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Modeling of Dissolution, Growth, and Coarsening of

Aluminum Nitride in Low-Carbon Steels


LEON M. CHENG, E. BRUCE HAWBOLT, and T. RAY MEADOWCROFT
A theoretically based model was developed by using numerical integration methods on a multiparticle
system to predict the dissolution and growth kinetics of nitrides and carbides in steels undergoing
heat treatment. This model takes fully into account the equilibrium thermodynamic properties of the
systems, the local equilibrium at the interface, curvature effects, and diffusion along the grain boundary.
Dissolution and coarsening are being treated as one continuous, simultaneous process. In the present
work, the model is applied to study the dissolution and coarsening behavior of aluminum nitride
(AlN) in Al-killed low-carbon steels. Theoretically predicted particle-size distributions are in good
agreement with the experimental measurements.

I. INTRODUCTION

DUE to their influence on recrystallization and grain


growth during thermomechanical processing of microalloyed steels, the precipitation of nitrides, carbides, or carbonitrides of microalloying elements such as niobium,
vanadium, titanium, or aluminum can have significant effects
on the mechanical properties of steels. Numerous studies
have been conducted to deal with the effects of these nitrides
or carbides on microstructure formation and the associated
mechanical properties of steels.[15] The size distribution of
nitride or carbide precipitates is an important microstructural
parameter in determining the mechanical properties of
microalloyed steels after a variety of thermomechanical processing treatments.
During reheating of the steels, the preexisting precipitates
may dissolve due to increasing solubility. In addition, there
is a tendency for the smaller particles to shrink and the
larger ones to grow. This process is known as coarsening
or Ostwald ripening and is driven by the minimization of
the total surface free energy of the system. Although models
have been developed for these two phenomena, they are often
modeled as two separate processes.[69] In reality, dissolution
and coarsening usually overlap and occur simultaneously.
In such a case, neither conventional dissolution nor Ostwald
ripening models can be applied.
In the present work, a theoretical model is proposed to
predict the dissolution, growth, and coarsening behavior of
nitrides or carbides in low-carbon and microalloyed steels
by using numerical integration methods on a multiparticle
system. Dissolution and coarsening are treated as one continuous, simultaneous phenomenon, and the two processes are
simulated in a natural sequence. This model takes into
account the equilibrium thermodynamic properties of the
system, the local equilibrium at the interface, curvature
effects, and diffusion along grain boundaries. The size of
a particular particle can be determined by simultaneously
solving a set of diffusion, equilibrium, and mass-balance
LEON M. CHENG, Postdoctoral Fellow, E. BRUCE HAWBOLT and
T. RAY MEADOWCROFT, Professors, are with the Department of Metals
and Materials Engineering, University of British Columbia, Vancouver,
BC, Canada V6T 1Z4.
Manuscript submitted December 7, 1999.
METALLURGICAL AND MATERIALS TRANSACTIONS A

equations for each individual particle. This model is applied


to study the dissolution and coarsening behavior of aluminum nitride (AlN) in Al-killed low-carbon steels. The predicted results are then compared to experimental
measurements made on the same system.
II. THEORETICAL MODEL
A list of symbols being used in the present model is shown
in Table I.
Based on the measured mean diameter and the standard
deviation of the initial distribution, an assembly of n particles
can be defined according to a presumed particle-size distribution. The form of the initial size distribution depends on
the initial experimental conditions. However, in most cases,
the distribution of nitrides or carbides in steels can be well
represented by either a normal distribution or a log-normal
distribution. For a normal distribution, the density function
can be written as

rn 5

1
(a 2 r)2
exp 2
2s2n
!2psn

[1]

where rn is the probability density of a normal particlesize distribution, a is an individual particle radius, r is the
arithmetic mean radius of the distribution, and sn is the
standard deviation. For a log-normal distribution, the density
function is

rl 5

1
(ln a 2 m)2
exp 2
2s2l
!2psla

[2]

where rl is the probability density of a log-normal particlesize distribution, m is the arithmetic mean of the distribution
of ln (a), and sl is the standard deviation of the normal
distribution of ln (a).
A. Precipitates in Matrix
For both dissolution and growth, the diffusion-controlled
transformation of a particle in a matrix requires the solution
of Ficks second law,
D2C 5

