Kovove Mater.

44 2006 181–184 181

Calculation of liquidus temperature for steel

by Le Châtelier-Shreder and van Laar-Bowen equations

J. Kavuličová1 *, D. Ivánová1 , J. Ďurišin1 , G. Sučik2 , M. Škrobian3

1
Department of Chemistry, Faculty of Metallurgy, Technical University of Košice, 042 00 Košice, Slovak Republic
2
Department of Ceramics, Faculty of Metallurgy, Technical University of Košice, 042 00 Košice, Slovak Republic
3
Department of Non-ferrous Metals and Waste Treatment, Faculty of Metallurgy, Technical University of Košice,
042 00 Košice, Slovak Republic

Received 24 March 2006, received in revised form 10 May 2006, accepted 10 May 2006

Abstract
This paper deals with the calculation of temperature of liquid phase in the Fe-admixture
binary systems. Two cases are considered in the calculations:
1. equilibrium of pure δ-iron with ideal melt of alloying element containing iron according
to the Le Châtelier-Shreder equation,
2. ideal solid solution of δ-ferrite with ideal melt of alloying element containing iron ac-
cording to modified van Laar-Bowen equation by distribution coefficients.
Decrease of melting point of δ-iron in the binary systems is calculated as the difference
between melting point of pure δ-iron and melting point of δ-iron containing 1 wt.% of alloying
element. The melting point decrease for the polycomponent system (steel) is calculated as
a sum of individual (binary) melting point decreases, which, consequently, gives the melting
temperature of low-alloyed steels.

K e y w o r d s : decrease of melting point, binary system Fe-X, liquidus temperature, steel,

distribution coefficients, ideal systems

1. Introduction 2. Calculation of melting point decrease of

iron in binary systems
Melting point is an important parameter in steel
casting because from it the optimal casting tempera- The fundamental principle of melting point calcu-
tures are derived and the course of solidification pro- lation takes stand on equality of chemical potentials
cess can be predicted. of iron and alloying elements at phase equilibrium δ-
Heterogeneous processes such as melting or solid- iron↔melt:
ification are described by the melting point of δ-iron,
temperature of melt and the decrease of melting point µδFe = µlFe , (1)
of δ-iron due to the presence of impurities and alloy-
TAV
ing elements [1–4]. The melting point of δ-iron Tδ−Fe µ0δ δ 0l l
Fe + RT ln xFe = µFe + RT ln xFe (2)
is 1811 K, the molar heat of melting at melting point
TAV
∆H1811,δ−Fe is 13 806 J ·mol−1 , molar entropy at melt- if ∆µ0Fe = µ0l 0δ TAV
Fe − µFe = ∆GFe (3)
TAV
ing point ∆S1811,δ−Fe is 7.62 J ·mol−1 ·K−1 [5]. if ∆GTAV TAV
= ∆HFe TAV
− T ∆SFe , (4)
Fe

*Corresponding author: tel.: +421 055 6022986; fax: +421 055 6321631; e-mail address: Jana.Kavulicova@tuke.sk
182 J. Kavuličová et al. / Kovove Mater. 44 2006 181–184

