ISSN 0036-0295, Russian Metallurgy (Metally), Vol. 2017, No. 6, pp. 472–476. © Pleiades Publishing, Ltd., 2017.

Original Russian Text © A.B. Korostelev, 2017, published in Elektrometallurgiya, 2017, No. 3, pp. 22–27.

THEORY
OF METALLURGICAL PROCESSES

Mechanism and Kinetics of Reaction Diffusion in Steels

under the Conditions of Simultaneous External
and Internal Oxidation
A. B. Korostelev
Dollezhal Scientific Research and Design Institute of Electrotechnics (NIKIET), Moscow, Russia
e-mail: korostelev@nikiet.ru
Received October 17, 2016

Abstract⎯Thermodynamic prerequisites for the formation of internal oxidation zones in multicomponent

alloys (metal-solvent + alloying element + insertion element (oxygen, nitrogen, carbon)) are presented. The
kinetics of changing the component concentrations upon the formation of one- and two-phase oxide layers
is shown. The boundary conditions for the formation of the internal oxidation zones are determined.

Keywords: steel, alloying element, diffusion, internal oxidation, structure, and phase composition
DOI: 10.1134/S003602951706012X

INTRODUCTION sideration of conditions for the formation of two-

The processes of formation of chemical com-
pounds in the diffusion zone (reaction diffusion) upon
the saturation of single-phase alloys with highly
mobile elements (oxygen, nitrogen, carbon, etc.) are
widely used in the practice of chemical thermal treat-
ment and in studying liquid–metal corrosion [1]. Lay-
ers of compounds growing in time, as a rule, according
to a parabolic law are formed in binary systems due to
reaction diffusion [2]. Single-phase layers of com-
pounds, which will be formed in the diffusion zone,
can be indicated on the basis of the corresponding
phase diagram. The theory of the diffusion growth of
layers was developed for this case [3] and shows good
correspondence with experiment.
One of the peculiarities of reaction diffusion in
three-component systems is the possibility of forming
two-phase regions along with the formation of single-
phase layers, namely, a solid solution containing
disperse particles of a compound (zones of internal
oxidation, nitration, borating, etc.). As will be shown
below, the knowledge of the phase diagram does not
allow one to predict the structure of the diffusion zone
unambiguously. For this purpose, it is necessary, on
the one hand, to have data on the kinetics of the pro-
cess. On the other hand, there are no theoretical mod-
els of reaction diffusion on the basis of which one can
determine the kinetics of growth of layers and two-
phase regions, the distribution of the number of
disperse particles in these regions, their average size,
and the phase volume.
The following data were published in [4]: the for-
mulation of a physical model for the process, the con-
phase regions in the diffusion zone, a closed system of
equations from the solution of which the kinetics of the
process and the main parameters of the diffusion zone
structure can be determined, and theoretical and exper-
imental studies of the main regularities of the reaction
diffusion process in three-component systems.
The phase composition of the diffusion zone can
be determined from the construction of a diffusion
trajectory on an isothermal section of a phase dia-
gram. A diffusion trajectory is obtained by the move-
ment of a figurative point from the alloy composition
on the saturated surface to its initial composition. This
trajectory shows how the component concentrations
changes in the diffusion zone, and the phase composi-
tion of the zone depends on the regions in the phase
diagram through which the diffusion trajectory passes.
The isothermal section of a phase diagram that is
typical of the M–B–O systems (M is the metal sol-
vent; B is the alloying element; and O is oxygen, car-
bon, boron, etc.) is shown in Fig. 1 [5]. Let the initial
composition of the alloy be x1 in this diagram and the
composition on the saturated surface be x.
We now consider examples for constructing a diffu-
sion trajectory for three most often cases of M–B
binary alloy saturation, where initial point x can be
localized as follows:
(1) in the two-phase region (Mv2Ov1 + Bω2Oω1),
(2) in the one-phase region Mv2Ov1, and
(3) in the one-phase region Bω2Oω1,

