks in the ana-
lysis.
A further example of successful use of the hypothesis is
the construction of a nonequilibrium free-energy function for
an alloy by the method of using the basic kinetic equation by
Vaks [11]. He used the hypothesis that the alloy is ergodic in
the form of the requirement that the detailed-balancing con-
ditions are met for transitions at all levels, but Martin ob-
served [12] that this requirement is not met under CIPS con-
ditions and the basic kinetic equation method is inapplicable.
The above brief discussion by Martin and Vaks on methods
of describing driven alloys is very similar in content to the
V. L. Gapontsev
discussion between Shtremel’ and Skakov. In that same pa-
per, Martin points out that the alloy ergodic hypothesis is not
met even in the absence of CIPS. In the simulation of the
method by Monte Carlo techniques, it was observed that
atomic configurations are encountered in the alloy evolution
from which the system does not emerge in a reasonable com-
puting time and that one is obliged to use manual treatments.
This is described as a technical point, although it indicates
that there are attractors in phase space, i.e., that the ergodic
hypothesis is violated. The discussion of this here is based on
the fact that it enables one to emphasize an important pro-
perty of a solid: retention of an acquired structure (in particu-
lar, of shape, since in the solid state matter retains the capa-
city to retain its shape). In a coarse-grained alloy shaped by
slow cooling of a liquid, the state may be considered as close
to equilibrium, with a limited number of structural possibili-
ties (restricted for example by Gibbs phase rule on the num-
ber of phases). For the nanostructural alloys formed by CIPS,
these constraints do not apply, and one gets a wide range of
structural and phase states. This leads to major difficulty in
using local methods of electron microscopy type. When one
interprets the data from averaging methods such as magnetic
ones, one inevitably encounters an ill-posed problem, and it
is necessary to formulate hypotheses on the possible local
states of the alloy.
A constructive approach to analyzing driven alloy forma-
tion processes consists in setting up a hierarchy of models in-
cluding semiphenomenological ones oriented to qualitative
description of a wide range of experimental data and local
models related to them, which describe processes at the
atomic level. For example, my model provides a quantitative
description of the relation between phase composition and
chemical composition for Ti – Cu [1]. Use was made of the
hypothesis of local equilibrium and its consequence the de-
pendence of the diffusion coefficients on the local values of
the atomic microparameters. This allowed me to introduce
effective values for the microparameters for crude descrip-
tion of the steady-state distribution of composition provided
that the difference in the partial diffusion coefficients does
not alter sign throughout the composition range. The latter is
obeyed for alloys with large differences in the atomic radii
and not to substantial positive enthalpies of mixing. Experi-
mental data have been processed to show that during CIPS
an alloy changes in thermodynamic properties: from an alloy
with restricted solubility it is transformed into an alloy with
unrestricted solubility [8]. However, one needs atomic mod-
els to describe the changes in local thermodynamic parame-
ters in CIPS.
On the other hand, it is technically impossible to analyze
the behavior of a driven alloy on the basis only of atomic
models because of the wide range of space-time scales for
the processes, which must incorporate all the possibilities:
vacancy fluxes, ballistic atomic jumps, twinning, diffusion
by the interstitial mechanism, grain-boundary diffusion, and
so on. Further, it is unclear how to organize the analysis of an
Reply to Comments by Yu. A. Skakov and M. A. Shtremel’
infinite set of simulation results for a set of qualitatively dif-
ferent situations (an alloy in CIPS is not ergodic and retains
various structural forms). Therefore, atomic models require
constraints defined by rough semiphenomenological models
that approximate to the experimental situations.
AN ANSWER TO SHTREMEL’S COMMENTS
I have given above some assumptions adopted in con-
structing the model. In Shtremel’s comments, an attempt is
made to enumerate these assumptions and analyze them.
They are given in the form proposed in direct citation of the
text [1], although that does not always correspond to reality.
