Philosophical Magazine Letters

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An analytical model of grain growth considering

the conjoint effects of precipitate pinning and
solute drag in steel

Joydeep Maity

To cite this article: Joydeep Maity (2022) An analytical model of grain growth considering the
conjoint effects of precipitate pinning and solute drag in steel, Philosophical Magazine Letters,
102:10, 307-323, DOI: 10.1080/09500839.2022.2123113

To link to this article: https://doi.org/10.1080/09500839.2022.2123113

Published online: 06 Oct 2022.

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PHILOSOPHICAL MAGAZINE LETTERS
2022, VOL. 102, NO. 10, 307–323
https://doi.org/10.1080/09500839.2022.2123113

An analytical model of grain growth considering the

conjoint effects of precipitate pinning and solute drag in
steel
Joydeep Maity
Department of Metallurgical and Materials Engineering, National Institute of Technology Durgapur,
Durgapur, West Bengal, India

ABSTRACT ARTICLE HISTORY

An analytical model is developed to explain the kinetics of Received 5 July 2022
grain growth in steel that takes into account all feasible Accepted 3 September 2022
prime phenomena; namely, surface energy reduction,
KEYWORDS
precipitate pinning effect and solute drag effect. The Grain growth in steel;
shapes of matrix grains and the precipitates are assumed precipitate pinning effect;
to be tetrakeidecahedron and spherical, respectively. A solute drag effect; analytical
single solute and a single type of precipitate are further model; effective migration
assumed to be responsible for the solute drag and the coefficient
precipitate pinning, respectively. An explanation of drag
energy is provided in terms of Gibbs free energy change
for solute segregation that eventually merges to the well-
known Langmuir–McLean relationship. The developed
model is validated in view of the existing database in
available literature. A new methodology of grain growth
analysis is accordingly proposed on the basis of the
conceptualised ‘effective migration coefficient’ of the system.

1. Introduction
In the context of conceiving physical phenomenon at condensed state, the
change in the size of individual crystals (called the ‘grain size’) with an aid of
thermal energy envisages a significant field of contemplation in polycrystalline
material at solid state; since the properties of materials (necessary for certain
application) are directly related to grain size. It was first realised by Beck [1]
and Smith [2] that the reduction in surface energy is the main driving factor
for the continuous growth of grains in a polycrystalline material. Meanwhile,
‘precipitate pinning’ [3–9] and ‘solute drag’ [10–15] were identified as the
two prime factors opposing the process of grain growth. Precipitate pinning
effect arises due to the pinning force exerted by the second phase precipitate
particle against grain boundary motion. On the other hand, the solute drag
effect is realised in view of the drag force exerted by the segregation (cluster)

CONTACT Joydeep Maity joydeep_maity@yahoo.co.in; joydeep.maity@mme.nitdgp.ac.in Department of

Metallurgical and Materials Engineering, National Institute of Technology Durgapur, 713209, Durgapur, West
Bengal, India
© 2022 Informa UK Limited, trading as Taylor & Francis Group
308 J. MAITY