C
t

[3]

VOLUME 31A, AUGUST 20001907

Table I. List of Symbols


a
ap , a
C
Cb
C`e
CI
CP , CM
d0
D
Db
f
K`, KI
NA
NS
r
R
VP
X P, X M
Zl
ZS
d
g
sn

mp , m
np , n
rl
rn
DE
DH

radius of particle
lattice parameters of precipitate and
matrix, respectively
concentration field
solute concentration within grain boundary
equilibrium solute concentration at planar
interface
solute concentration in the matrix at the
interface
solute concentration in precipitate and in
matrix, respectively
mean grain diameter
bulk matrix diffusivity
grain boundary diffusivity
volume fraction of precipitate
solubility product for planar and nonplanar
precipitate/matrix interface,
respectively
Avogadros number
atoms/unit area of surface
arithmetic mean radius of the particle
size distribution
gas constant
molar volume of precipitate
concentration of precipitate forming element in precipitate and matrix,
respectively
lattice coordination number
bonds per atom across the interface
grain boundary thickness
precipitate/matrix interfacial energy
standard deviation of the particle size
distribution
shear moduli of precipitate and matrix,
respectively
Poissons ratio of precipitate and matrix,
respectively
probability density of a log-normal size
distribution
probability density of a normal particle
size distribution
heat of solution of precipitate
heat of formation of precipitate

Fig. 1Schematic diagram of the solute concentration in the vicinity of


(a) a dissolving precipitate and (b) a growing precipitate.

where D (assumed to be independent of composition) is the


interdiffusion coefficient in the matrix, and C 5 C(r, t) is the
concentration field in the matrix surrounding the precipitate.
For an MX-type precipitate in an Fe-M-X ternary system,
where M is the substitutional alloy element (e.g., Nb, V, Al,
etc.) and X is the interstitial element (e.g., C and N), the
diffusivity of the interstitial elements is usually several
orders of magnitude higher than that of the substitutional
elements. It is reasonable to assume that the kinetics of the
particle dissolution and/or coarsening process is controlled
by the lower diffusion rate of the substitutional alloying
element, and the concentration gradient of the interstitial
element in the matrix can be ignored. For simplicity, all
precipitates are assumed to be spherical and to remain so
during dissolution/growth. For such a spherically symmetrical system, Eq. [3] becomes
D

1 r

2 C
2

1908VOLUME 31A, AUGUST 2000

2 C
C
5
r r
t

[4]

For precipitates in a finite matrix, the precipitates are


assumed to be uniformly distributed in the matrix. For mathematical simplicity, each particle can be considered to be at
the center of a spherical cell with a radius of l, where 2l is
the initial average interparticle distance. Let a be the radius
of a particle within the spherical cell. If l .. a, then, within
a short period of time, the solute concentration at the cell
wall (CM) can be approximated as a constant, although it
changes slowly with time. Under this situation, the boundary
conditions for Eq. [4] become
C 5 CI when r 5 a

[5a]

C 5 CM when r 5 l (l .. a)

[5b]

and

Schematic concentration profiles around a precipitate in


these conditions are shown in Figure 1, where CP is the
solute concentration in the precipitate and CI is the solute
concentration in the matrix at the particle/matrix interface.
If CI and CM are assumed to be constants, then the concentration profile can be determined by following the stationary
interface (invariant size) approximation[10] developed by
Whelan. In this approach, the diffusion field around a precipitate with radius of a is assumed to be the same as that
which would exist if the precipitate/matrix interface had
been fixed at a from the start, i.e., by restricting the diffusion
field to have no memory of the past motion of the interface.
Thus, if CI and CM are assumed to be constants, then Eq.
METALLURGICAL AND MATERIALS TRANSACTIONS A

[4] can be solved to obtain the concentration profile for r


$ a:

a
r2a
C 2 CM 5 (CI 2 CM) erfc
r
2!Dt

[6]

where the complementary error function, erfc (x), is


defined as
erfc (x) 5

2
!p

exp (2t2)dt

[7]

