Development of new welding materials on the base of mathematical modeling

of metallurgical processes
Part 1. Phase Interaction Analysis and Development of the Basic Model.
M. Zinigrad, V. Mazurovsky
Colledge of Judea and Samaria, Ariel, Israel
The development of new electrode coating compositions is the topical area in the
current research, especially when we consider such problems as the welding of
special-purpose steels and alloys, built-up layers with special properties, or specific
maintenance works. The brief review of currently existing calculation techniques for
electrode coating compositions demonstrates that they are based on the experimentally
deduced dependence which allows to calculate the chemical composition of built-up
metal (weld metal) using so called transition coefficients (Ref. 21) or assimilation
coefficients (Ref. 22) In some cases the attempt is made to take into consideration
some redox reactions in the welding zone (on molten metal-slag boundary in the
welding pool) (Ref. 21, 23). Usually, however, the composition of built-up metal is
calculated using the mixture method without taking into consideration physicochemical processes in the welding pool (Ref. ? ). This approach can be appropriate in
order to forecast the chemical composition of built-up metal or to calculate electrode
coating for the welding of low-alloy steel and carbon steel, but leads to erroneous
results for high-alloy steel and alloys or for built-up layers with special properties. In
the latter case the considerable amount of experimental work can be required in order
to develop the new composition of electrode coating which can take months or even
years.
During the last decade both the increasing potential and the availability of personal
computers opened new possibilities for the solution of the above-mentioned problems,
and along with it we can consider the computer modeling of physico-chemical
processes in the reaction zone connected with technological parameters of the welding
process. Computer modeling used now for industrial chemical processes study and for
the analysis of real technologies allows us to decrease the amount of time and the
amount of labor needed for the research, as well as makes it possible to carry out
experiments which cannot be performed or can be performed only with great difficulty
on a real object. The development of computer technology and its accessibility have
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made it possible to solve problems for which there were previously no known methods
of solution or these methods were so tedious that they proved to be unsuitable for the
practical application. Computer approach is especially valid for physicochemical
processes since their complexity stems from the simultaneous occurrence of a
considerable number of physical and chemical processes involving liquid, solid, and
gas phases, as well as the high temperatures, the complex character of the
hydrodynamic and heat fluxes, and the nonstationary nature of the processes. This
complexity is manifested in the large number of parameters determining the course of
the processes and in the fact that the variation of a few parameters causes the variation
of many others. Such complex physicochemical objects are studied by constructing
models, i.e., simplifying systems, which reflect the most significant aspects of the
object under consideration.
Computer Modeling as an Up-to-date Approach to New Welding Materials
Development.
One of the most promising directions of physicochemical objects computer
modeling is the usage of these models for welding technologies analysis which is
represented in (Ref. 1-19). The first stage of these modeling is generally
thermodynamic models construction. This stage is very important both for ascertaining
the fundamental possibility of the combined occurrence of particular chemical
processes and for listing the most important thermodynamic characteristics. If the rates
of the chemical reactions are sufficiently high, the composition of the reactant mixture
at the outlet of the chemical reactor should be fairly close to the equilibrium
composition and can be found by thermodynamic methods. There are several
approaches to the creation of thermodynamic models. They include the employment of
polymer theory to model complex multicomponent systems, modeling for the purpose
of constructing phase diagrams, the construction of statistical thermodynamic models,
the determination of the enthalpy and other thermal characteristics, the modeling of
melting processes and structure-building processes.
When there are no or only few theoretical data on the process being modeled, the
mathematical description can take the form of a system of empirical equations obtained
from a statistical study of the real process.

A correlation between the input and output parameters of the object is established as
a result of such a study. Naturally, the employment of statistical models is restricted by
the width of the range of variation of the parameters studied.
In recent years mathematical modeling has been applied not only to the
investigation of theoretical aspects of physicochemical processes, but also to the
analysis of actual technologies.
The areas of the prediction and optimization of the composition and properties of
materials obtained in different technological processes are especially promising (Ref.
1-4, 17). Some of the results were obtained from the modeling of the process of the
formation of a weld pool (Ref. 1), from the modeling of weld metal transformations
(Ref. 18, 19), and from the modeling of processes involving the segregation of
nonmetallic inclusions in steel, the interaction of particles during welding (Ref. 4), and
diffusion-controlled kinetics (Ref. 2, 16, 17).
Important results were obtained from the studies of the physical
and chemical parameters of welding processes (Ref. 16) and
development of kinetic model of alloy transfer (Ref. 17).
By determining the chemical composition of the weld metal
researchers have developed

