Journal of Alloys and Compounds 420 (2006) 117–120

A model for the prediction of lattice parameters of

iron–carbon austenite and martensite
N.N. Rammo a,∗ , O.G. Abdulah b
a Materials Science Directorate, Ministry of Science and Technology, PO Box 765, Baghdad, Iraq
b Physics Department, College of Science, University of Sulaymania, Iraq

Received 11 November 2004; received in revised form 18 October 2005; accepted 21 October 2005
Available online 18 January 2006

Abstract
Prediction of lattice parameters of interstitial iron–carbon austenites and martensites as a function of carbon concentration and temperature are
given. The model is based on the two assumptions that the change in lattice parameters of the pure Fe phase is due to the occupation by carbon
atoms to the octahedral holes in the fcc austenite and the bct martensite; and on the relative change in length and vacancy concentration at the
lattice sites that are in thermal equilibrium. The predicted lattice parameters of the Fe–C martensites are in a good agreement with the experimental
data. However, the preparation procedures of the austenites at room temperature, causes crystal defects thereby dropping the experimental values
by 0.25% from the purely ideal predicted values. The model also yield the tetragonality (c/a) of the martensite as a function of C atoms/100 Fe
atoms, defined by the ideal ratio c/a = 1 + 0.01XC .
© 2005 Elsevier B.V. All rights reserved.

Keywords: Lattice parameters; Iron–carbon system; Interstitial solid solution

1. Introduction of lattice parameters as a function of carbon concentration and

The austenite to martensite phase transformation is of major
importance in manufacturing and forming steels. The transfor-
mation involves a change in the crystal structure from fcc to
bcc [1,2]. A considerable number of literature on determining
the lattice parameters of the Fe–C in terms of concentration and
temperature by the devotion of X-ray diffraction [3] and neutron
diffraction [4] exist. More recently the redistribution of carbon
during transformation in terms of time, temperature and decom-
position of austenite in ferrite and pearlite has been recently
studied by 3D neutron depolarization [5].
As most literature data on lattice parameters are centered on
experimentation, a theoretical approach should be valuable. To
that end, a model for the theoretical prediction of lattice parame-
ters of substitutional solid solutions has been reported for binary
alloys [6]. However, the little availability of literature on the
prediction of lattice parameters of interstitial Fe–C solid solu-
tions, initiated the interest to present a model for the prediction
∗ Corresponding author.
E-mail address: saadramo 8888@yahoo.com (N.N. Rammo).
temperature, this approach would be the aim of this work.
1.1. Model for austenite Fe–C
In the fcc structure, the largest holes are at the centers of
the cube edges and the cube centers (Fig. 1). The holes are
surrounded by six metal atoms that form the centers of an octahe-
dron. From Fig. 1 if rFe is the radius of iron atoms, the octahedral
holes will just contain spheres of radius 0.414 rFe . The intro-
duction of carbon atoms with radius rC slightly greater than this
value, will slightly distort the cubic structure into some lower
symmetry particularly if the number of carbon atoms is insuffi-
cient to fill the octahedral holes [7].
The change in lattice parameters due to occupation of carbon
atoms in octahedral holes is
√

a = [2(rFe + rC ) − 2 2rFe ]
If the maximum solubility of carbon in ␥-Fe is 10 at.% [8], and
there are four unit cells that contribute in an individual octa-
hedron. The lattice parameters of austenite phase in terms of

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118 N.N. Rammo, O.G. Abdulah / Journal of Alloys and Compounds 420 (2006) 117–120

1.3. Lattice parameters versus temperature

It is known that the presence of defects in a crystalline lattice

tends to change the lattice dimensions. In cubic case with ran-
dom distribution of defects, the relative lattice parameters
a/a
and the relative change of length of the sample
L/L, can be
interpreted in terms of total concentrations of vacant lattice sites
Cv and of occupied interstices Ci according to [9]:
 