We consider his comments:
a) “the material diffusion flux (2) occurs on an equilib-
rium diffusion interphase boundary and is proportional to
the square ... of the width L”. This assertion is his conclusion
made from (2). The misunderstanding is related to the inter-
pretation in [1] of the linear dimension L of the spatial corre-
lation of composition as the width of equilibrium diffusion
for the grain boundaries. That interpretation is quite simply
verified by applying (2) to equilibrium conditions in an alloy
with restricted solubility, where JA = 0 and JV = 0. The result-
ing equation gives the composition distribution profile in
equilibrium diffusion phase boundaries with width of L. The
diffusion fluxes intersect that boundary if there is a deviation
from equilibrium.
b) “at a certain stage in the strain, there is an increase in
the diffusion coefficient by 14 orders of magnitude.” That as-
sertion is not an assumption but instead an experimental fact
cited from a reference (see [6] in the references in [1]).
c) “it should be related to vacancy generation.” This as-
sertion caused an adverse reaction on his part: “intensive
plastic strain actually produces premelting vacancy concen-
trations of about 10 – 5 to 10 – 4 (not 10 – 2 ). They are mea-
sured directly by positron annihilation (and also by differen-
tial scanning calorimetry and from the residual electrical re-
sistance: these concentrations are concerned at room tempe-
rature for days but supermobility is not in question).”
All these methods give values for the residual vacancy
concentration averaged over the volume. On that basis, the
peak value of the local vacancy concentration (in the source
regions) during CIPS can only be related to the fact that it
should be higher than 10 – 5 – 10 – 4. Numerical estimates in-
dicate that under CIPS conditions vacancy concentrations of
one are attained in and near regions of tensile stress concen-
tration [7]. Consequently, a permissible estimate has been
taken as 10 – 2, which is close to the Lindeman limit of
5 ´ 10 – 2 corresponding to lattice failure and recovery. This
means an increase in atomic diffusional mobility (hypotheti-
cal) during CIPS by 16 orders of magnitude.
d) and also “with reduction in the vacancy migration ac-
tivation energy” by 12 and 20%. He said instead: “the reduc-
tion in the vacancy migration activation energy is found sim-
ply by fitting...”
255
That reduction in the vacancy migration activation en-
ergy does not appear by fitting but simply is it. The question
is that of the calculated magnitude for this reduction. It is re-
alistic and agrees with the following: reduction in the
Debye – Waller factor as demonstrated by experiment in
CIPS [13]; estimates of the energy in microstrains in
nanostructural alloys produced during CIPS [14]; and reduc-
tion in the vacancy migration activation energy in shearing
bands as calculated by means of the electron density func-
tional [7].
e) “the distances between vacancy sources and sinks ...
are much less than the vacancy diffusion length.” In his opin-
ion, that is impossible: “if a nonequilibrium vacancy is able
to avoid many sinks, then what forces drive it?”
The vacancy diffusion length is DV t ; from the condi-
tion L ^ DV t (where L is the mean distance between va-
cancy sources and sinks) it follows that a steady-state va-
cancy distribution is established in time t between them with
a constant concentration difference, which is the driving
force of the diffusion.
f) the vacancy flux “is induced between adjoining discli-
nations differing in sign” when “the main modes of plastic
strain are grain-boundary slip and grain rotation.” He has:
“nobody has observed the generation of vacancies by discli-
nations and even in models it is not clear whence vacancies
occur.”
My model is intended from the start to describe CIPS
stages when on all the experimental data one finds driven
grain-boundary slip and grain rotation [6]. This is not an ar-
bitrary assumption but instead is a conclusion from a survey
of experimental data. Vacancy fluxes between triple junc-
tions between grains, in which disclination poles are local-
ized, is not an additional hypothesis but instead a direct con-
sequence of taking the general case for the messenger CIPS
mechanism, with the requirements for retaining the continu-
ity of the medium during strain and the dependence of the
vacancy concentration on local stresses. Nobody has ob-
served not only the generation of vacancies by disclinations
but also the network of disclinations generated during CIPS.
This does not prevent their being used in describing plastic
strain [5]. The most valuable result from the [1] model is
possibly also that it assists in the experimental observation of
disclination networks. According to the model, in CIPS in al-
loys there is decoration of the disclination network by re-
gions with differing chemical and phase compositions.
g) “vacancy fluxes with differing partial diffusion coeffi-
cients lead to composition redistribution between adjacent
vacancy sources and sinks” (the inverse Kirkendahl effect).
