Diffusion Foundations Submitted: 2018-01-20

ISSN: 2296-3642, Vol. 18, pp 49-54 Revised: 2018-05-12

doi:10.4028/www.scientific.net/DF.18.49 Accepted: 2018-05-13
© 2018 Trans Tech Publications Ltd, Switzerland Online: 2018-09-05

Modeling of Liquid-Liquid Demixing Curve

in Lead-Zinc Binary System
Naceur Amel1,a*, Adjadj Fouzia2,b
1
Faculty of Material Sciences, Biskra University, Algeria.
2
Faculty of Material Sciences, Batna University, Algeria
a
naceuramel@gmail.com, bfouzia.adjadj2009@gmail.com

Keywords: Thermodynamic Calculation, Modeling, Demixing Curve, Phase Diagram, Newton –

Raphson Method.

Abstract. In this work we discussed the modeling of the demixing curve in the liquid state in the
Lead – Zinc binary system. We are interested to recalculate the free energies relating on Pb-Zn
alloys for several temperatures based on the thermodynamic data collected in the bibliography. This
calculation allows us to trace the curve of phase separation from a program after obtaining the mole
fractions corresponding to the common tangent to the curve of the free energy with two minima at
different temperatures. To do this, we used the Matlab 7.1 as the programming language and the
Redlich – Kister polynomial as a mathematical model of development. The results obtained are very
satisfactory by comparing them with those of the bibliography.

Introduction
The immiscible metallic alloys in the liquid state are provided with very special properties:
thermal, electrical and mechanical. They are used as contacts materials, electrical current switches,
superconductors, friction alloys, solid lubricants coatings to prevent corrosion also they can be used
as temporary forces support axes propellers of boats and submarines [1-9].
There are a lot of binary and ternary metal systems with a demixing in the liquid state [10-14]. A
three phase invariant reaction that occurs in some binary system is monotectic reaction in which a
liquid transforms to another liquid and a solid. Two liquids are immiscible over certain range of
compositions.
It is necessary to use modeling in the phase diagrams to specify the extent of the phase domains
and their thermodynamic properties. For an experimental phase diagram, it is not always essential to
study all the alloy compositions which requires a significant time and a high cost.
The modeling allows, by using certain experimental points, to complete the phase diagram.
The present work was performed in order to optimize the liquid miscibility gap in the Zinc –
Lead binary alloys. A set of thermodynamic data for liquids solutions where evaluated by
optimizing previous experimental data on phase diagram and thermodynamic properties. The
demixing curve was optimized using CALPHAD method (CALculation of Phase Diagrams) [15]
and polynomial Redlich – Kister [16] to describe the excess Gibbs energy of the liquid phase.
The free enthalpy of mixture is connected to the enthalpy ΔH and the entropy ΔS of mixture by
the expression:
∆G = ∆H − T∆S (1)
The ideal entropy of mixture is given by:
∆S id = − R( x A log x A + x B log x B ) (2)
Where R is the gas constant.
The enthalpy of mixing is given by:
∆H = ∆H 0 x A x B (3)
Where ΔH0 represent the interatomic interactions.

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50 Functional Materials: Technological Aspects of Production and Processing

For positive values of ΔH0, the free Gibbs enthalpy curve takes the shape of fig. 1, which present
tow minima ɸB1 and ɸB2 where the common tangent in this tow points corresponds to:
∂G = ∂G (4)
∂φ φ ∂φ φ
B1 B2

Fig. 1: Energetic condition of system with limited miscibility

Thermodynamic Model
1. Pure elements
Gibbs energy of pure elements have nowadays been well assessed and they are collected in
database compiled by Dinsdale [17]. In present work we have used these functions.
The Gibbs energy function of elements i (i = Zn, Pb) in the liquid phase are of SGTE (Scientific
Group Thermodata Europe) format:
(5)
Where:
are absolute and the relative Gibbs energy of the element i in the liquid
phase.
is the molar enthalpy of the element i at 298.15 K in its standard element reference
(SER) state.
2. Liquid solution phase
The liquid solution phase was described by the regular solution model with Redlich – Kister
equation [16] the Gibbs energy for 1 mol of atoms is described as the sum of three terms: reference
(ref ) Eq 6 , ideal (id) Eq 7 and excess (exc) Eq 8

(6)

(7)

(8)
Where R is the gas constant, and are the mole fraction of element Zn and Pb
respectively.
(l = 0,1,2,…) are the interaction parameters which have been taken as temperature
dependant and can be written as . are the parameters to be optimized.
 Diffusion Foundations Vol. 18 51

Program application to Zn–Pb system

Fig. 2: Binary Zn-Pb experimental equilibrium phase diagram [19]

Optimization Resultants and Discussion

The free enthalpy of mixing is expressed by the following expression:
∂G ( x , T ) G( x , T ) − G( x , T )
2
= 2 1 (9)
∂x x −x
2 2 1