of solute atoms (not the precipitate) against the motion of grain boundary.
Henceforth, these two aspects have been studied at rigour by many investi-
gators over several decades.
A series of significant studies has been carried out on the pinning effect of
second phase precipitate particle against grain boundary motion; especially
by Zener [3], Hillert [4] and Gladman [5]. Taking into account the specific
surface energy of the grain boundary and the size of the spherical precipitate
particle, Zener [3] conceived the pinning force exerted by the particle with
an analogy of surface tension. However, the resultant driving force appeared
to be an overestimated one in Zener-model. Subsequently, Hillert [4] tried to
correlate energy change and grain growth with a concept of critical radius
beyond which the energy would tend to decrease. Accordingly, this approach
found an application only in a situation where large grains tend to consume
small grains, such as a situation in secondary recrystallisation. Furthermore,
Gladman [5] came forward with a more detailed conceptualisation by at first
formulating the energy changes accompanying the unpinning process and hen-
ceforth that for accompanying grain growth. Thereafter, these two aspects are
combined to finally evaluate the overall energy change for grain growth and the
critical radius initially conceptualised by Hillert [4]. However, this formulation
proceeded towards a mathematical complicacy and the kinetics of grain growth
in terms of grain size variation as a function of holding time could not be for-
mulated analytically taking into account the precipitate pinning effect despite
several subsequent attempts by other investigators [6–9].
The study on solute drag effect was initiated by Lucke and Detert [10]
through the conceptualisation of an higher energy state brought to the segre-
gated solute as a consequence of grain boundary movement, thereby resulting
in the so-called drag force. In this attempt, a velocity (grain growth rate)-depen-
dent drag force was proposed that could not match the experimental result
exhibiting a lower value of time exponent. Cahn [11] followed by Hillert and
Sundman [12] opined this deviation as a manifestation of a transition from a
high-velocity extreme to a low-velocity extreme. This confusion persisted for
a long time as Drolet and Galibois [13] found a significant deviation of exper-
imental results from the proposed theory at very high velocities. In accordance,
Burke [14] followed by Grey and Higgins [15] introduced a velocity-indepen-
dent drag force along with velocity-dependent counterpart. However, in all
these foregoing approaches, amidst many debatable issues originated in view
of exemplifying the physical meaning of drag force through the forces acting
at an atomic level, the straightforward kinetic expression of grain growth
appeared to remain elusive. Moreover, a mathematical complicacy was realised
in the form of an infinite integral while conceiving the drag force in terms of
negative potential gradient. The necessary terms for quantitative analysis;
such as ‘intrinsic drag coefficient’, ‘intrinsic mobility’, ‘chemical potential of
solute at grain boundary’, etc. are usually not known for a particular system.
 PHILOSOPHICAL MAGAZINE LETTERS 309

As a consequence, these approaches could not lead to an ultimate expression of

grain growth kinetics in the form of grain size variation with time.
The first analytically derived relationship that directly correlates grain size
(D, expressed in terms of average grain diameter) with holding time (t) was
the Beck’s relationship [1]. This popular approach, in its initial conceptualis-
ation, expressed as D to be proportional to t0.5 for a grain size significantly
greater than the initial grain size. However, this approach was based on only
the primary consideration of the reduction in surface energy of a polycrystalline
solid with the progression of grain growth. Unfortunately, both the grain
growth opposing factors (‘precipitate pinning’ and ‘solute drag’) were
ignored as its prime limitation. As a consequence, in a real polycrystalline
solid containing solute and precipitate particles, the time exponent (n) is sig-
nificantly lowered down from 0.5. This practically converted Beck’s relationship
to a mere empirical relationship with D proportional to tn. Till date no analyti-
cally derived relationship is available that directly correlates the fundamental
aspects of grain growth in terms of the driving factor (reduction in surface
energy) and the opposing factors (precipitate pinning effect and solute drag
effect). Of course, non-analytical numerical modelling based complex computer
simulation techniques have been proposed [16–20]. However, these approaches
are far away from an easy-to-conceive fundamental analytical approach where
correlation among all parameters can be conceived with high clarity and ease.
In an initial analytical approach by the present author [21], the solute drag
effect is included along with the surface energy reduction aspect so as to
develop an analytical model for grain growth in steel. However, it did not
provide a detailed fundamental explanation of ‘drag energy’ in terms of
Gibbs free energy change for solute segregation. Most importantly, the precipi-
tate pinning aspect was not included in this analytical model. Accordingly, the
present research aims at developing a complete analytical model for the first
time that conceives all factors of grain growth; namely, reduction in surface
energy, precipitate pinning effect and solute drag effect. The model is validated
in terms of existing database on grain growth in steel along with a proposition
of futuristic data analysis with regard to newly conceptualised ‘effective
migration coefficient’ of the system. The analytical approach is chosen due to
its inherent ability to fundamentally correlate all parameters dealt within the
chosen system without requiring any numerical, empirical or semi-empirical
approximation technique. Steel being a significant engineering material of
wide application range, the grain growth in steel is provided the prime focus
in data analysis.