He has: “... the inverse Kirkendahl effect has been thor-
oughly examined on irradiation with the same stationary va-
cancy concentrations of 10 – 4 and higher temperatures in the
segregation layer of about 10 nm thickness which have been
attained in hundreds of hours and not in the supposed
10 min.”
256
It is incorrect to compare the actions of the inverse
Kirkendahl effect in the irradiation and in the case of CIPS,
as the situations differ in topology and physics. In the first
case, the vacancy sources are distributed in the grain vo-
lumes, with the boundaries unconditional sinks, since at high
temperatures there is guaranteed equilibration along the
grain boundaries. One gets a three-dimensional treatment
with bulk sources. Under those conditions, the gradient in the
vacancy concentration pattern is localized in a narrow region
near the grain boundaries and in fact the inverse Kirkendahl
effect is only slight in the grain volume. It influences the
grain boundaries together with the action of interstitial atom
diffusion, as this also occurs to the boundaries, which leads
to thin nonequilibrium grain-boundary segregations. In my
model, the vacancy sources and sinks are localized, and the
grain boundaries are not in equilibrium and are not uncondi-
tional vacancy sinks, as their role is dependent on the local
stress tensor values. The concentration pattern in the bulk
with distinct sources and sinks is topologically equivalent to
a field with planar surfaces of constant concentration, so one
can use a one-dimensional approximation for semiquanti-
tative description. The action of the inverse Kirkendahl ef-
fect covers the entire volume of a crystallite. The stationary-
profile settling time is dependent on the nonequilibrium va-
cancy flux density. In irradiation experiments, it is small be-
cause of the low source throughput. If we assume the va-
cancy concentration differences considered in the model and
the reduction in the vacancy migration activation energy, we
get values for the flux densities providing the observed ef-
fects during the time of experiments on shearing under pres-
sure. There is no systematic evaluation of the total action
time in other methods of mechanoactivation, but the values
given for the cold strain rate coincide with those appearing in
shearing under pressure (e& £ 1 sec – 1 ). Higher values of are
attained in explosive welding and impact loading. New fea-
tures arise under these conditions, whose analysis falls out-
side the framework of the model. The model may also be
used when the alloy has not attained a steady state. The qua-
litative form of the results is not altered, while the specifica-
tions for vacancy mobility are eased.
h) “the steady-state distributions of composition between
sources and sinks coincide with the stationary composition
distributions arising on the action of a constant vacancy dif-
ference.” That assertion is not an assumption and is the result
of studies on the dependence of the solutions to the diffusion
equations on the boundary conditions [8].
i) “when there is a large difference in the atomic radii of
the alloy components... marked concentration-dependent
microstresses arise and the lattice becomes unstable, which
leads to the production of an amorphous state or the occur-
rence of x-ray amorphous alloys with maximally small
grains.” That assertion simply expands Bernal’s amorphi-
zation model. Its use here is justified by experimental studies
on the dependence of microstrain and mean grain sizes on al-
V. L. Gapontsev
loy composition when there is a large difference in the
atomic radii [14].
CONFLICTS BETWEEN THE BALLISTIC MODEL
AND EXPERIMENT
In the criticism of [4], references are made to papers
dealing with the ballistic mechanism for the formation of
driven alloys (here references [15, 16]). Shtremel’ considers
that the authors of those papers have finally resolved the
question of the mechanoalloying mechanism by examining
the process at the atomic level “... by the method of molecu-
lar dynamics without any arbitrary assumptions.” Detailed
analysis of those researches however leads to conflicting
conclusions. They discussed the possibility of alloy flaking
by the ballistic mechanism. In Martin’s survey [12], he ana-
lyzed the action of that mechanism on thermodynamically
distinct alloys. The following were used: equations of diffu-
sion type with an additional term describing the ballistic
atomic jumps; Monte Carlo simulation; and the use of the
average molecular field method. It was found that the steady
state of a driven alloy is either complete mixing (in the
low-temperature limit) or self-organization of structures
formed by competition between the thermodynamic tenden-
cies to decomposition and the mechanical mixing. In all
these cases, the alloy is homogeneous at the mesoscale level
(the linear scale equal to the mean distance between disloca-
tion source and sink). This conclusion was not doubted for
more than 20 years up to the appearance of papers by Lund
and Schuh such as [15].3 They used a two-dimensional simu-
lation to observe exfoliation in the action of the ballistic
mechanism. That conclusion raised sound doubts and was re-
jected on the basis of a three-dimensional model based on the
molecular dynamics method [16].