Due to mass conservation of the solute in the matrix, the


flux of solute at the interface is equal to the rate of loss (or
gain) of solute in the precipitate. Thus, for a spherical particle, the condition of flux balance at the interface can be
written as
24pa2(CP 2 CI) da 5 24pa2D

C
? dt
r r5a

[8]

which can be rewritten to obtain the rate of migration (or


velocity) of the precipitate/matrix interface (v) as
v5

da
C
D
?
5
dt
CP 2 CI r r5a

[9]

Having obtained C/r from Eq. [6], da/dt can be obtained


from Eq. [9] as
1/2

1 1 22

[10]

CI 2 CM
CP 2 CI

[11]

da
D
D
5 2k ?
1
dt
a
pt
with
k5

In Eq. [10], the term in t21/2 arises from the transient part
of the diffusion field. For a steady state, Eq. [10] becomes

12

da
D
5 2k ?
dt
a

[12]

Equation [10] is the solution for an isolated particle in an


infinite matrix, where both CI and CM do not vary with
time. However, under local equilibrium conditions at the
precipitate/matrix interface, the GibbsThompson equation
shows that the equilibrium composition in the matrix at the
curved precipitate/matrix interface, CI , varies with precipitate radius, a, as[11]
2gVp
CI 5 Ce` ? exp
RTa

1 2

[13]

where g is the precipitate/matrix interfacial energy, Vp is the


molar volume of the precipitate, R is the gas constant, T is
the absolute temperature, and Ce` is the equilibrium solute
concentration at a planar interface. To take into account the
effect of curvature on dissolution and growth kinetics, Aaron
and Kotler[7] replaced the constant CI in Eq. [11] by Eq.
[13]. In the case of dissolution, the presence of the curvature
effect tends to speed up the rate of dissolution, being particularly important for small particles.
For an MX-type precipitate, the solubility product for a
nonplanar precipitate/matrix interface (KI) can be written
as[12]
METALLURGICAL AND MATERIALS TRANSACTIONS A

KI 5 [M]I[X]I 5 K` ? exp

4gVp

1 RTa 2

[14]

where [M]I and [X]I are the equilibrium contents (in wt


pct) of M and X, respectively, in the matrix at the curved
precipitate/matrix interface; and K` is the solubility product
for a planar interface. Values of K` can be derived from
experimental data or calculated from thermodynamic data.
Moreover, the volume fraction of precipitates such as
AlN, NbC, etc. in industrial-grade microalloying steels is
usually very low (typically on the order of 1024 to 1023),
and the diffusion fields surrounding the precipitates would
not seriously overlap. However, the average solute concentration in the matrix will still vary with time due to the
dissolution or growth of the precipitates. In the case of
dissolution, the increase of solute concentration in the matrix
tends to slow down the rate of dissolution. As the solute
concentration increases and reaches the equilibrium value,
then the total volume fraction of the precipitates will remain
constant. On the other hand, in the case of a growing precipitate, the decrease of solute concentration in the matrix tends
to slow the growth rate. If the solute concentration in the
matrix is fixed, the particles will never stop shrinking (or
growing), which does not agree with reality.
Therefore, in an attempt to take into account the variation
of average solute concentration in the matrix and its effect
on the rate of dissolution and growth, CM in Eq. [11] is
replaced by the average solute concentration in the matrix.
Although, strictly speaking, Eq. [10] is only valid when k
is a constant (i.e, CP , CI , and CM are all constants), it is
reasonable to believe that[7,12] within a very short period of
time, Eq. [10] can still be a good approximation for the rate
of dissolution (or growth) for the case where both CI and
CM change only slowly with time. During the calculation,
both CI and CM are updated after each infinitesimal increment
of time. For the system considered in this study, the variation
of the average solute concentration in the matrix is small
compared to the change in CI due to the curvature effect at
the precipitate/matrix interface.
If there is no new precipitate formed during dissolution
or coarsening, the volume fraction of precipitates at time (t) is
n

f(t) 5 f0 ?