2. Analytical modelling approach

In a polycrystalline alloy, while the specific surface energy reduction is the
prime driving factor for grain growth, grain boundary pinning by precipitate
310 J. MAITY

particles and solute drag originated from the segregation (not precipitation)
of solute at grain boundary are the two opposing factors for grain growth.
Therefore, in this modelling approach, the overall free energy change per
mole (DG) for grain growth is envisaged as the summation of the surface
free energy change per mole (DGs ) in absence of any other hindrance, the
free energy change per mole (DGp ) accounting for the ‘pinning effect’ due
to the presence of second phase precipitate particles at grain boundary and
the free energy change per mole (DGd ) accounting for the ‘solute drag’
arising as a consequence of the solute segregation at grain boundary. There-
fore,
DG = DGs + DGp + DGd (1)
It is understood from basic thermodynamic principles that the overall free
energy change (DG) must be negative for a spontaneous grain growth
process. Of course,DGs , as the main driving energy for grain growth, is nega-
tive. On the other hand, DGp and DGd , the opposing energy terms, are posi-
tive so as to retard the process of grain growth. During grain growth, the


dD
grain growth rate , for an average grain diameter ‘D’ at an isothermal
dt
holding time ‘t’, may be considered to be proportional to overall free energy
change as per classical theory of growth [22]. Accordingly,
dD
/ −DG
dt
dD
= −KDG = −K(DGs + DGp + DGd ) (2)
dt
In case of spontaneous grain growth, for a negative overall free energy
change (DG), the right hand side of the expression supposes a negative
sign for an eventual positive grain growth rate and a positive proportionality
constant ‘K’.
Furthermore, the following three prime assumptions are taken for formu-
lation of the analytical model.

(i) The matrix grain has a tetrakeidecahedron shape.

(ii) The precipitate takes up a spherical shape.
(iii) A single solute and a single type of precipitate are responsible for the
solute drag effect and the precipitate pinning effect, respectively.

2.1. Formulation for DGs

The shape of each grain in a real alloy system is not necessarily the same
throughout. With regard to standard literature [5], a regular space filling
 PHILOSOPHICAL MAGAZINE LETTERS 311

shape which approximates a real metal grain is the ‘tetrakeidecahedron’.

Accordingly, the matrix shape is considered to be tetrakeidecahedron as
a refinement to the previous work of the present author [21]. In case of
a grain of tetrakeidecahedron shape, the volume (V), surface area (A),
edge length (L) and effective diameter (D) are related in the following
manner [5].
√ √
A = (6 + 12 3)L2 ; V = 8 2L3 (3)
Again,
√
D= 6L (4)

Equation (3) and Equation (4) lead to:

A = 4.4641D2 ; V = 0.7698D3 (5)
Accordingly, in this consideration with the tetrakeidecahedron shape of
grain and expressing DGs in terms of the specific grain boundary surface
energy (s), molar volume of matrix (V0 ) and the grain diameter (D) in
earlier manner [21], we finally get:
3.866sV0
DGs = − (6)
D

2.2. Formulation for DGp

As opined by Gladman [5], in consideration of a spherical precipitate par-
ticle of radius rp and diameter dp to be in contact with the grain boundary
surface, the particle must lie within +rp length around the grain boundary
surface. This, in turn, accounts for 2rp nv , i.e. dp nv number of particles per
unit area of grain boundary surface [5]. Indeed, nv is the number of particles
per unit volume. This is again related to the volume fraction of the spherical
4
(assumed shape) particles present at grain boundary, fp , as: fp = nv × prp3 .
3
Accordingly,
3fp 3fp 6fp
nv = =
3 = 3 (7)
4prp3 dp pdp
4p
2
Therefore, the number of particles per unit area of grain boundary surface,
6fp dp 6fp
na = dp nv = = 2 (8)
pdp 3 pdp
312 J. MAITY

Now, since each spherical particle has a surface area of 4prp2 , i.e. pdp2 , the
effective fraction of grain boundary surface area that accounts for pinning by
particle,
6fp
fgb = na × pdp2 = × pdp2 = 6fp (9)
pdp2