The parameter L influences these processes, which is the
size of the spatial composition correlation region. It arises as
the radius of the kernel for the functional for the transition
frequencies in deriving the equation for the flux of matter
(expression (2) in [1]) [8, 17]. This approach is equivalent to
the free-energy functional method for inhomogeneous alloys.
The value of L is dependent on the minimal rate of decrease
in the physical field and thus on the dimensions of the space.
In three-dimensional space, it may be estimated as L3 » 6a,
while in two-dimensional space L2 » 20a, where a is the lat-
tice parameter. In a three-dimensional model [16], the edge
length of a cubic cell is 40a, which exceeds L3 by almost an
order of magnitude, while in a two-dimensional model [15],
the edge length of a square cell is (20 – 30)a, which agrees as
to order of magnitude with L2. The effects of thermodynamic
forces are maximal at lengths of order L. The accidental
3
In Shtremel’s comments, the reference was given not to [15] but
to a paper similar in content by the same authors. The replacement
is related to the discussion in [15, 16], which is important for this
topic.
Reply to Comments by Yu. A. Skakov and M. A. Shtremel’
choice of two-dimensional cell size predetermined the partial
character of the results in [15]. The accidental “correct”
choice of size for the three-dimensional cell predetermine the
general character of the conclusions obtained in [16]: on the
action of the ballistic mechanism “a large enthalpy of mixing
and a large discrepancy between the lattice parameters of the
segregation and matrix do not prevent complete forced mix-
ing.” In all other cases, forced mixing is inevitable in this
mechanism. Nevertheless, experiment records the direct op-
posite: flaking in CIPS in alloys in the systems Fe – Cr – Ni
[18] and Pd – Ni [19]. This casts doubt on the suitability of
the ballistic mechanism as the basis for the generation of
driven alloys.
The second conflict between the ballistic model and ex-
periment, which has been repeatedly pointed out in the dis-
cussion by Skakov, is the dependence of the formation order
for intermetallides on the relation between the partial diffu-
sion coefficients of the components at the stage preceding the
formation of a supersaturated solid solution.
The third conflict between this model and experiment is
that anomalous phase transitions in CIPS are related to a late
stage in strain, where e > 3 and d g < 200 nm (formation of
supersaturated solid solutions, formation and decomposition
of intermetallides, amorphization, cyclic amorphous
phase-crystallite transformations, and layering in homoge-
nous solid solutions), where e is the true logarithmic degree
of strain and d g is the mean grain diameter (see survey in
[8]). In that stage, the dislocation creep mechanism no longer
works (it is the basis of the ballistic mechanism) because dis-
location glide is hindered by interactions between them, and
the main modes of plastic strain become grain-boundary slip
and rotation [6]. In the absence of quasihydrostatic compres-
sion, those mechanisms in a polycrystalline medium lead to
microcracking and subsequent brittle failure. Compression
for example in CIPS in Bridgman anvils or on cold rolling
and all-sided forging or mechanoactivation in ball and vibra-
tional grinders, or equal-channel angular and screw pressing
will lead to anomalous structural and phase relationships as
an alternative to brittle failure.
The ballistic model for a driven alloy uses by default ar-
bitrary assumptions, and in particular has the basis that the
processes are not influenced by the following: a) structural
state of the polycrystalline material (grain sizes and so on, al-
though one is considering bulky nanostructural alloys); and
b) stages in the strain and the dominant mechanism (although
one is considering CIPS). The difficulties with the ballistic
model have led me to draw up an alternative model which
I have used to apply to particular systems in [1].