1 2
o Vi (t)

i51
n

o Vi0

[15]

i51

where f0 is the volume fraction of precipitates at t 5 0, Vi (t)


and Vi0 are the volumes of particle i at time 5 t and 0,
respectively. During the calculation, CM(t) is approximated
by the average solute concentration in the matrix, which can
be determined from f(t) and the total solute content in the
system, i.e.,
CM(t) 5

CT 2 CPf(t)
1 2 f(t)

[16]

where CT is the total solute concentration. For a stoichiometric MX-type precipitate, CP is a constant and is equal to
1/V PM, where V PM is the partial molar volume of the substitutional alloy element in the precipitate.
It can be seen from Eq. [10] that a precipitate is dissolving
when k . 0 and growing when k , 0. Since CI is a function
of a and CM is a function of time, then k 5 k(a, t). Therefore,
VOLUME 31A, AUGUST 20001909

as described in the previous section. The other is the solution


for the grain boundary only. Moreover, it is assumed that
the diffusion of solute along the surface of the precipitate
is sufficiently rapid that the spherical shape is maintained.
The concentration profile in the grain boundary can be
determined by examining a volume element within the
boundary,[13] such as that shown in the lower- right-hand
corner in Figure 3. Let Nr and Nr1dr be the number of atoms
per unit time entering and leaving the volume element at
the points r and r 1 dr, respectively; dNc be the amount of
solute per unit time diffusing from the boundary element to
the bulk matrix, and dNb be the change in amount of solute
in the boundary element per unit time. Conservation of solute
implies that
Nr 2 Nr1dr 2 dNc 5 dNb

[17]

Since
Fig. 2Schematic concentration fields showing the effect of particle size
on the transformation mode, i.e., dissolution or growth, of an individual
particle.

Nr 5 2Db Ac
dNb 5 dAc

Cb
r

[18]

Cb
t

[19]

and dNc can be approximated[14] as


dNc '

Fig. 3Schematic diagram of a precipitate located on a grain boundary.

for a multiparticle system, whether an individual particle


may dissolve or grow depends on its radius, as illustrated
in Figure 2. Thus, it is possible that one particle dissolves
while some other particles are growing at the same time.
Moreover, each individual particle may have a different
growth or dissolution rate. The size of each individual precipitate (ai) can be determined by integrating Eq. [10] numerically for each precipitate.
B. Precipitates on Grain Boundaries
When a particle is located on a grain boundary, both
grain-boundary and bulk diffusion can occur simultaneously.
During dissolution, solute atoms can flow from the particles
surface to the matrix or can diffuse along the grain boundary.
The solute atoms can also flow from the grain boundary to
the matrix. Similar situations also arise for a growing particle, but, instead of flowing away from the particle, the solute
atoms flow toward the particle. A dissolving particle located
on a grain boundary is shown schematically in Figure 3.
In the present model, a grain-boundary precipitate is considered to be a sphere with a thin slab of material (i.e., grain
boundary) attached along its equator,[13] as shown in Figure
3. When both grain-boundary and bulk diffusion occur, the
concentration field can be approximated as the sum of two
solutions. One solution is that without the grain boundary,
1910VOLUME 31A, AUGUST 2000

4D
(C 2 CM)dAs
d0 b

[20]

where Cb 5 Cb(r, t) is the solute concentration within the


grain boundary; CM is, again, the average solute concentration in the matrix; Db is the grain-boundary diffusivity; d is
the thickness of the grain boundary; Ac and dAs are the
cross-sectional area and surface area of the volume element,
respectively; and d0 is the mean grain diameter.
If we consider a ring of grain boundary at a distance of
r from the precipitate, then
AC 5 2prd

[21]

dAs 5 2prdr

[22]

and
Using Eqs. [17] through [22] and assuming that dr/d , 1,
one can obtain
Db

1 r

2Cb
2

1 Cb
C
4D
(C 2 CM) 5 b [23]
2
r r
dd0Db b
t

Within a short period of time, CM can be assumed to be


constant. With the boundary conditions that
Cb 5 CM when r .. a

[24a]