Again, for any grain having tetrakeidecahedron shape the surface area-to-
volume ratio,
A 4.4641D2 5.8
SV = = = (10)
V 0.7698D3 D
Therefore, finally taking into account the specific particle/matrix interfacial
energy (si ), i.e. the energy of the particle/matrix interface per unit area, and
molar volume (V0 ), the free energy change per mol (DGp ) accounting for the
‘pinning effect’ due to the presence of second phase precipitate particles at
grain boundary is given as:
6fp × 5.8 × si × V 0 34.8fp si V0
DGp = fgb × SV × si × V0 = = (11)
D D

2.3. Formulation for DGd

Although the present author provided the expression for solute drag in earlier
work [21], the fundamental origin of drag parameter needs to be established in
terms of the Gibbs free energy change for solute segregation. The phenomenon
called ‘solute drag’ is a consequence of solute segregation (not precipitation) at
grain boundary. The change of state pertaining to solute segregation may be
conceived in the following manner.
Solute at normal state ⇌ Solute at segregated state.
Following the most generalised approach [22], the Gibbs free energy change
(DGseg ) for this change of state is represented as:
aseg Xseg
DGseg = −RT ln = −RT ln (12)
anor XB
Following the most conventional way, the activity of solute at normal state
(i.e. at bulk solution), anor , is replaced by the mole fraction of solute in the
bulk solution, XB . Similarly, the activity of solute at segregated state, aseg , is
replaced by the mole fraction of solute at segregated state, Xseg . As usual, R
and T are the molar gas constant and absolute temperature, respectively. To
proceed further with this formulation, two more factors are considered;
 PHILOSOPHICAL MAGAZINE LETTERS 313

namely, the fraction of grain boundary site occupied by solute in reality (Xgb )
and the fraction of grain boundary site occupied by solute at saturation
(Xgb,s ). Next to this, a fundamental material balance is conceived by the
present author. Indeed, out of Xgb fraction of solute, (Xgb XB ) fraction of
solute is supposed to be supplied from the bulk solution. Therefore,
(Xgb − Xgb XB ) fraction of excess solute is segregated at grain boundary; which
as per material balance must be equal to Xseg (Xgb,s − Xgb ), since (Xgb,s − Xgb )
is the excess occupation fraction available considering solute saturation to be
the maximum limit of segregation.
Therefore,

Xgb − Xgb XB = Xseg (Xgb,s − Xgb ) (13)

Accordingly,

Xgb (1 − XB )
Xseg = (14)
(Xgb,s − Xgb )

Putting this value in Equation (12) and proceeding further we get:


 DGseg
Xgb XB −
= e RT (15)
Xgb,s − Xgb 1 − XB

This relationship (Equation (15)) derived here independently by the present

author is in agreement with that proposed by Langmuir and McLean [23,24].
This relationship has been readily used to analyze solute segregation in
different systems [25].
Now, since ‘segregation’ results in ‘drag’ to oppose grain growth, DGd is
equal in magnitude but opposite in sign to that of DGseg . Furthermore, repre-
senting the term (RT) as (PV0 ), i.e. in terms of pressure (P) and molar
volume of matrix (V0 ), we get:

Xseg Xgb (1 − XB )
DGd = −DGseg = PV0 ln = PV0 ln (16)
XB XB (Xgb,s − Xgb )

Xgb may be conceived as the ratio of the ‘thickness of solute segregation at grain
j
boundary’ (j) to the ‘grain diameter’ (D) as: Xgb = .
D
Accordingly,

j(1 − XB )
DGd = PV0 ln (17)
DXB (Xgb,s − Xgb )
314 J. MAITY

Now, the ‘drag parameter’ (x) may be introduced as:

j(1 − XB )
x= (18)
XB (Xgb,s − Xgb )
x
Therefore, DGd = PV0 ln .
D
Henceforth proceeding in an earlier manner [21] and neglecting the
higher order terms of the Taylor series expansion of the originated exponen-
tial term, we obtain:
xPV0
DGd = − PV0 (19)
D