472
 MECHANISM AND KINETICS OF REACTION DIFFUSION IN STEELS 473

where the stoichiometric coefficients of metal oxides

are designated by index v and those of the alloying ele-
ment are designated by index ω.
In the first case, a continuous layer of a mixture of 1. Bω2Oω1 + Mγ2Oγ1 α 2. Bω2Oω1 + Mγ2Oγ1 Bω Oω + α α
2 1
phases Mv2Ov1 + Bω2Oω1 is observed on the surface,
and the ratio between the phases and their chemical O
composition changes according to a diffusion trajec-
tory in the interval [x, Q] with the distance from the M γ2 O γ1 + O
Bω2Oω1 + O
saturation surface. Then, the trajectory passes through Bω2Oω1+
the three-phase region (α + Bω2Oω1 + Mv2Ov1). Since
M γ2 O γ1 + O
no three-phase region can be formed in the diffusion
zone of a three-component system, concentration M γ2 O γ1 Bω2Oω1
x
Mγ2Oγ1 + Bω2Oω1
jumps are observed at the boundary of the layer x x
(Mv2Ov1 + Bω2Oω1) with solid solution α. Taking into Q α + Bω2Oω1 + α + Bω2Oω1
account that thermodynamic equilibrium is usually Mγ2Oγ1
α + M γ2 O γ1
established within a comparatively short time at inter- β + Bω2Oω1
faces, the concentrations of the components in a solid α+β+
Bω2Oω1
solution at the boundary with the continuous layer G
E
should correspond to the point of ternary equilibrium E 2 α+β β
and the concentration jumps are (Q–E). M B
x1 x0 x1 α

As will be shown below, a trajectory in the interval

[E, x] can pass either immediately through the single-
phase α region (curve 1) or first through the two-
phase (α + Bω2Oω1) region in the interval [E, G] and,
then, in the interval [G, x1] through the single-phase
region (curve 2). The structures obtained in the first
and second cases are schematically presented in Fig. 1.
If point x lies in the single-phase region Mv2Ov1 or
Bω2Oω1), the diffusion trajectory passes through the
regions where the corresponding compound exists,
i.e., the two-phase region (α + Mv2Ov1 or α + Bω2Oω1)
and the α region. As in the case considered above,
either a solid solution or the internal oxidation zone
(α + Bω2Oω1 or Mv2Ov1 + α) can follow the continu-
ous layer of the compound. Thermodynamic equilib-
rium also takes place at the interface within a compar-
atively short time, and the equilibrium concentrations
of the components in the solid solution can be deter-
mined from the intersection point of the solubility line
of the solid solution with the conode originating from
the intersection point of the trajectory with the solu-
bility line of oxide.
Thus, depending on the position of a diffusion tra-
jectory in the phase diagram, the structure of the dif-
fusion zone behind the continuous layer can be both
one-phase and two-phase. Therefore, it is necessary to
establish under which saturation conditions a diffu-
sion trajectory passes through the corresponding two-
phase region and the internal oxidation zone is
formed.
It is known that the supersaturation of a solid solu-
tion is a necessary condition for the formation and
growth of second-phase particles. Supersaturation is
Fig. 1. Scheme of an isothermal section of the phase dia-
gram of a three-component M–B–O system.
state. Then, the measure of supersaturation can be
defined as follows:
⎡⎛ a ⎞ m ⎛ a ⎞ n ⎤
L = ln ⎢⎜ Aρ ⎟ ⎜ Bρ ⎟ ⎥ , (1)
⎢⎣⎝ a A ⎠ ⎝ aB ⎠ ⎥⎦
where aA, aB and a Aρ , aBρ are the current and equilib-
rium thermodynamic activities of components A and
B, respectively, forming compounds AmBn. From the
theory of phase transformations, we have
L = 2σ V m kTRK . (2)
Here σ is the surface tension coefficient of a nucleus of
the new phase, Vm is the molecular volume of the
formed compound, RK is the radius of the critical
nucleus, and T is the temperature.
It is seen from Eqs. (1) and (2) that RK is finite and
positive for a suprsaturated solid solution (L > 0). At
equilibrium, L = 0 and RK is infinitely high.
In the considered case of reaction diffusion, where
thermodynamic equilibrium is observed at the bound-
aries continuous layer–two-phase sublayer and two-
phase sublayer–solid solution and the measure of solid
solution supersaturation is L = 0 at these boundaries,
the condition for supersaturation is the maximum of
function L(x),
∂L ∂x x = x = 0, (3)
max

indicated by the deviation of the free energy of a super-

saturated solid solution from its value in equilibrium ∂ 2L ∂ x 2 < 0; x ≥ y1 (t ) , (4)