Cb 5 CI when r 5 a

[24b]

and

eq. [23] can be solved to obtain the concentration profile


within the grain boundary as
Cb 5

CI 2 CM
K (br) 1 CM
K0(ba) 0

[25]

where

b5

!D

4D
b dd0

[26]

METALLURGICAL AND MATERIALS TRANSACTIONS A

and the modified Bessel function, K0(x), can be approximated as

p 2x
e
2x

Table II. Chemical Composition of DQSK Steel (Weight


Percent)
C

Mn

Si

Al

Cr

[27]

0.038

0.30

0.009

0.040

0.008

0.033

0.0052

when x $ 1. Although Eq. [27] is only valid for large x


values, the error in using this approximation is small (i.e.,
less than 10 pct), even when x , 1.
Considering the mass conservation of the solute over the
whole surface of the particle, the condition of solute balance
over the surface of the particle can be written as

with

K0(x) '

2 2padDb

C
r r5a

24pa2 (Cp 2 CI) da 5 24pa2D

Z 2

[28]

Cb
dt
r r5a

where C(r 5 a, t) 5 Cb (r 5 a, t) 5 CI. Combining Eqs.


[25] through [28] with the results from the previous section,
the growth (or dissolution) rate of the precipitates can be
approximated as
da
D dDb dDbb
Db
5 2k
1 2 1
1
dt
a
4a
2a
pt

1/2

1 22

[29]

C. Interfacial Energy

g 5 gc 1 gst

[30]

The chemical component, which corresponds to the energy


associated with a fully coherent interface, is given as
DENSZS P
(X 2 X M)2
NAZl

[31]

where DE is the heat of solution of the precipitate, NS is the


number of atoms per unit area of surface, Zl is the lattice
coordination number, ZS is the number of bonds per atom
across the interface, NA is the Avogadros number, and X P
and X M are the concentration (mole fraction) of the precipitate-forming element in the precipitate and matrix, respectively. The term DE can be evaluated from the respective
heat of formation (DH ), using DE 5 2DH.
The structural component, gst, in Eq. [30] is associated
with the array of interfacial dislocations which accommodate
the mismatch lattices between the two phases. It can be
estimated[16,17] as

gst 5

2pT
3(1 2 n*)

[33]

1
1
1
5 1
m* m mP

[34]

2
1
1
5 1
a* a aP

[35]

and

n* 5

1
(n 1 nP)
2

[36]

where, T is the volume misfit between the two lattices; m


and mP are the shear moduli of the matrix and precipitate,
respectively, n and nP are the Poissons ratio of the matrix
and precipitate, respectively, and a and aP are the lattice
parameters of the matrix and precipitate, respectively.
III. APPLICATION AND DISCUSSION

For crystal-crystal interfaces, the atomic matching ranges


from perfect matching in fully coherent interfaces, to lessperfect matching in semicoherent interfaces, and finally to
random matching in fully incoherent interfaces. The energy
of an interphase boundary depends on many parameters,
e.g., interfacial misfit, the type of atomic bonding between
and within the phases, etc. Turnbull[15] considered the interfacial energy of semicoherent interphase boundaries to consist
of two additive parts: a chemical term (gc) for the coherent
interface and an additional structural term (gst) due to the
cross-grid of edge dislocations, as follows.

gc 5

C5

m*a*
(1 1 C 2 (1 1 C2)1/2)
2p2

METALLURGICAL AND MATERIALS TRANSACTIONS A

[32]