2.4. Formulation for final kinetic expression

Finally, from Equation (2), Equation (6), Equation (11) and Equation (19) we
get:
dD 3.866sV0 34.8fp si V0 xPV0
= −KDG = −K( − + + − PV0 )
dt D D D
dD 1
= (3.866sV0 K − 34.8fp si V0 K − xPV0 K) + PV0 K (20)
dt D
Equation (20) is, therefore, the derived expression for grain growth rate


dD
.
dt
Let,
L = 3.866sV0 K − 34.8fp si V0 K − xPV0 K; N = PV0 K (21)
Accordingly,
dD L
= +N (22)
dt D
While examining Equation (22), the unit of ‘L’ is observed to be m2 s‒1, a typical
unit similar to that of ‘diffusion coefficient’. Since the process of diffusion involves
a long range migration of atoms; ‘L’, in this context of grain growth, may be
termed as ‘effective migration coefficient’. The prime significance of effective
migration coefficient stems from the fact that it inherits all fundamental par-
ameters pertaining to the mechanism of grain growth (including precipitate
pinning and solute drag) in its inherent expression (Equation (21)).
Now,
dD

 = dt
L
+N
D
 PHILOSOPHICAL MAGAZINE LETTERS 315

Integrating between relevant limits considering initial grain diameter as Di

(at t = 0),
D t
dD

 = dt
Di L
+N 0
D
 
ND − L ln (ND + L) D
=t
N2 Di
   
ND − L ln (ND + L) NDi − L ln (NDi + L)
− =t
N2 N2


1 L ND + L
(D − Di ) − 2 ln =t (23)
N N NDi + L

This is the final expression analytically developed by the present author to

ascertain the progress of grain growth in alloy systems.

3. Validation and futuristic proposition

As evident in the resultant expression representing grain growth (Equation
(23)) together with the system-dependent parameters engulfed in the
expressions of ‘L’ and ‘N’ (Equation (21)), a strong system-specific experimental
database is required to validate the model. On rigorous literature survey, the
experimental work of Wu et al. [26] is chosen first as the most conducive
one that takes into account the alloy steel containing 0.26 wt.% C and 0.49
wt.% V for grain growth study carried out at 950°C. This choice is quite
obvious since in such a system containing dissolved solute (C) as well as
strong carbide forming alloying element (V), the undissolved VC would
provide the pinning effect, while carbon would pose the solute drag effect
during the grain growth study. It also maintains a correspondence to our
third assumption of a single solute and single type of precipitate responsible
for the solute drag effect and the precipitate pinning effect, respectively.
Now, the necessary support of database as obtained from standard literature
is narrated below.
Specific grain boundary surface energy of austenite (matrix), s = 3.798 Jm−2
[27].
Molar volume of austenite (matrix), V0 = 5 × 10−6 m3 mol−1 [28].
Pressure, P = 105 Nm−2 (corresponding to 1 atmospheric pressure of
environment for solid state grain growth).
Furthermore, as per standard literature [21], for steel containing 0.2 wt.% C
(carbon content closer to the steel chosen) nearer to 950°C temperature of grain
growth,
316 J. MAITY

K = 2 × 10−9 mmol J−1 s−1 ; and x = 88 × 10−6 m.

Now, the prime undissolved precipitate particle (p) causing pinning effect
during grain growth at 950°C is VC. According to literature [29], the specific
interfacial energy (si in Jm−2 ) pertaining to austenite matrix-VC particle is
expressed in terms of temperature (T in K) dependency as per following
equation.

si = 1.1292 − 0.5088 × 10−3 T (24)

At T = 1223 K (950°C), si = 0.5069 Jm−2 .
Besides, the volume fraction of the undissolved carbide particles (fp ) segre-
gated at grain boundary may be obtained using the following relationship pro-
posed in standard literature [26].


AM + xAC rFe
fp = (M − Meq ). . (25)
AM 100rp

where M is the concentration of the metallic element of carbide in steel (in

wt.%); Meq, the equilibrium concentration of the metallic element of carbide
in austenite matrix (in wt.%); AM, the atomic weight of the metallic element
of carbide; AC, the atomic weight of carbon; x, the atomic ratio of the metallic
element to carbon in carbide; ρFe, the density of iron (solvent); and ρp, the
density of carbide particle.
In the concerned steel under investigation [26], the concentration of
vanadium, M = 0.49 wt.%; the equilibrium concentration of vanadium at 950°
C as per concerned literature [26], Meq = 0.25 wt.%; atomic weight of vanadium,
AM = 50.94 amu [30]; atomic weight of carbon, AC = 12.01 amu [30]; in case of
VC, x = 1; density of iron,
rFe = 7.87 × 103 kgm−3 [30]; density of VC, rp = 5.77 × 103 kgm−3 [31]. In
accordance, putting all these values in Equation (25) we get: fp = 4.045 × 10−3 .
Now, as per Equation (21), the above ascertained values provide the values of
‘L’ and ‘N’ as:

L = 5.812 × 10−14 m2 s−1 ; N = 10−9 ms−1 (26)

The values of all these significant parameters are listed in Table 1. Putting these
values of ‘L’ and ‘N’ in Equation (23) with an initial grain size of 5 µm
(Di = 5 × 10−6 m) [26], the holding time (t) to achieve a grain size of
7.94 µm (D = 7.94 × 10−6 m) comes out to be 294 s. This is very close to the
holding time of 300 s required to attain the said grain size of 7.94 µm as per
the experimental work of Wu et al. [26]. In this regard, a comparative plot is
shown in Figure 1. The deviation in terms of holding time appears to be of
only 2%. Accordingly, the utility of the proposed analytical model is primarily
justified. Moreover, the present model being fundamental by nature, all the
necessary temperature and time dependent database of different system-
Table 1. The values of significant parameters used in the model.
Specific grain boundary Specific interfacial
surface energy of Molar volume of Proportionality Drag energy for austenite Volume fraction of
austenite austenite Pressure constant parameter matrix-VC undissolved VC particles Evaluated ‘L’, Evaluated ‘N’,
(s),Jm−2 (V0 ),m3 mol−1 (P),Nm−2 (K),mmol J−1 s−1 (x),m (si ),Jm−2 (fp ) m2 s−1 ms−1

PHILOSOPHICAL MAGAZINE LETTERS

3.798 5 × 10−6 105 2 × 10−9 88 × 10−6 0.5069 4.045 × 10−3 5.812 × 10−14 10−9

317
318 J. MAITY

Figure 1. Validation of the developed model with respect to reported experimental work [26]
for a steel containing 0.26 wt.% C and 0.49 wt.% V as the prime alloying elements.

specific parameters may not be readily available always in literature. However,

instead of Equation (23), consideration of the easy-to-conceive relatively
simpler form as given in Equation (22), would be viable to use in a wider
domain including real time application in industry. In this approach a plot of



dD 1
grain growth rate versus the inverse of grain size would straightway
dt D
ascertain the system-specific parameters ‘L’ and ‘N’ as the slope and the inter-


dD
cept to the ordinate axis, respectively. Indeed, is the slope of D versus t
dt
plot. Since this theory is now being conceptualised by the present author, the


dD
-data are not directly reported by any available literature except a
dt
recent work by the present author [21]. Still, if we keenly inspect D-t plots
available in various literature [8,9,17], the slopes appear to be of the order of
10‒9 m s‒1. With regard to foregoing calculation on the basis of the work of
Wu et al. [26], putting the values of ‘L’ and ‘N’ (as per Equation (26)) in
Equation (22), at t = 300 s and D = 7.94 × 10−6 m, we get:
dD
= 8.3199 × 10−9 ms−1 . This is again of the same order (10‒9 m s‒1) as
dt
inspected from other literature [8,9,17]. This observation further justifies a
bright feasibility of the futuristic application of Equation (22) as a major
outcome of the present analytical model.
 PHILOSOPHICAL MAGAZINE LETTERS 319

Now, similar to the expression of diffusion coefficient, ‘L’ may be expressed

as:
Q
−
L = L0 e RT (27)
Accordingly,
Q
ln L = − + ln L0 (28)
RT
where Q is the activation energy for grain growth; R, the molar gas constant
(8.314 J mol‒1 K‒1); T, the absolute temperature. Since this theory is being con-
ceptualised by the present author for the first time, the database on ‘L’is only
available in a recent work [21] where the present author studied the grain
growth behaviour of hypoeutectoid plain carbon steels of different carbon
content at various temperatures ranging from 930°C to 1080°C. In absence of
any carbide or nitride forming alloying elements (fp = 0), solute drag effect
was the only factor to retard grain growth. With regard to that database of
1
‘L’ [21], lnL versus plots are hereby generated. This is shown in Figure 2
T
(a)–(b). The resultant expressions are given below.
2456
For 0.05wt.%C steel: ln L = − − 28.23 (29)
T
3280
For 0.2wt.%C steel: ln L = − − 27.69 (30)
T


