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Alternative to mould powder in the continuous casting of steel

Negative Results · March 2015

DOI: 10.13140/RG.2.1.4749.1444

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Ankit Soni
Reliance Industries Limited, Hazira
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 Alternative to mould powder in the continuous
casting of steel

Introduction:
Mould powders are essential for the stability of the continuous casting process steel.

The main function of mould powders are:

I. Protection of steel from oxidation

II. Thermal insulation of steel meniscus
III. Absorption of inclusions from the steel
IV. Lubrication of the steel shell (strand)
V. Control of mould heat transfer between the steel shell and the mould.

First three functions can be achieved by properly choosing the tundish covering material.
So the two main functions of mold powder are strand lubrication and control of mould
heat transfer in the horizontal direction between the steel shell and mould (typically Copper
mould in Tata Plant) which directly affect the quality of surface and stability of the casting
process.

Typical composition of mould powder:

Components Wt. (%) Components Wt. (%)
CaO 25-45% FeO 0-6%
SiO2 20-50% MgO 0-10%
Al2O3 0-10% MnO 0-10%
TiO2 0-5% BaO 0-10%
C (coke or carbon black) 1-25% Li2O 0-4%
Na2O 1-20% B2O3 0-10%
K2O 1-5% F 6-10%

Fluorine in mould powder has a great influence on the mould powder properties and also has
hazardous effect on the environment.

Advantages of Fluorine:
I. Lowers the melting point of mould powder (enhances lubrication property of mould
slag).
II. To decrease the viscosity of mould slag. (helps in formation of continuous and stable
slag film)
III. Enhances the crystallization of slag film.

Disadvantages of Fluorine:
I. Emission of volatile component like SiF4 and NaF.
II. Fluorine Reacts with cooling water leading to the formation of HF.

These disadvantages are hazardous for plant personal and environment and also lead to
the severe corrosion of caster.
Due to these disadvantages, there is an urgent need to suppress these hazardous fluorine
containing emissions. In order to remove the fluorine from the mould flux, it is necessary
to find a replacement that can replicate the fluxing functions carried out by Fluorine.

Majority of mold powder are of CaO-SiO2-CaF2 system. In this system, fluorine is an

essential component. In this system, crystalline layer of cuspidine crystal (Ca4Si2O7F2) are
formed in a glass matrix.
 A slag film of mould powder consists of solid part at the mould side and a liquid
part at the strand side. Liquid part of slag film assists in strand lubrication and the
solid (crystalline) part act as a thermal barrier to control the horizontal heat
transfer.
 The liquid part moves together with the strand and is mainly responsible for the slag
consumption in casting. Crystalline part of slag majorly remains intact with mould
surface (i.e. there is meager relative motion between mould and crystalline part).

Lubrication of steel shell (strand)

Presence of Liquid part of slag film is responsible for strand
lubrication. Lack of lubrication will result in increased friction
between the strand and mould which leads to effects like rupturing
of steel shell, sticking of the strand and breakouts of the liquid steel
at mould exit.

Control of mould heat transfer: The huge temperature gradient

between liquid steel and mould surface (> 1000oC) leads to very
high rate of heat transfer and variation in local heat transfer.
Uncontrolled heat transfer may lead to-
 Formation of longitudinal facial crack.
 Poor surface quality of the product.
 Non uniform mechanical properties within the bulk of
product.
 Residual stresses.

Mould heat transfer during casting is principally determined by

I. Thickness of slag film and
II. the presence of crystal in slag film
Solidification assists in reduction of horizontal mould heat transfer due to the formation
of:
 Rough mould flux interface (i.e. wrinkle) between slag and the mould, causing a
contact resistance.
 Conductive resistance due to the thickness of mould slag between liquid steel and
mould during the heat removal.
  According to latest research increased reflectivity by crystallization will lead to more
scattering of radiation i.e. reduction in radiative heat transfer between liquid metal
shell and mould surface.

Conclusion from the study

The strand lubrication mainly depends on two properties of liquid mould slag
 Melting point
 Viscosity
Substitute of fluorine should focus on these properties mould flux to enhance
lubrication

1. According to the latest research done by the scientific community, it was found that
we can use different oxides such as B2O3, Li2O and Na2O, in order to substitute CaF2
the mould powders contained increase amount of Na or Li together
with B in order to guarantee a low melting point and low viscosity.

 Mould fluxes are silica based synthetic slags. Silica exists as

a network composed of tetrahedra of Si surrounded by four
oxygen (SiO4) 4- and consequently, are known as network
formers.
 Fluorine replaces a bonding-oxygen ion, thereby breaking the
silicate chains, and consequently lowers the viscosity and
melting point.
 So, the best replacement for fluorine to ensure same level of
melting point and viscosity for better lubrication would be
basic oxides.
 When basic oxides (alkaline earth and alkali metal oxides)
are added, a weaker single bond between oxygen and silica is
formed, lowering the activation energy and reducing the
 viscosity of the system.
 The most obvious candidates are B2O3 and Na2O.