The theoretical model described in the preceding section is


being applied to the dissolution and coarsening of aluminum
nitride (AlN) in both austenite (g) and ferrite (a). Experiments and calculations are carried out on a commercially
produced, drawing-quality special Al-killed steel obtained
from US Steel (Pittsburgh, PA). The chemical composition
of this steel is given in Table II.
A. Experiments
After hot rolling, the material used in the present work
was initially coiled at a coiling temperature of 650 8C. Specimens 4 3 4 3 6 mm were machined from the as-received
coil sheet. To study the dissolution and coarsening of AlN
precipitates in austenite, specimens (encapsulated in evacuated quartz capsules) were first isothermally annealed in a
furnace at temperatures between 650 8C and 750 8C for 24
hours to obtain different initial particle-size distributions.
These annealed specimens were then heat-treated at a temperature between 1000 8C and 1200 8C (either in a highpurity argon atmosphere or encapsulated in quartz capsules)
for increasing holding times and were then rapidly cooled
by water quenching.
Another set of specimens was first solution treated at 1250
8C for 30 minutes and then isothermally annealed at 700 8C
for times ranging from 1 hour to 1 week, to study the coarsening behavior of AlN precipitates in ferrite.
The characterization of the resulting AlN particle sizes
and distributions and the microanalysis of these precipitates
was then accomplished by using transmission and scanning
transmission electron microscopy examination on carbonextraction replicas of the specimens. To prepare the replicas,
specimens were first ground and then polished with diamond
VOLUME 31A, AUGUST 20001911

Table III. Diffusion Coefficients of Al in Austenite and


Ferrite, D 5 D0 exp (2Q/RT )
D0 (m2/s)

Phase
Austenite, matrix
Austenite, grain boundary
Ferrite, matrix
Ferrite, grain boundary

Q (kJ/mol) Reference

24

2.51 3 10
3 3 1024
5.31 3 1028
5.82 3 1028

253.4
167.4
196.5
143.8

20
22
21
22

The diffusion coefficients of Al in a bulk matrix[20,21] or


along a grain boundary in austenite and ferrite are shown
in Table III. For diffusion of Al along a grain boundary,
because of the lack of experimental data, self-diffusion data
for Fe along a grain boundary are being used.[22] The equilibrium between AlN and the Fe-Al-N system can be determined by using thermodynamic data for AlN and regular
solution models of the Fe-Al and Fe-N binary systems.[2328]
Since the concentrations of both Al and N are very low,
ternary interaction parameters and the Al-N interaction
parameter are neglected during the calculation. The solubility products of AlN in austenite and ferrite are calculated
as[19]
log Kg` 5 log ((wt pct Al) (wt pct N)) 5 4.5989 2

11,568
T
[37]

and
log Ka` 5 6.1061 2

14,442
T

[38]

respectively.
For the interfacial energy of AlN in a-Fe and g-Fe, the
heat of formation of AlN can be derived from the numerical
data in Reference 29. Other data used for the calculation
are summarized[3034] in Table IV.
C. AlN in Austenite
Fig. 4Flow chart illustrating the logic of the program.

paste (6 and 1 mm). After etching in a 2 pct Nital solution


for 5 seconds and coating with a thin film (,20 nm) of
carbon, the specimens were then etched in a 5 pct Nital
solution until the replicas lifted off. Detailed descriptions of
the experimental procedures and the results are described
elsewhere.[18,19]
B. Predictions
The predictions are based on an initial 2000-particle
assembly. A flow chart for the computer program is shown
in Figure 4. During the calculation, based on the values of
a and CI for each particle, as well as CM , at time t, the new
values of all a terms at t 1 Dt can be determined using Eqs.
[10] or [29], where Dt is an infinitesimal increment of time.
The new value of CM at t 1 Dt can also be calculated from
the new volume fraction. By repeating these calculations for
each time step, the size evolution of each particle can then
be obtained.
1912VOLUME 31A, AUGUST 2000

Both measured and predicted size distributions of AlN,


after the steel has been soaked at 1000 8C for different
holding times, are shown in Figure 5. The initial size distribution, as shown in Figure 5(a), is obtained by annealing the
coil material at 700 8C for 24 hours. By fitting to the measured size distribution, a normal distributed particle size is
establishedusing the measured values of mean radius and
standard deviationto initiate the simulation. Comparing
the predictions to observations at t 5 1800, 3600, and 5400
seconds (Figure 5(b) through (d)), a reasonably good agreement is obtained. Although there are differences between
the measured and predicted mean size, the distributions are
very similar. Based on these size distributions, the mean
diameter of the AlN is calculated and plotted as a function
of holding time in Figure 6. It can be seen that the calculated
mean diameter of the AlN particles decreases during the
early stage of annealing and then increases.
These predictions suggest that once the specimen is rapidly heated to the test temperature, all particles start to dissolve (decrease in mean diameter) initially, due to the high
solubility and low solute concentration in the matrix (i.e.,
high k values). As the precipitates dissolve, the solute concentration in the matrix, CM , increases (i.e., the volume
METALLURGICAL AND MATERIALS TRANSACTIONS A