RUSSIAN METALLURGY (METALLY) Vol. 2017 No. 6

474 KOROSTELEV

Continuous In turn, the thermodynamic activities of the com-

layer α + 3ω2Oω1 ponents in the solid solution are related to the concen-
α trations of these components Ci (i = 1, 2) according to
Φ
C2(γ1) the Wagner equations
C2(γ) C20
Φ
C20 ai = C i exp ( ε iiC i + ε ijC j ) , (i, j = 1, 2; i ≠ j ) , (7)
where εij are the interaction parameters. For low con-
centrations of a highly mobile impurity (oxygen, car-
Φ Φ C2(γ1) bon, nitrogen) and an alloying element, Eqs. (7) are
C10 C1(γ1)
simplified according to the limiting Debye–Hückel
law applicable to strongly diluted solutions as follows:
C1(γ1)
C1(γ)
a1 ≅ C1 exp ( − ε12 C 2 ) ; a2 ≅ C 2. (8)
0 y1(t) u(t) x
Here ε12 is the parameter of the oxygen–alloying ele-
ment interaction and ε12 < 0, because, in the case con-
sidered, the alloying element has a higher affinity to
oxygen than the solvent metal.
Fig. 2. Scheme of the distribution of the component con- The component concentrations in the solid solu-
centrations (index 1 refers to oxygen, index 2 refers to an
alloying element) in the scale of the solid solution of the
tion C1(x, t) and C2(x, t) can be determined from the
alloy (y1 is the coordinate of the cinder–internal oxidation solution of the diffusion problem. Let us consider the
zone boundary, and y is the coordinate of the internal oxi- process for the short times within which no noticeable
dation zone–solid solution boundary). decrease in the supersaturation occurs due to the
nucleation and growth of compound particles; in
addition, we have y1 ≅ 0 (Fig. 2). This allows us to use
where x is the distance from the saturated surface and a system of equations of three-component diffusion in
y1(t) is the coordinate of the boundary of the continu- the solid solution for the calculation of Ci (i = 1, 2).
ous layer.
Taking into account Eqs. (8), this system of equations
Therefore, the problem is reduced to the determi- takes the form
nation of dependence L(x) and the elucidation of the
∂ C1 ∂C ∂ C2
2 2
conditions under which Eqs. (3) and (4) take place, as = D11 21 + D12 ;
applied to the formation of the zones (α + Bω2Oω1) ∂t ∂x ∂x 2 (9)
and (α + Mv2Ov1). ∂C 2 ∂ 2C 2
= D22 ,
∂t ∂x 2
CONDITIONS FOR THE FORMATION where Dii (i = 1, 2) are the diffusion coefficients.
OF THE INTERNAL OXIDATION The solution of system (9) with the initial and
ZONE (α + Bω2Oω1) boundary conditions
In the case of formation of disperse particles of C i ( 0, t ) = C i ; C i ( x, 0) = C i ;
eq eq
alloying element oxide Bω2Oω1 with a small homogene-
C i ( ∞, t ) = C i ; C i = 0 (i = 1, 2) ,
0 0
ity region, function L is determined from the following
equation (O is component 1, B is component 2):
gives the following equations for the component con-
( ),
centrations:
L = Φ ( a1, a2 ) − Φ eq a1eq , a2eq (5)

where
eq ⎡ eq D
C1 ( x, t ) = C1 − ⎢C1 + 12 C 2 − C 0 ⎥
⎣ D11
eq
(
2 ⎤

⎦
)
(10)
(
Φ eq a1eq , a2eq ) − In {( ) ( ) } = ΔG
a1eq
ϖ1
a2eq
ϖ2
kT × erf λ +
2 D11 D11
D12 eq
(
C 2 − C 0 erf
2 λ
2 D22
);

is the equation of the solubility line, where ai and aieq (

C 2 ( x, t ) = C 2eq − C 2eq − C 02 erf ) λ ;
2 D22
(i = 1, 2) are the current thermodynamic activity of the
ith component and its equilibrium value, respectively, λ=x t.
and ΔG is the free energy of formation of compound
Bω2Oω1. Let us substitute Eqs. (10) into Eqs. (8) and expand
Φ(λi) (Eq. (6)) into a series in powers of C i1 − C ieq , i =
Φ ( a1, a2 ) = ln {( a1 ) ( a2 ) ϖ } .
ϖ1 2
(6) 1, 2. We restrict our consideration to the linear expan-