the kinetic model (Ref. 17) Basing on

this model the authors described the transfer of alloying elements

between the slag and the metal during flux-shielded welding. The
model also takes into consideration the practical welding process
parameters such as voltage, current, travel speed, and weld
preparation geometry. The model was tested experimentally for
transfer Mn, Si, Cr, P, Ni, Cu, and Mo.
In our opinion the problem of modeling complex objects with
consideration of the kinetics of the chemical processes occurring
them is more complicated.
This applies both to diffusion processes (Ref. 17) and especially to the
analysis of the kinetics of complicated heterogeneous reactions.
A more complete, adequate description of actual chemical processes requires the
construction of a mathematical model which takes into account the diffusion of all the
components in the complex multicomponent system, the kinetics and mechanism of the
individual chemical reactions, the special features of their simultaneous occurrence,

and the influence of heat transfer and the hydrodynamics, as well as the influence of
the engineering parameters and other factors. There is presently a large amount of
experimental and theoretical data, which make it possible to solve such problems.
The present research is also intended to be devoted to the development of
mathematical models of such a type on the basis of a new method for the kinetic
analysis of reactions in multicomponent systems.
The main problem which the technologies cited solve is the production of deposited
metal (welds, coatings, etc.) with a required composition and assigned properties. At
present time, these problems are generally solved empirically, i.e., either by means of
technological experiments or by the statistical treatment of existing experimental data.
Such an approach requires great expenditures of time and resources and the
consumption of considerable amounts of expensive materials. In addition, the results
of such researches have a random character and are far from optimal.

Peculiarities of Proposed Approach, Objects, and Stages of the Research

The approach employed in the present research fundamentally different from the
above mentioned ones. The mathematical model of the physicochemical processes
developed and the computer program written on its basis will make it possible to run
a large number of variants within a short time without considerable expenses and to
select the optimal variant, which provides products with the required composition and
properties. Such a result cannot be obtained, in principle, even after the performance
of hundreds of technological experiments.
The use of such a program permits to investigate the possibility of replacing
expensive metallic components metal- and oxide-containing industrial waste products,
something which is practically impossible to do under the empirical approach.
In the most welding materials the expensive components are
generally used. Such as ferroboron, ferrochrome, ferromolibdenum,
ferrotitanium, ferrotungsten, ferrovanadium, ferrosilicon, etc., and
pure metallic and oxide powders.
The cost of these components is usually greater then the cost of
other raw materials such as electrode rods (in case of most manual
welding) or steel band in case of flux cored welding processes.

Therefore, the replacement of expensive components with industrial

waste products saves considerable consumption of these expensive
materials.

The research is carried out in three stages: 1) mathematical description of the

process being studied, i.e., construction of the mathematical model; 2) development of
an algorithm for solving the problem, i.e., a procedure for determining the numerical
values of the output parameters; 3) establishment of the equivalence of the model to the
process being studied. Special attention was focused on the stage of constructing the
model, which was based on a thorough analysis of the physicochemical essence of the
phenomena being described and on constructing based on the model computer
program.
From these considerations the following problems of the work were defined:
- to develop a mathematical model of industrial welding processes on the basis of a
thermodynamic and kinetic analysis of the metallurgical processes, involving the metal,
slag, and gas;
- to use the model and the computer program, written on its basis, to optimize welding
technologies employing coated electrodes;
-to optimize the composition of electrode coatings which produce welded joints with
the preset composition;
- to develop a fundamentally new class of electrodes, which coating contain industrial
waste products instead of expensive components.
The object of modeling for the analysis of the physicochemical processes, taking
place during welding, is a system which includes the following phases: metal, oxide
melt (slag), gas, and solid phases, in which various chemical and physical processes
take place.
Phase Interaction Analysis
Metal-slag interaction in the process of arc welding exerts a substantial impact on
the chemical composition of built-up metal (weld metal) which ultimately determines
the working characteristics of weld metal or built-up layer. The consideration of this
interaction in the process of electrode coating development which can ensure the
preset composition of weld metal is based on the mathematical modeling of the
welding technological process, taking into account the following features of the
process:

- metal-slag interaction at two consecutive stages - electrode (drop) and welding

pool - which differ in temperature, geometrical and hydrodynamic parameters;
- continual renewal of interacting phases (molten metal and slag) at each stage through
the melting and crystallization of base and adding materials;
- simultaneous occurrence of all reactions at each stage and their interplay.
Since it is impossible to built a model describing a process with the absolute
adequacy, we offer some assumptions and simplifications. Thus in the model under
consideration basing on the experimental data for the stationary welding conditions the
following assumptions were made:
- within the phases under consideration there are not any gradients of chemical
potential (the ideal mixing of phases);
- while considering the interaction between gas and slag phases we take into account
only the reactions with hydrogen and nitrogen;
- metal-slag reactions surfaces for each stage are kinetically homogeneous.
Figure 1 is a scheme showing the interaction of phases with regard to these
assumptions.