Fig. 1. Position of octahedral holes in fcc structure.
L
a
3 − = Cv − Ci
L a
carbon concentration is then Usually Ci can be neglected because Cv , the vacancy concen-
⎡ ⎤ trations at lattice sites are the dominant point defects that are
√
√ 2(rFe + r C ) − 2 2r Fe in thermal equilibrium. Therefore, the change in lattice param-
a = 2 2rFe + ⎣ ⎦ XC (1) eters for pure element as a function of temperature would then
4 × 10 become:
 
Cv (T )
where XC is the number of carbon atoms per 100 iron atoms.
a(T ) = α
T − aO
3
where α is the thermal expansion coefficient, and aO is the orig-
1.2. Model for martensite Fe–C
inal lattice parameter.
The octahedron of the fcc austenite (Fig. 2a) as it transforms
to martensite by the distortion of dipoles that are aligned along 1.4. Lattice parameters versus concentration and
one expanded axis, i.e. the tetragonal c-axis (Fig. 2b) ends up temperature
with body-centered tetragonal (bct) structure.
Thus the increase in
c due to occupied carbon is Combination of changes due to carbon concentration with
changes due to temperature in a model yield an expression for
2(rFe + rC ) − 4rFe the lattice parameters of the interstitial solid solution as

c = √
3 a(X, T ) = as (X) +
aA (T )XA +
aB (T )XB (4)
and the decrease in
a is
where as (X) represent the lattice parameters at concentration X,
4rFe T represents the temperature and the subscripts A and B refer to

a = √ √
3 − 2(rFe + rC ) solvent and solute, respectively.

The lattice parameters of martensite in terms of carbon concen- 2. Results

tration becomes:
⎡ √ ⎤ For simplicity, the hard sphere model is considered in the
4rFe ⎣ 2(rFe + rC ) − 4rFe / 3 ⎦ derivation of lattice parameters in terms of atomic radii of the
c= √ + XC (2)
3 4 × 10 atoms involved.
In order to consider values of atomic radius of iron, we have
⎡ √ √ ⎤ used Ruffa’s [10] approach of Morse potential in the functional
rFe 4r Fe / 3 − 2(r Fe + r C ) form:
a = 4√ − ⎣ ⎦ XC (3)
3 4 × 10 V (rn ) = D(1 − e−a(r−rn ) )2 (5)
where D and a are the well potential and inverse width, respec-
tively, rn is the nearest-neighbor distance; to calculate the
nearest-neighbor distance via the approximate formula intro-
duced by [11]:
   
2h 2D 1/2
ΘD = a (6)
k µ
where ΘD is the Debye temperature, k, the Boltzman constant,
µ, the atomic mass and D and a have the same definition though
a contains rn as arn .
Calculation of nearest-neighbor distance using Ruffa’s effec-
Fig. 2. The structure of martensite. tive Morse potential for metallic iron has yield a value of
 N.N. Rammo, O.G. Abdulah / Journal of Alloys and Compounds 420 (2006) 117–120 119

Table 1
Thermal expansion coefficients of allotropic iron and graphite ␣T = A + BT + CT2

Element A 10−6 /K B 10−9 /K2 C 10−11 /K3 Range of temperature, K Ref.

␥-Iron 24.7 0 0 T ≥ 1000 Onink et al. [4,15]

␣-Iron 11.45 14.0 −1.089 272–970 Krishnan et al. [13]
Graphite 1.3 0 0 273–773 Krishnan et al. [13]
2.2 0 0 733–1273 Krishnan et al. [13]

Fig. 3. Lattice parameters of Fe–C austenite as a function of carbon concentration: (a) at room temperature; (b) for different temperature.