Table IV. Data Used for Calculation of Interfacial Energy for AlN in a-Fe and g-Fe[3034]
Parameter

g-Fe (Fcc)

AlN (Hcp)

Lattice parameter (nm)

a 5 0.3111
c 5 0.4975

a 5 0.364

Shear modulus, m (MPa)

1.28 3 105

8.1 3 104 ? 1 2 0.91 ?

Poissons ratio, n

a-Fe (Bcc)
a 5 0.2866

T 2 300
1810

2 3.2 3 10

22

\
when T . 573 K

0.25

0.29

T 2 300
1810
(T 2 573)2
2 2.4 3 1022 (T 2 923)2

6.4 3 104 ? 1 2 0.81 ?

\
when T . 923 K

0.29

(a)

(b)

(c)

(d )

Fig. 5Evolution of size distribution of AlN particles after soaking at 1000 8C for (a) t 5 0 s, (b) t 5 1800 s, (c) t 5 3600 s, and (d ) t 5 5400 s.

fraction of AlN decreases) and gradually reaches a stable


level. The predicted volume fraction of undissolved AlN
particles in the steel is shown in Figure 7. The total volume
fraction decreases very quickly during the early stage of
annealing and then stays at an almost constant level throughout the rest of the annealing. The calculated size evolution
of four selected AlN particles is shown in Figure 8. It can
be seen that, after the initial stage, the dissolution rates of
the smaller ones (particles C and D) decrease as CM increases
(lower k values). However, as the particles become very
small, the curvature effect causes the dissolution rate of
these particles to increase rapidly. While the smaller particles
are completely dissolved, the larger ones (A and B) start to
coarsen after shrinking slightly in the early stage (CI becomes
lower than CM , i.e., k changes from 1ve to 2ve). Moreover,
it can also be seen in Figure 8 that particle B, as it becomes
one of the smaller particles among the remaining particles,
METALLURGICAL AND MATERIALS TRANSACTIONS A

starts to shrink near the end of the simulation, while particle


A keeps growing. These predicted behaviors indicate the
capability of the present model to treat dissolution and coarsening as one continuous process with no clear separation
between these two.
The size evolution of AlN at two other temperatures, 1100
8C and 1175 8C, is shown in Figure 9. Although they have
the same initial size distribution, because of the higher solubility and higher diffusivity, the mean size of AlN at 1100
8C is much larger than that at 1000 8C for the same holding
time. However, for the case of 1175 8C, the soaking temperature is sufficiently high to dissolve all AlN particles. From
Eq. [37], the equilibrium solution temperature for AlN in
this steel is determined to be about 1120 8C. Thermodynamic
properties of the system not only determine the equilibrium
condition, but also play a major role in the dissolution or
growth rate.
VOLUME 31A, AUGUST 20001913

(a)

Fig. 8Size evolution of four selected AlN particles during soaking at


1000 8C.

(b)

(a)

Fig. 6(a) Variation of mean diameter with reheating time at 1000 8C.
(b) Calculated mean diameter for the first 1000 s at 1000 8C.

(b)
Fig. 9Variation of mean diameter of AlN particles with reheating time
at (a) 1100 8C and (b) 1175 8C, after an initial 24 h annealing at 700 8C.
Fig. 7Variation of AlN volume fraction with reheating time at 1000 8C
(after 24 h at 700 8C).