b) If the limiting equilibrium distribution coeffi-

 cient of i-th admixture in iron is inserted into Eq. (10),
xδ TAV
∆HFe 1 1 the following formula for melting temperature can be
ln Fe = − TAV , (5) derived:
xlFe R T l Tδ−Fe
xδ
kilim = lim il , (13)
TAV
∆HFe xi →0 x
i
Tl = . (6)
TAV xδ
∆SFe + R ln Fe TAV
xlFe l(14) ∆Hδ−Fe
Twi =1% = . (14)
TAV
1 − kilim xli,wi =1%
1) If iron and alloying element behave in melt ∆Sδ−Fe + R ln
1 − xli,wi =1%
ideally and the solidified phase is pure δ-iron, i.e.
xδFe = 1, then the melting point can be calculated The melting temperature decrease of δ-iron caused
using Le Châtelier-Shreder equation derived below in by the addition of 1 wt.% of alloying element can
Eq. (7): be calculated as the difference between melting point
of pure iron and the temperature of melt containing
TAV
∆Hδ−Fe 1 wt.% of admixture:
Tl = 
TAV − R ln 1 − xl
. (7)
∆Sδ−Fe i
TAV
∆Twi =1% = Tδ−Fe − Twl i =1% = 1811 − Twl i =1% . (15)
It is common practice to express the change in melting
point for 1 wt.% of alloying element as follows: The values of melting temperature decrease for
1 wt.% of the individual alloying elements for
1 1) ki = 0, Eq. (9),
Mi P(E)
2a) ki = ki , Eq. (12),
xli,wi =1% = , (8)
1 100 − 1 P(E)
+ where ki is the distribution coefficient of admixing
Mi MFe
element in iron at the peritectic or eutectic tempera-
ture. Alternatively, temperature of minimum on the
where MFe = 55.847 g ·mol−1 [5]. solid and liquid curves can be used (Fe-V, Fe-Cr, Fe-
-W);
TAV
l(9) ∆Hδ−Fe 2b) ki = kilim , Eq. (14)
Twi =1% = TAV − R ln (1 − xl
. (9)
∆Sδ−Fe i,wi =1% )
are summarized in Table 1 in columns 6–8. To compare
the calculated values with experimental ones, the data
from different authors are given in columns 9–11.
2) If iron and alloying element behave ideally in
both melt and solid phases the basis of melting point
calculation is given by van Laar-Bowen equation in its
3. Calculation of melting temperature
general form:
decrease of iron in polycomponent (steel)
TAV
systems
∆Hδ−Fe
Tl = . (10)
TAV 1 − xδi If no interaction between alloying elements is pre-
∆Sδ−Fe + R ln
1 − xli sumed the rule of additivity can be applied, i.e. the
total temperature decrease is the sum of individual
a) If the equilibrium distribution coefficient of i-th temperature decreases for each alloying element:
alloying element in iron is taken as isothermal ratio of

molar fractions of i-th alloying element in solid xδi and ∆Ttotal = ∆Twi =1% × %i, (16)
liquid phase xli [4, 6] then the calculation of melting
temperature for 1 wt.% of admixture can be carried
out as follows: T l = Tδ−Fe
TAV
− ∆Ttotal = 1811 − ∆Ttotal . (17)
xδ
ki = il , (11)
xi

TAV
∆Hδ−Fe 4. Discussion
l(12)
Twi =1% = . (12)
TAV
1 − ki xli,wi =1% The melting point decreases of iron calculated us-
∆Sδ−Fe + R ln
1 − xli,wi =1% ing Le Châtelier-Shreder equation are too high due to
 J. Kavuličová et al. / Kovove Mater. 44 2006 181–184 183

T a b l e 1. Melting point decrease of binary systems (iron-admixture) for 1 wt.% of admixing element ∆Twl i =1% taken
P(E)
from literature and calculated for 1) ki = 0, 2a) ki = ki , 2b) ki = kilim

∆Twl i =1%
P(E)
Alloying Mi xli,wi =1% ki kilim
element (g · mol−1 ) [6] [6] 1) 2a) 2b) [6] [7] [8]