Q
The activation energy values as obtained from slopes − for steels of
R
different carbon content are presented in Figure 3. The activation energy
values obtained (20 kJ mol‒1 and 27 kJ mol‒1) are quite expectedly one order
lower than the reported activation energy (157 kJ mol‒1) for lattice diffusion
of carbon in γ-iron [30], since the solute drag effect of carbon (solute) is

Figure 2. Kinetic plot pertaining to temperature-dependent grain growth to find out activation
energy for (a) 0.05 wt.% C steel, (b) 0.2 wt.% C steel.
320 J. MAITY

Figure 3. Evaluated activation energy for grain growth in (a) 0.05 wt.% C steel, (b) 0.2 wt.% C
steel.

primarily associated to the segregation of solute at grain boundary. Indeed, the

reported activation energy for grain boundary segregation of solute in steel is
one order lower than that for lattice diffusion [32]. Although the literature
on activation energy for grain boundary segregation of carbon in steel is
rarely available, the reported activation energy for grain boundary segregation
of phosphorous in steel is sometimes found as low as 33 kJ mol‒1 [32–35].
Carbon, as an interstitial solute, is expected to exhibit a little lower activation
energy than that, but of the same order persistent to the analysis of research
result (Figure 2(a)–(b)) with the conceptualisation of ‘effective migration coeffi-
cient’. Furthermore, it is observed that the activation energy for grain growth
increases with increasing solute (carbon) content, thereby indicating enhanced
effect of solute drag. These expected trends commensurate to the basic physical
principle elucidate a bright scope of the present analytical model for futuristic
application by techno-scientific community.
In majority of steels, carbon is an essential alloying element. Therefore, the
solute drag effect is usually unavoidable in common steels. However, if
carbon-free nitrogen containing ferrous alloy is developed in a special situation
where all alloying elements precipitate as nitrides, a sole effect of the precipitate
pinning would be presumed. In such a situation, in absence of drag effect (x = 0),
the effective migration coefficient (L) is likely to be enhanced (as per Equation
(21)). This would augment the rate of grain growth as per Equation (22). Of
course, further advancement of the present model for the presence of more
 PHILOSOPHICAL MAGAZINE LETTERS 321

than one segregated solute and various kinds of precipitate particles beyond the
prime assumption taken would open up the scope for future work in this field.

4. Conclusion

i The development of a complete analytical model to explain grain growth

kinetics is finally made feasible for the first time considering all major
phenomena in occurrence; namely, surface energy reduction, precipitate
pinning effect and solute drag effect. The final analytical expression
takes into account all fundamental parameters; such as specific grain
boundary surface energy of matrix, specific matrix-particle interfacial
energy, volume fraction of the precipitate particle and drag parameter.
ii The overall free energy change is conceived as a conjoint effect of the surface
free energy change, the free energy change accounting for precipitate
pinning effect and the free energy change accounting for solute drag effect.
iii The surface free energy change is conceived in terms of specific grain
boundary surface energy, molar volume of matrix and grain diameter
taking into account a tetrakeidecahedron shape of grain. On the other
hand, specific matrix-particle interfacial energy, volume fraction of the pre-
cipitate particle, molar volume of matrix and grain diameter are used to
express free energy change accounting for precipitate pinning effect.
iv A detailed explanation of the free energy change accounting for solute
drag effect is provided in terms of Gibbs free energy change for solute seg-
regation that eventually merges to the well-known Langmuir–McLean
relationship. Eventually, a ‘drag parameter’ is conceived to express the
free energy change accounting for solute drag effect together with
pressure, molar volume of matrix and grain diameter.
v Finally, the developed model is validated with regard to the existing data-
base in available literature. An intriguing methodology of grain growth
analysis is also proposed on the basis of the conceptualised ‘effective
migration coefficient’ of the system.

Disclosure statement
No potential conflict of interest was reported by the author(s).

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