RUSSIAN METALLURGY (METALLY) Vol. 2017 No. 6

 MECHANISM AND KINETICS OF REACTION DIFFUSION IN STEELS 475

sion terms, which corresponds to small deviations graphic studies, an alloy with 20 wt % Cr is saturated
from equilibrium in Eq. (5), and obtain with chromium (C 2eq > C 20 ) and no internal nitration

L (λ) =
ω1
eq
C1
{ (C 0
2 )
− C 2eq ε12 C1eq
zone is formed. In all other cases, chromium is
removed from the samples to form an internal nitrid-
ing zone. The higher the difference between C 20 and
⎡ dC eq 1 ⎤ erf λ
× ⎢1 − 1eq eq ⎥
(11) C 2eq , the larger the zone width.
⎣ dC 2 ε12 C1 ⎦ 2 D22
eq 0 eq
(
− ⎡⎣C1 + ε12 C1 C 2 − C 2 ⎤⎦ erf λ ,
eq

2 D11
) } CONDITIONS FOR THE FORMATION
OF THE INTERNAL OXIDATION ZONE
where (α + Mv2Ov1)
In the case of formation of the internal oxidation
dC1eq
eq
dC 2
= −
C1eq
ω1C 2
eq (
ω2 − ε12 C 2 ω1 .
0
(12) ) zone containing metal-solvent oxides Mv2Ov1 with a
small homogeneity region, function L is determined
The substitution of Eq. (11) into Eqs. (3) and (4) from the following equation:
and their solution show that L has a maximum when
the following conditions are fulfilled: L = Ina1v1a3v 2 = Δ G1 kT , (16)
where a1 ≅ C1 exp ( − ε12 C 2 ) and ΔG1 is the free
(C 0
2 )(
− C 2eq C1eq ε12 − dC1eq dC 2eq ) > 1, energy of formation of compound Mv2Ov1. Using the
C1 + C1 ε12 C 2 − C 2
eq eq
( 0 eq
) earlier manipulations, we can show that L(λ) in
inequality (15) has a maximum if condition (13) is ful-
(
C1eq + C1eq ε12 C 20 − C 2eq > 0. ) (13) filled; in addition, we have

dC eq dC1
eq
= C 0 (
v 1C 3eq ε12 + v 2)> 1, (17)
The derivative 1eq determined by Eq. (12) is usu-
dC 2
eq
dC 2
1
(
v 1C 3 − v 2C1
eq eq
)
ally lower than zero. In this case, Eq. (13) leads to the
following inequalities: since C 3eq @ C1eq . The consequences of Eqs. (13) and
(17) are as follows:
C 2eq > C 21; (14)
C 2eq > C 20, (18)
dC1eq D22 C1eq
< − ε12 C1eq . (15) −1
eq
dC 2 (
D11 C 20 − C 2eq ) 1 > C eq − C 0 > ⎛ v 1 D11 + ε ⎞ ,
( )
⎜v D 12 ⎟ (19)
ε12
2 2
⎝ 2 22 ⎠
It follows from inequalities (14) and (15) that the
two-phase region (α + Bω2Oω1) is formed if the initial That is, the formation of disperse particles (α +
concentration of the alloying element in the solid solu- Mv2Ov1) in the diffusion zone requires that the initial
tion C 20 is higher than its equilibrium value established concentration of the alloying element C 20 is higher
at the boundary “continuous layer–solid solution.” than its equilibrium value C 2eq at the boundary “con-
The slope of the solubility line in an isothermal section tinuous layer–solid solution.” As can be seen from
of the phase diagram at the point with coordinates C1eq inequality (19), the higher (by absolute value) the
parameter of the alloying element–oxygen interaction
and C 2eq should be higher than the critical value, ε12, the worse the conditions for the nucleation of
dC1
eq
D22 C1
eq oxides Mv2Ov1.
= − ε12 C1 .
eq
eq
dC 2 cr D11 C 2 − C 2
0 eq
( ) As applied to the isothermal section of the phase
diagram shown in Fig. 1, the results obtained allow us
The conclusion that the condition for the forma- to conclude the following.
tion of disperse particles of the second phase is the ful-
fillment of inequality (14) was checked by a series of CONCLUSIONS
experiments on internal nitriding of Fe–Cr alloys. The
essence of the experiment was as follows. Alloy sam- (1) If point x lies in the region (Mv2Ov1 + Bω2Oω1),
ples with different initial contents of chromium i.e., behind a continuous layer of a mixture of these
(20, 30, 40, 50, and 60 wt %) were subjected to simul- phases, the two-phase region (α + Bω2Oω1) forms for
taneous chromium plating and nitriding from an Fe– all alloys (if inequality (15) is fulfilled) with the initial
25 wt % Cr–NH4Cl mixture at 1100°C. As shown by content of the alloying element that is higher than its
the data of X-ray spectral microanalysis and metallo- concentration at point E, whereas the region (α +