TOPIC SIGNIFICANCE
These topics have major significance from the viewpoint
of choosing approaches to describing CIPS action on solids,
but one must agree with Shtremel’ that the subject of discus-
sion is not altogether consistent. As regards the temperature
257
dependence of any of these processes accompanying
mechanoactivation, we note that when the temperature is re-
duced one gets not only a monotone increase in the mixing
(ballistic mechanism) and a monotone reduction in the diffu-
sion transport (classical diffusion), but also one may get
nonmonotone dependence on temperature with a maximum
effect in the region of room temperatures. The effects of in-
duced diffusion are dependent not only on the diffusion coef-
ficients but also on the operation of the vacancy sources,
which has a temperature dependence related to the plastic
strain mechanism. Experiment shows [19, 21] anomalous
temperature dependence for layering and diffusion in CIPS
on alloys. However, we are not solely concerned with possi-
ble temperature dependence in mechanoalloying. From the
[1] model a new approach has recently been proposed to the
radiation stability and strain stability of constructional
austenitic steels [20]. This considers stability as a kinetic ef-
fect associated with the concentration dependence of the par-
tial diffusion coefficients. According to the traditional view-
point, the stability of these steels is related to thermodynam-
ics: in a certain composition area, the martensite transforma-
tion occurs on strain. These two concepts have been dis-
cussed in the last two years at seminars at the Institute of
Metal Physics, Urals Branch, RAS. Any form of resolution is
impossible without experimental study of the stability in the
strain martensite (it undoubtedly is formed at early stages in
the strain) in relation to the effects of mechanical mixing and
diffusional layering. The [1] model stimulates such research.
NEED FOR EXPERIMENTAL TEST
OF MODEL PREDICTIONS
The driven-alloy formation mechanisms cannot be deter-
mined only by comparing the capacities of models to explain
existing experimental evidence. It is necessary to obtain fore-
casts from the model and perform experimental checks. In
the case of models for localized vacancy sources/sinks, that
is possible for the Ti-Ni system when sheared under pressure
[22]. The phase composition distribution obtained after CIPS
has already been given a quantitative explanation by the
model and this has provided for determining the boundaries
of the existence regions for solid solutions and the conse-
quent effective microparameters [1, 8]. If specimens after
CIPS are subjected to moderate annealing (diffusion length
should not exceed 10 nm), then the model applies that a quite
definite distribution of phases should arise to decorate the
three-dimensional dislocation network localized at triple
junctions. It is dependent on the average specimen composi-
tion, but in all cases there should be a spatial network of
segregations of almost pure titanium. If one joins two adja-
cent segregations of titanium by a straight line, one should
find the following segregations on it: a) Ni> 50Ti< 50 (Ti,
NiTi2, NiTi, Ni3Ti, Ni, Ni3Ti, NiTi, NiTi2, Ti); b) Ni40Ti60
(Ti, NiTi2, NiTi, Ni3Ti, NiTi, NiTi2, Ti); c) Ni30Ti70 (Ti,
NiTi2, NiTi, NiTi2, Ti); d) Ni25Ti75 (Ti, solid solution of Ni in
258
Ti, Ti). These qualitative conclusions are based on analyzing
a family of curves for the composition distribution (of the
type shown in Fig. 2 in [1]), and are affected by the equilib-
rium phase diagram for the Ni – Ti system. They can be sup-
plemented with quantitative estimates for the relative dimen-
sions of the phase segregations and the relative positions in
which they are localized. If the forecast is confirmed, it will
be necessary to adopt the hypotheses forming the basis of the
model, including the messenger CIPS mechanism. A nega-
tive result will require the construction of a different
semiphenomenological model oriented to explaining the ex-
perimental data accumulated in the 1970s in research on in-
tensive plastic strain. In my opinion, this cannot be a model
that incorporates only the ballistic mechanism. In such form
it will conflict with experiment and denote premature aban-
donment of thermodynamic methods and the mechanics of
continuous media in describing classically deformed solids.
I am indebted to Professors Yu. A. Skakov and M. A. Shtre-
mel’ for undertaking the task of criticizing the paper.
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