∂G ( x , T ) G( x , T ) − G( x , T )
1
= 1 2 (9’)
∂x x −x
1 1 2

The consideration of all points extracted from phase diagram (x1, x2, T) and the use of Eq. 9 and
Eq.9’, conduct us to an over-determined system of equation in 2(n+1) unknown (Al and Bl with l =
0,…,n). This type of system can be written as (Eq. 10):

(10)
Where:
X is the unknown vector to be determined: with l = 0,…, n (n is the development
order)
is the unknown coefficients matrix.
is a constant vector.
The resulting system is linear and can be written in matrix form (Eq.10):
The resolution of the system of Eq. 10 consists; firstly, to make the system determined by using
the least squares method by using the following formula:

(11)

Where: is the transposed matrix of the matrix

The resolution of the new linear system of Eq.11, leads us to the determination of the
coefficients.
52 Functional Materials: Technological Aspects of Production and Processing

The stable equilibrium points between two phases at temperature T are determinate by using the
following system of equilibrium equations Eq.12 and Eq. 13:

(12)

(13)

n  l +1  x1 (1 − x1 )   x (1 − x 2 )     x (1 − x 2 )  
∑ ( Al + Bl T ) (1 − 2 x1 )  1 + 2l  − (1 − 2 x 2 ) l +1  1 + 2l 2   + RT  log 1  = 0 (15)
l =0   (1 − 2 x )²   (1 − 2 x )²    x (1 − x )  
  1   2    2 1 

  x1  n   x (1 − x )   
( x − x ) RT log  + ∑ ( A + B T ) (1 − 2 x )l + 11 + 2l 1 1 −

1 2   (1 − x )  l = 0 l l  1  (1 − 2 x )²   
  1    1 

 n 
 RT ( x log( x ) + (1 − x ) log(1 − x ) + x (1 − x ) ∑ ( A + B T )(1 − 2 x )  + (16)
1 1 1 1 1 1 l l 1
 l=0 
 n 
 RT ( x log( x ) + (1 − x ) log(1 − x ) + x (1 − x ) ∑ ( A + B T )(1 − 2 x )  = 0
2 2 2 2 2 2 l l 2
 l=0 
Witch return to resolve a nonlinear system of equations at different temperature with two
unknowns ( ) Eq. 14 and Eq.15 using the Newton – Raphson method described
briefly in the following

If is the initial value, the successive approximations of the solutions are obtained
according to the formula:

These points x1 and x2 are solutions of the equations Eq.15 and Eq.16 above different
temperature and are used to plot the liquid-liquid demixing curve.
The development at order 3 by using the 6 first equations in the forme of Eq.15 permits the
determination of al and bl coefficients. This results are regrouped in Table.1:
Table 1: The optimized parameters for the liquid in Zn – Pb system
phase Term
L0 = 64040.312-105.396*T
L1=679655.356-670.208*T
Liquid
L2=-207662.736+155.964*T
L3=-176858.245+74.548T*
 Diffusion Foundations Vol. 18 53

An example of free enthalpy curve of mixing that we have succeeded to draw using optimization
coefficients resulting from our program at various temperatures is given in fig. 3.
4
x 10
0

-0.2
T= 900°C
-0.4
Free Enthaply (J)

-0.6

-0.8

-1

-1.2

-1.4

-1.6

-1.8

-2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
at % Pb
Fig. 3: Calculated curve of free enthalpy of liquid mixing for Zn-Pb system at T=900°C
The points of double common tangent obtained at different temperature, through our program,
help us to retrace the demixing curve. Fig. 4 represents demixing curve extracted from the
experimental equilibrium phase diagram of Zn-Pb system and that calculate.
Experimental curve
Calculat curve
900
850
800
750
700
Temperature °C

650
600
550
500
450
400
350
300
0,0 0,2 0,4 0,6 0,8 1,0
Atomic percent Lead

Fig. 4: Comparison between the experimental miscibility gap [18] and

that calculated for Zn-Pb system [this work]
Table 2 summarizes the results of characteristic points of demixing compared with other works.
Table 2: Comparison of our results with different works
Exemple [18] [19] [20] This work
Critical temperature Tc, [K] 1071 1073 1071 1071.412
Critical composition xc 0.28 0.30 0.28 0.2801
54 Functional Materials: Technological Aspects of Production and Processing

Our results agree well with those obtained experimentally especially those of Y. Plevachuk
and al [21].

Conclusion
The liquid miscibility gap modeling by using Redlich-Kister polynomial as mathematical model
and MATLAB 7.1 as programming language was the subject of this work.
We presented the modeling results of the zinc-lead binary system. The results made it possible to
define the temperature and the composition of the critical point, i.e. the maximum of the demixing
curve, which is often difficult to determine experimentally.
On the experimental side, the simulation of phase diagrams can constitute a direct link between
the modeling of a binary systems and the phases behavior.
Comparisons between the calculated and experimental results showed that the experimental data
can be reasonably described by the present thermodynamic description.

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