RUSSIAN METALLURGY (METALLY) Vol. 2017 No. 6

476 KOROSTELEV
Mv2Ov1) is formed for all alloys (if inequality (19) is
fulfilled) with the initial content of the alloying ele-
ment lower than its concentration at point E.
(2) If point x lies in the region Mv2Ov1, the two-
phase region (α + Mv2Ov1) is formed behind a contin-
uous layer of this phase for the alloys (if inequality (19)
is fulfilled) in which the initial concentration of the
alloying element is lower than its concentration at the
intersection point of the corresponding conode with
the solubility line separating the α and (α + Mv2Ov1)
regions of the phase diagram.
(3) If point x lies in the region Bω2Oω1, the two-
phase region (α + Bω2Oω1) is formed behind a contin-
uous layer of this phase for all alloys (if inequality (15)
is fulfilled) in which the initial concentration of the
alloying element is higher than its concentration at the
intersection point of the conode with the solubility
line separating the α and (α + Bω2Oω1) regions of the
phase diagram.
(4) If conditions (1), (15), (18), and (19) are not
fulfilled, a continuous layer of the corresponding
phase (or a mixture of phases) borders upon a single-
phase region: a solid solution α. The approach consid-
ered makes it possible to qualitatively determine the
structure and phase composition of the diffusion zone
under specified saturation conditions of a binary alloy.
However, it is most important to calculate the change
in the parameters of the structure in time (thickness of
RUSSIAN METALLURGY (METALLY)
the continuous layer, internal oxidation zone, number
of oxide particles, their average size, the total volume
in each cross section of this zone). These data can be
obtained from the solution of the corresponding
closed system of equations, which was presented for
the case of formation of the internal oxidation zone
(α + Bω2Oω1) in [4].
REFERENCES
1. J. Zhang, “Oxygen control technology in application of
liquid lead and lead–bismuth systems for mitigating
materials corrosion,” J. Appl. Electrochem. 43 (8),
755–771.
2. N. A. Azarenkov, S. V. Litovchenko, I. M. Neklyudov,
and P. I. Stoev, “Corrosion and Protection of Metals.
Part 1. Chemical Corrosion of Metals” (KhNU, Kharkiv,
2007).
3. B. S. Bokshtein and A. B. Yaroslavtsev, Diffusion of
Atoms and Ions in Solids (MISIS, Moscow, 2005).
4. M. G. Isakov and A. B. Korostelev, Mechanism and
Kinetics of Reaction Diffusion in Melts. Theoretical Stud-
ies of Metallurgical Processes: Monography, Ed. by
A. B. Korostelev (MGB-MI, Moscow, 2011).
5. C. Wagner, “Reaktionstypen bei der Oxydation von
Legierungen,” Z. Electrochem. 63, 772–790 (1959).
Translated by E. Yablonskaya
Vol. 2017 No. 6