0.24815 nm for bcc iron and 0.25224 nm for fcc iron. These 2.2. Fe–C martensite
were transferred to atomic radii and employed in the model cal-
culations of austenite and martensite with the atomic radius of As in the case of austenite, atomic radius for ␣-iron calcu-
0.071 nm for carbon in graphite [12]. lated from pair potential and thermal expansion coefficient from
Table 1 are used. Values of lattice parameters a and c versus
carbon concentration at room temperature plotted as shown in
2.1. Fe–C austenite
Fig. 5 together with the relevant experimental values [2,8,14,16],
indicate that the derived model predict the a parameter values
Calculation of lattice parameters of austenite is proceeded
very much in accordance with the experimental, whereas the
with the relevant thermal expansion coefficient for ␥-iron pre-
c parameter values appear slightly higher. Usually the marten-
sented in Table 1.
site is prepared by quenching and heat treatment, which would
The room temperature lattice parameters versus carbon con-
cause reduction in crystal defects and relief of stresses between
centration per 100 Fe atoms plotted as shown in Fig. 3,
the atoms. However, aging play a role in the redistribution of
together with the relevant experimental values [2,14], indi-
cate that theoretical values of lattice parameters are gener-
ally larger than the experimental values over the entire car-
bon concentration considered. This is due to the assumption
made that the specimen is pure austenite and has regular struc-
ture; whereas in practice, formed austenite at room tempera-
ture is usually prepared by very rapid quenching in brine or
liquid nitrogen. This sort of preparation procedure undoubt-
edly causes crystal defects. The concentrations of these defects
depend upon the starting and final temperature of quenching and
time taken. Thus the increase of defects concentration, whether
vacancy or interstitial, causes the apparent decrease in the lattice
parameters.
In regard to the lattice parameters versus temperature for dif-
ferent carbon concentrations shown in Fig. 4 together with the
experimental data reported by [15], the prediction model fits Fig. 4. Lattice parameter of austenite as a function of temperature for different
neatly within the experimental error of the measurements. concentrations.
120 N.N. Rammo, O.G. Abdulah / Journal of Alloys and Compounds 420 (2006) 117–120
Fig. 5. Lattice parameters of Fe–C martensite as a function of carbon concen-
tration at room temperature.
carbon atoms [17] and that aged specimens lead to decrease of
the c parameter, and minute decrease in the a parameter [18,19].
It is also noted that the experimental data exhibit large scat-
ter from each other. The scatter have several origins, impurities
dissolved in the martensite matrix, experimental errors due to
different methods for lattice parameters determination and tem-
perature uncertainty that pertain to data by which lattice param-
eters were evaluated.
2.3. c/a versus concentration
The tetragonality of the Fe–C martensite lattice as predicted
by the ideal ratio c/a from expressions (2) and (3) is given by:
c/a = 1 + 0.01XC
It is interesting to depict the formula presented by [20] for the
as measured ratio c/a as:
c/a = 1.000(±0.005) + 0.0096XC
which obviously in a very good agreement with ideal ratio. Again
the very slight lower experimental ratio is due to the means and
accuracy of establishing the data.
2.4. Limitation of the model
The hard sphere model utilized to predict lattice parameters
of iron–carbon system yield lattice parameters of martensite
in good agreement with the experimental data with no prime
concern on the origin of the atomic radii whether drawn from
potential or crystallographic data. For the austenite at high tem-
peratures, the model works well as it considers lattice dimen-
sional changes and vacancies at lattice sites. Only the room
temperature lattice parameters of austenite appear to be higher
by 0.25% of experimental data. One of the reasons is that the
geometrical arrangement of the hard sphere model of the closely
packed fcc impose the apparent enlargement of the lattice, where
in reality the atomic arrangement may be distorted a little by
defects causing more efficient packing thereby contracting the
lattice to lower experimental values. The other point of discus-
sion is that even with the use of pair potential to account for the
atomic interaction, a satisfactory solution is still beyond reach
for the room temperature austenite. The problem may be perused
by introducing many-body (three or four) potential energy
functions.
3. Conclusion
In addition to the prediction of lattice parameters of both
austenite and martensite in terms of concentration and temper-
ature by the proposed models, they nevertheless serve as guide
lines for the estimation of level of crystal defects that most
probably originate from treatment procedures of the steels. It
can also be applied to similar interstitial solid solutions such as
iron–nitrogen.
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