1 2 3 4 5 6 7 8 9 10 11

B 10.811 0.0496 0.07 0.045 95.2 89.0 91.2 98 – 90

C 12.0107 0.0449 0.17 0.19 86.4 72.6 70.9 86.6 65 73
N 14.007 0.0387 0.28** – 74.7 54.7 – – – –
O 15.9994 0.0341 0.17 0.15 66.0 55.3 56.6 – – 11 for 0.16 %
Al 26.9815 0.0205 0.85 0.88 40.0 6.2 4.9 11.8 – 3
Si 28.0855 0.0197 0.82 0.66 38.5 7.1 13.4 13.9 8 12
P 30.9738 0.0179 0.31 0.14 35.0 24.4 30.2 32.3 30 28
S 32.065 0.0173 0.013 0.062 33.8 33.4 31.8 30.5 25 30
Ti 47.867 0.0116 0.62 0.35 22.8 8.7 14.9 14.9 – 18
V 50.9415 0.011 1* 0.87 21.6 0.0 2.8 2.9 2 2
Cr 51.9961 0.0107 1* 0.9 21.0 0.0 2.1 2.1 1.5 1
Mn 54.9380 0.0102 0.72 0.69 20.0 5.7 6.3 6.2 5 3
Ni 58.6934 0.0095 0.77 0.69 18.7 4.3 5.8 5.6 4 3.5
Co 58.9332 0.0095 0.85 0.84 18.7 2.8 3.0 3 – 1.8
Cu 63.546 0.0088 0.52 0.78 17.3 8.4 3.8 3.8 5 7
As 74.9216 0.0075 0.39 0.21 14.7 9.0 11.7 11.8 – 14 for 0.5 %
Nb 92.9064 0.006 0.27 0.37 11.8 8.6 7.5 7.5 – –
Mo 95.94 0.0058 0.99 0.73 11.4 0.1 3.1 3.1 – 2
Sn 118.71 0.0047 0.26 0.28 9.3 6.9 6.7 6.7 – 10 for 0.03 %
Ta 180.948 0.0031 0.32 0.44 6.1 4.2 3.4 3.5 – –
W 183.84 0.0031 1* 0.83 6.1 0.0 1.0 0.9 – <1
P(E)
Remarks: * value of distribution coefficient at minimum on the curves of solidus and liquidus; ** value of kN taken from
[8]

the fact that the solid phase obtained during solidific- It is recommended to calculate melting point de-
ation is not, typically, pure δ-iron. crease of low-alloyed steels, such as deep-drawing,
The binary systems of chromium-iron, vanadium- transformer, micro-alloyed or structural steels, accord-
-iron and tungsten-iron show minimum on the solid ing to the following formula:
and liquid curves at which the temperature distribu-
tion coefficients are equal one. Consequently, values l
Tsteel = 1811 − 72.6 × %C − 7.1 × %Si − 5.7 × %Mn
of melting point decrease calculated according to Eq.
(15) are zero. In this case, therefore, it is recommended − 24.4 × %P − 33.4 × %S − 2.1 × %Cr
to read the melting point decrease directly from the − 2.8 × %V − 6.2 × %Al − 8.4 × %Cu
phase diagrams. They are 1.26 ◦C per 1 wt.% of chro- − 4.3 × %Ni − 2.8 × %Co − 8.6 × %Nb (18)
mium, 2.4 ◦C per 1 wt.% of vanadium and 0.68 ◦C per − 4.2 × %Ta − 8.7 × %Ti − 9 × %As
1 wt.% of tungsten. Another possibility is to calculate
the melting point decrease using limiting distribution − 1 × %W − 6.9 × %Sn − 54.7 × %N
coefficients as it is done in Table 1, column 8. The − 0.1 × %Mo − 55.3 × %O − 89 × %B.
calculated melting point decreases (Table 1, columns
7 and 8) agree reasonably with the literature values in
Table 1, columns 9–11. Acknowledgements

This project was carried out with the financial support

5. Conclusion of grant-in-aid VEGA 1/3205/06.

The van Laar-Bowen equation (12), modified by References

(16), (17), (values from Table 1, column 7), is recom-
mended for the calculation of the melting point de- [1] KIJAC, J.: High-temperature Processes of Steel Pro-
crease of δ-iron (1 wt.% of admixture) – Eq. (18). duction. Emilena Košice 2006.
184 J. Kavuličová et al. / Kovove Mater. 44 2006 181–184

[2] GEDEONOVÁ, Z.—JELČ, I.: Metallurgy of Cast- [6] DRÁPALA, J.—KUCHAŘ, L.: Hutnícke listy, č. 4–7,
iron. Košice, HF TU 2000. 2000, p. 59.
[3] ŠMRHA, L.: Solidification and Crystallization of Steel [7] ROESER, W. M.—WENSEL, H. T.: Journal of Re-
Ingots. Praha, SNTL 1983. search of the National Bureau of Standards, 26, 1941,
[4] KUCHAŘ, L.—DRÁPALA, J.: Metallurgy of High- p. 273.
purity Metals. Košice, Nadace R. Kammela 2000. [8] MYSLIVEC, T.: Physico-chemical Principles of Steel-
[5] DINSDALE, A. T.: Calphad, 15, 1991, p. 319. making. Praha, SNTL 1971.