The dissolution and coarsening of AlN at 1000 8C were


also studied with a different initial size distribution. In these
tests, specimens were first solution treated at 1250 8C for
30 minutes and then quenched to and held at 650 8C for
24 hours to obtain the initial distribution. In this case, the
measured initial size distribution is best fitted by a lognormal distribution for the simulation. Figure 10 shows the
variation of mean particle size with reheating time. The size
distribution of AlN particles for different times at the soaking
temperature is shown in Figure 11. Although the mean sizes
are different (due to a different initial size), the curve shown
1914VOLUME 31A, AUGUST 2000

Fig. 10Variation of mean particle size with reheating time at 1000 8C


(after initial annealing for 24 h at 650 8C).
METALLURGICAL AND MATERIALS TRANSACTIONS A

(a)

(b)

Fig. 12Variation of mean diameter of AlN particles with annealing time


at 700 8C.

for up to 7 days. Scanning electron microscopy micrographs


of the specimens indicate that there is no significant difference in the ferrite grain size throughout the test, possibly
due to the pinning effect of the AlN precipitates. Therefore,
during the calculation, the average ferrite grain size is taken
to be constant (d0 ' 10 mm), and the precipitates are considered to be stationary along the grain boundaries (i.e., precipitates remain on the grain boundaries throughout the
annealing). The size evolution and distribution of AlN precipitates are shown in Figures 12 and 13, respectively.
In the present model, it is assumed that no new nucleation
occurs during the annealing. For this test condition, it has
been determined[19] that precipitation should be completed
within about 30 minutes. Thus, a log-normal size distribution
is established from the measured size distribution of AlN
precipitates after 1 hour at 700 8C (Figure 13(a)) to initiate
the simulation.
As shown in Figure 12, the coarsening of AlN particles
is rapid during the early stage of annealing and slows at
longer times. Moreover, unlike the previous cases, there is
no initial decrease of the mean diameter at early annealing
times. This indicates that the growth mechanism is dominated by coarsening throughout the whole period.
IV. SUMMARY

(c)
Fig. 11Evolution of the size distribution of AlN particles (initially
annealed for 24 h at 650 8C) after soaking at 1000 8C for (a) t 5 0 s, (b)
t 5 3600 s, and (c) t 5 7200 s.

in Figure 10 is similar in shape to that in Figure 6. Both


curves exhibit an initial drop in mean size followed by an
increase of the mean size (i.e., shifting from a dissolutiondominated to coarsening-dominated process).
D. AlN in Ferrite
The capability of the present model to simulate the size
evolution of second-phase particles along grain boundaries
is demonstrated by the study of the coarsening of AlN precipitates along ferrite grain boundaries during annealing of the
steel at 700 8C. Specimens were first solution treated at 1250
8C for 30 minutes and then quenched to and held at 700 8C
METALLURGICAL AND MATERIALS TRANSACTIONS A

A theoretically based model is developed to predict the


dissolution and coarsening behavior and to simulate the sizedistribution evolution of nitrides or carbides in microalloyed
steels. In this model, dissolution and coarsening are being
treated as one continuous, simultaneous process. A set of
diffusion, equilibrium, and mass-balance equations are
solved simultaneously for each individual particle. In the
case of precipitates on grain boundaries, the effect of grainboundary diffusivity is also considered.
Calculations and experiments are carried out for AlN dissolution and coarsening in both austenite and ferrite. Various
initial size distributions and reheating temperatures are used
in the tests. The predictions and the measurements are in
good agreement. These results lend support to several aspects
of the model and to the assumptions incorporated in the
model. However, to improve and to generalize the current
model, further studies on the effects of actual spatial distribution of the precipitates and the influence of the overlapping
diffusion fields are necessary.
VOLUME 31A, AUGUST 20001915

REFERENCES

(a)

(b)

(c)
Fig. 13Evolution of the size distribution of AlN particles after soaking
at 700 8C for (a) t 5 1 h, (b) t 5 20 h, and (c) t 5 164 h.

ACKNOWLEDGMENTS
The authors acknowledge with gratitude the financial support received from the Natural Sciences and Engineering
Research Council of Canada (NSERC).

1916VOLUME 31A, AUGUST 2000

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METALLURGICAL AND MATERIALS TRANSACTIONS A