Direction of welding

Electrode rod

Drop

Slag film

Electrode coating

Weld arc

4
7

c
5

Molten metal pool

Molten slag pool
Slag
Weld metal
Base metal

Figure 1. Interaction of phases in MMA-welding process

On the scheme figures denote the direction of material transfer, and letters denote
the interaction of phases:
1 - melting of the electrode rod and formation of a drop;
2 - melting of the electrode coating and formation of slag film over the drop;
3 - transfer of the drop metal (which has reacted with slag film at the stage of
transfer) to the metal pool;
4 transfer of the slag film (which has reacted with the drop metal at the stage of
transfer) to the slag pool;
5 - melting of base metal;
6 - crystallization of slag pool;
7 - crystallization of metal pool;
a, b - redox reaction at slag-metal boundary in a welding drop;
c, d - redox reaction at slag-metal boundary in a welding pool.
Development of the Basic Model
The welding process has a stage-like character, and it goes without saying. It should
be only specified that the stage of electrode melting as well as the existence of the drop
are of considerable importance. At this stage we already observe that the reactions of
interaction between phases exert considerable effect on the changes in the chemical
composition of molten metal and slag incoming to the welding pool, for which pool
they provide the starting chemical composition of incoming electrode metal and slag.
Regardless of the process stage and phase type the material balance of elements can be
described by the following equation:

[ E i ]inp
inp

100

V out

m j d[ E i ]
[ E i ]out
I Ei S j M Ei

j
100
100 d

where:
V inp

- the input speed of i-th element incoming to the phase, g/s;

V out

- the output speed of i -th element out of the phase, g/s;

[ Ei ] inp

- the concentration of i -th element in the incoming flux, wt %;

[Ei ] out - the concentration of i -th element in the outgoing flux, wt %;

(1)

I Ei j
at

- the rate of passage of the i -th element through a phase boundary of area

Sj

j-th stage, mol / cm2 s;

Sj

- the area of the reaction surface at j -th stage, cm2;

M Ei

- elements molecular (atomic) mass, g/mol.

mj

d [Ei ]
- the accumulated amount of an element in the phase volume under the
100
d

non-stationary conditions, and therefore in our case equals to zero;

Thus for each stage of the welding process we can compute the concentration of an
element (metal phase) or its oxide (slag phase).
The stage of electrode melting (the electrode drop)
Metal Phase
From (1) follow the material balance equation for the metal phase of the electrode
drop:
V e [ E i ]e V e [ E i ]d 100 S d I E i d M E i

(2)

where:
Ve

- the speed of electrode melting, g/s;

[Ei ] e - the elements concentration in the electrode rod, wt %;

[Ei ] d - the elements concentration in the drop metal, wt %;

Sd

- the area of the drops reaction surface, cm2;

I Eid

- the rate of passage of the i -th element through a phase boundary of slag film

drop metal, mol / cm2 s;

M Ei

- elements molecular (atomic) mass, g/mol.

Then the concentration of the element in drop metal is defined as:

[ E i ]d [ E i ]e 100

S d I Eid M Ei

(3)

Ve

Slag Phase
By analogy with the preceding:

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( E in O m ) d ( E in O m ) c 100

S d I E id M E inOm

(4)

(1 )nVc

where:
( Ein Om ) d

- oxide concentration in slag film, wt %;

( Ein Om ) c

- oxide concentration in electrode coating, wt %;

f
Kc

- the share of slag which did not interact at the drop stage,

where:

- relative slag film mass;

Kc

- relative coating mass.

Vc

- the speed of coatings melting, g/s .

The Stage of the Pool

Metal Phase
From (1) follow the material balance equation for the metal phase of the welding
pool:
V e [ E i ]e V bm [ E i ]bm V cr [ E i ] p 100 S p I E i p M E i

(5)

where:
[Ei ] bm

- the concentration of i-th element in base metal, wt %;

[ E i ] p - the concentration of i-th element in welding pool, wt %;

V cr

- the crystallization speed of metal pool, g/s;

V bm

- the melting speed of base metal, g/s;

Sp

- the area of pools reactive surface, cm2;

I Ei p

- the rate of passage of the i -th element through a phase boundary of slag pool

metal pool, mol / cm2 s;

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Hence the concentration of i-th element in welding pool is:

[Ei ] p

V e [ E i ]e V bm [ E i ]bm 100 S p I E i p M E i

(6)

V cr

Slag Phase
By analogy with the metal phase concentration of i-th oxide in welding pool is