Comparison between various properties of fluorine free mould powder and

commercially used mould powder is shown below:
(These conclusion are based on experiments performed in conference paper [4] that we came
across while studying)

Properties
Horizontal heat transfer between
steel shell and mould surface
Melting rate of mould powder
Viscosity
SEN erosion rate
Powder consumption rate
Conclusion
Higher heat extraction with the fluorine-free mould
powder
The melting rate of Fluorine-free mould powder was
similar to commercial one.
Viscosity of fluorine free mould powder is similar to
the viscosity of commercial one.
Erosion rate is higher for fluorine free mould powder
(not definitive)
The average powder consumption rate of fluorine
free mould powder is lower than commercial one.

Note:
Main problem of using fluorine free mould powder is reduction in horizontal heat transfer

2. It was also found that it is difficult to replace fluorine containing components

(mainly CaF2) from mould powders with some other substitute to have same
crystallization properties as the fluorine containing mould powders, without
affecting its other function.
For example:
 Suggestion to use CaO-SiO2-TiO2 (CaTiO3 pervoskite as its main
crystallization component) system instead of CaO-SiO2-CaF2 system.
But recently it has been reported that mould powder result in operational
disadvantages such as decrease in strand lubrication due to the formation of
high melting point compound of Ti(C,N) and TiN. [1]

 Researcher in Korea mentions the use of large amount of boron (around 30%
of B2O3). In mould powders with this composition the slag crystallization were
realized sufficiently but it also has been reported that the presence of Boron in
mould slag erodes SEN (submerged entry nozzle) [2]

Presence of a continuous slag film between the steel shell and the strand is essential for the
two important functions strand lubrication and the control of mould heat transfer.
But sadly these functions are conflicting i.e. improving one of these function by changing
mould powder have an opposite impact on the other. So we have to compromise between the
“strand lubrication” and the “control of mould heat transfer”.

Motivation for an idea

1. Controlling mould heat transfer is bit difficult to achieve with fluorine free mould
powders as compared to strand lubrication.
2. Functions of mould powders like strand lubrication and horizontal mould heat transfer
are contradicting in nature (i.e. enhancing one degrade the other)

These two motivations encourage us to develop an idea to tackle the problem of fluorine in
mould powder.

The idea is
“To achieve only one desired function of mould powder which is easy to attain (i.e. strand
lubrication) with fluorine free mould powder and to control horizontal heat transfer
between steel shell and mould by some other method i.e. coating copper with TBC’s
(thermal barrier coating of ceramic crystals like pervoskite)”. [3]

There has been lot research is going on since last two decades on the development
ceramic TBC’s like pervoskite coatings in order increase the efficiency of gas turbines.

So, instead of searching for fluorine free mould powder that can lubricate strand
and form crystalline layer on mould side (heat transfer control).
We can use readymade copper moulds coated with thin layer of these thermal
barrier coatings on its inner surface along with recently developed fluorine free
mould powder for continuous casting process.
 References:
[1] Formation of TiN and Ti(C,N) in TiO2 containing, fluoride free, mould fluxes at high Temperature Q. Wang1,
Y. J. Lu*1, S. P. He1, K. C. Mills2 and Z. S. Li3

[2] S-Y. Choi, D-H. Lee, D-W. Shin, S-Y. Choi, J-W. Cho and J-M. Park, Properties of Fluorine free glass system
as a mold flux: viscosity, thermal conductivity and crystallization behaviour. Journal of Non-Crystalline Solids,
345&346 (2004) 157-160.

[3] New Generation Pervoskite Thermal Barrier Coating Materials W. Ma, M.O. Jarligo, D.E. Mack, D. Pitzer, J.
Malzbender, R. Vaßen, and D. Stover

[4] Development of fluorine free mould powder for using in continuous casting of billets – preliminary industrial
test
Daniel dos Reis Silva 2 Suzana Lancelote de Freitas 3 Jeferson Leandro Klug 4 Márcia Maria da Silva Monteiro
Pereira 5 David Jose Rihl6 Nestor Cezar Heck 7 Antônio Cezar Faria Vilela 8 Detlef Jung

[5] Impact of Fluorine Free Mould Flux use on Continuous Casting Process
Maria Carolina Campello Bezerra(2) Cláudio Antônio Goulart Valadares (3) Ivan Penna Rocha (4) José Roberto
Bolota (5) Marcelo Carboneri Carboni (6) Ivan Luis de Mattos Scripnic (7) Carlos Roberto Santos (8) Keneth
Mills(9) David Lever (10)

[6] Y. Tsukaguchi, M. Hanao, M. Kawamoto, C. Liebske and J.A. Kromhout, Melilite

Crystallization of High Basicity and High Viscosity Mold Flux. CAMP-ISIJ, 21 (2008)
826-829

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