( E in O m ) p

nV [(1 )( E in O m ) d ( E in O m ) e ] 100 S p I E i M E inOm

(7)

VcrS n

From (3), (4), (6), (7) one can see that in order to compute the chemical composition
of phases we need to know rate of passage of the i -th reagent through a phase
boundary of slag metal I R ( where: Ri - reagent, i.e. Ei or EinOm and j - the stage of
ij

the process ), which can be computed using the method of kinetic analysis (Ref. 20) for
the reactions at the molten metal-slag boundary, the latter being generalized as:
n
1
[ E i ] ( FeO ) ( E in O m ) [ Fe ]
m
m

(8)

If stoichiometry coefficient n = 1, the rate of passage of the i th element through a

phase boundary (Ref. 20):
I Ei

x m K im [ E i ] ( E i O m )
x m K im
I

lim
Ei

( E i Om ) ,
I Elimi Om

(9)

with n = 2
I Ei

2 4
,
2

where

x m K im [Ei ] 2
I Elim
i

2 x m K m [ E ]2
i
i

lim
Ei

2( E i 2 O m )
I Elimi 2Om

x m K im [ E i ]2 ( E i 2 O m )

12

(10)

( FeO )
[ Fe ]

( [Fe] and (FeO) are concentrations of iron and iron oxide

correspondingly on slag metal boundary);

Ki - the coefficient, including:
- the reaction equilibrium constant (8) of the i th element;
- activites coefficients

- coefficients of recalculation of molar concentration into weight ones.

Limiting diffusion rates of the components in the metal and the slag (Ref. ):

I Rlimi Ri D R0.i5

R i Ri

(11)

100 M Ri

where:

Ri

- convection constant, s-0.5

Ri

- the concentration of i-th element or oxide, wt %

Ri

- reagents density, g/cm3;

DRi

- reagents diffusion coefficient, cm2/s;

MRi

- reagents molecular (atomic) mass, g/mol.

For the solution us task take into account the obvious stoichiometry correlationf
followed from the reaction (8):
I FeO I i

m
I E m I E in Om
n i

(12)

The system of the above equations (3,4,6,7,10,12) presents the general

mathematical model of physico-chemical processes of the manual metal arc welding.
In actual practice the solution of this problem allows to compute the chemical
composition of built-up metal provided that we know the electrode formula and the
type of base metal. Rather often, however, we are faced with the inverse problem when
it is necessary to compute such an electrode formula that can give us the required
chemical composition of built-up metal in the process of welding (or building-up) of
specific metal (hereafter, the opposite problem).

13

The computation is based on the above model. The initial stage of the solution (the
preliminary computation) determines the initial formula of an electrode. Using it as a
base one can easily compute the chemical composition of built-up metal and forecast
its properties. If the results of this computation do not satisfy the verification criteria,
then appropriate corrections are introduced into the initial formula whereupon it
becomes the intermediate formula. The computation is repeated, and the results are
again checked. This procedure is repeated until (after n iterations) the desirable results
are gained and the final formula of an electrode is obtained.
Conclusion
The mathematical model of welding technology process on the basis of the kinetic
analysis method [20] had been developed.
The model takes into consideration:
- stage-by-stage implementation of the welding process;
- continuous renovation of interacting phases;
- simultaneous running of all reactions and their mutual influence;
- physico-chemical properties of the interaction phases;
- hydrodynamic conditions of the welding process;
- interconnection between welding process parameters (welding conditions) and
kinetics of reactions.
The proposed method can be applied to the development of new compositions of
welding materials (electric coatings, flux cored wires, welding fluxes). The practical
implementation of this approach is considered in Part 2.
References:
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Mashinostroenie, 1973, 448 pages.
2. Potapov N.N. Metal Oxidation at Fusion welding, Moscow, Printing house
Mashinostroenie, 1985, 216 pages.
3. Potapov N.N. The Metallurgy of Welding. Welding and Welding Materials. The
Handbook in 3 Vols. Ed. by V.I.Volchenko. Vol.1
14

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David

L.,

Influence

of

welding

flux

on

the

pyrometallurgical; physical and mechanical behavior of weld

metal,

Gov.Rep.

Announce.

Abstr.No.647,023.

15

Index

(U.S.),

1986,

86(21).

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on

HSLA

steelweld

metal

chemistry,

Weldability

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22. Liao F.C., Lui S., Olson D.L., Effect on titanium nitride
precipitates on the weldability of nitrogen enhanced Ti-V
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multicomponent metal with slag under diffusion conditions, Izvestiya Ac. Nauk
USSR. Metal, 1979, 6, 21-27.

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