FACTORS AFFECTING

CALCIUM WIRE RECOVERY

COLLEGE: NATIONAL INSTITUTE OF TECHNOLOGY,JAMSHEDPUR

1.) NAME: ROHIT KUMAR (VT20222356)
ROLL NO. : 2019UGMM021
2.) NAME: AMMAN AKHTAR (VT20222183)
ROLL NO. : 2019UGMM033
Under the Guidance of SPARSH Sir, Sr.Manager (SMLP)
PERSONAL NUMBER: 197380
EMAIL ID: [email protected]
DEPARTMENT: LD3 & TSCR
INDEX
• INTRODUCTION
• CALCIUM WIRE RECOVERY IN LADDLE STEEL LADLE
FURNCE
• VAPOUR PRESSURE OF CALCIUM
• THEORITICAL ASPECTS OF CALCIUM TREATMENT OF
STEEL
• FACTORS AFFECTING Ca RECOVERY
• EXPERIMENTAL ASPECT OF CALCIUM TREATMENT OF
STEEL
• CONCLUSION
• REFERENCES
INTRODUCTION
There have been significant changes in the specification of steel products. The
service requirement of these products have become more and more severe
over the last two decades. Specifications are now more rigid to
meet the product requirements. Customer’s
demand has led to stringent steel quality with respect to composition in a
narrow range, high degree of cleanliness, absence of segregation ,low gas
content etc. The increasing demand for high-quality steel products has led to
the continuous improvement of steel making practices. There is a special
interest in the control of non-metallic inclusions due to their harmful effect on
the subsequent stages and their great influence on the properties of the final
product. Through the control of the amount, size and chemical composition of
the inclusions it is possible to obtain a final product of good quality. There is an
emerging trend of reducing total non metallic residuals(C,S,N,O,P,H) to very
low levels. Secondary steelmaking has played a vital role in meeting these
requirements Treatment of liquid steel with calcium in ladle refining process
has become an important means of deoxidation, desulphurization to very low
levels and to control the shape, size and distribution of oxide and sulphide
inclusions .Benefits directly attributable to calcium treatment include greater
fluidity, smoother continuous casting by reducing nozzle block age and
improved cleanliness, machinability ductility and impact strength in the final
product. Calcium injection into liquid steel helps to liquefy the alumina. In this
process, nozzle clogging is also reduced; particularly in billet and thin slab
casting where the steel must pass through narrow refractory spaces. In the
presence of sulphur, calcium also forms calcium sulphide and Mn S may
precipitate on the Ca S nuclei (sulphide shape control). Introduction of calcium
in steel has always been a challenge to steelmakers due to low melting point
(848oC), low boiling point (1484 o C) and extremely low solubility. The
solubility of calcium in liquid iron (Fe) is reported to be 300 ppm at 1600 o C
and 1 atm of calcium vapour pressure . Under practical steelmaking conditions,
the concentration of dissolved calcium depends upon; the time available for
the reactions to approach equilibrium, stirring conditions, temperature and
composition of liquid steel at the time of calcium injection, Vaporisation of
calcium at steelmaking temperatures and its low solubility in iron are
apparently the main causes of a low calcium recovery.
 CALCIUM WIRE RECOVERY IN STEEL LADLES
FURNACE

Development of continuous casting process (for billets, blooms, slabs,

thin slabs and thin strips) and newer products need stringent quality
control during steel making to ensure smoother casting operation as
well as to allow casting at higher speeds. Calcium treatment of steel in
secondary refining, thus, has become necessary with the increase in
continuous casting ratio and nowadays is a well established method to
transform oxide and sulphide inclusions in steel to less harmful
inclusions which can have even beneficial effects to steel properties.
Nozzle blockage problems in continuous casting can be minimized by
transformation of solid alumina inclusions in to liquid calcium
aluminates for aluminum killed steels. Also, introduction of calcium in
low aluminium (<0.005% Al) - Si killed steel results in reduced porosity in
cast products by reducing the dissolved oxygen content as it is a very
strong deoxidizer as well Introduction of calcium in liquid steel is
difficult due to it’s low density, low melting and boiling temperature and
higher vapour pressure These problems have led to the development of
special addition technique like cored wire injection which comprises of a
continuous steel tube filled with calcium bearing materials Metallurgical
Company Limited is pioneer in production of cored wire technology and
manufactures whole range of cored wires including that of Ca based
cored wire for application in steel making. In normal practice recovery of
Ca is in the range of 12-15% with cored wires of Ca-Fe, Ca-Fe-Al and Ca-
Si. Introduction of newly developed high performance pure calcium (
Ca>98%) cored wires have resulted in enhanced average calcium
recovery of more than 24% during treatment in ladle furnace.
 VAPOUR PRESSURE OF CALCIUM
Vapour pressure of Calcium at three different temperature is given in Table below and data for
temperature range between 1550- 1650 deg C is presented in the below Figure:

*VAPOUR PRESSURE OF CALCIUM AT DIFFERENT INJECTION TEMPRETURES

From the above it can be inferred that the vapour pressure of Calcium at treatment temp of 1575
and 1600 deg C is 1.4 and 1.81 atm respectively. If the calcium is released, before the melting of
sheath, at a depth of more than 2.0 meters for treatment temp of 1575 deg C and at a depth of
more than 2.4 meters for treatment at 1600 deg C then the loss of calcium due to burning at top of
ladle will be minimized as the ferro-static pressure will be higher than vapour pressure of calcium.

THEORETICAL ASPECTS OF CALCIUM TREATMENT OF STEEL

Alumina inclusions occur as deoxidation products in the aluminium-based deoxidation of steel Pure
alumina has a melting point above 2000°C, i.e., these alumina inclusions are present in a solid state
in liquid steel. The addition of calcium to steel which contains such inclusions changes the
composition of these inclusions from pure alumina to CaO-containing calcium aluminates, as it can
be observed from the CaO-Al2O3 binary system, shown in Figure. The melting point of the calcium
aluminates will decrease as the CaO content increases, until liquid oxide phases occur at about 22%
of CaO, i.e., when the CaO.2Al2O3 compound is first exceeded at 1600ºC. The liquid phase content
continues to increase as CaO content rises further and is 100% at 35% of CaO. The minimum melting
temperature for the liquid calcium aluminates is around 1400°C.

* CaO-Al2O3 Phase Diagram [3]

Thermodynamically, if sulfur or oxygen is dissolved in the steel at moderate levels, or if Al2O3

inclusions are present in steel, calcium will react with these. According to Larsen Ca will react with
oxygen or sulfur until the contents of reactants are very low (< 2ppm). Reaction of calcium when
introduced in steel can be represented by following set of equations: Ca(l) = Ca (g) (i)

Ca(g) = [Ca ] (ii)

[Ca] +[O] = CaO (iii)

[Ca] +[S] = CaS (iv)

[Ca]+ (x+1/3)Al2O3=CaO*xAl2O3 + 2/3 [Al] (v)

(CaO)+2/3[Al] +[S]=(CaS) +1/3 (Al2O3) (vi)

One of the critical questions is whether or not calcium added to steel will react with sulfur by
reaction (iv) and form CaS or modify Al2O3 to liquid Calcium aluminate by reaction (v). The
formation of calcium sulphide can occur if calcium and sulfur contents are sufficiently high. Since
calcium has higher affinity for oxygen than for sulfur, the addition of calcium initially results in a
more or less pronounced conversion of the alumina into calcium aluminates until the formation of
calcium sulphides starts as the addition of calcium continues. For steels with low “s” content
reaction will take first followed by reaction[6].

PHASES PRESENT DURING REACTION OF CALCIUM WITH ALUMINA

INCLUSIONS

Composition of various phases along with their melting point is given below . Main aim is to obtain
maximum content of C12A7 liquid inclusions

FACTORS AFFECTING Ca
RECOVERY
To realize the benefits of cored wire injection, it is imperative that the filling material is released at
such a depth in the ladle that the resultant residence time is highest . The wire parameters which
have been reported to influence the distance travelled are wire speed, diameter, packing density of
powders, casing thickness etc. Also, the steel temperature and steel grade is reported to influence
the depth of release of the filler material. Sibasa have studied calcium recovery and efficacy of
calcium treatment using dimensional analysis and electron microscopy. Industrial data during Ca-Si
cored wire injection in aluminium killed steel have also been analysed. Calcium recovery was found
to increase with increased Si content, while it decreased with increase in bath temperature and
calcium recovery was maximum at a wire speed of 200 meter/minute.

CALCIUM CORED WIRES MANUFACTURED

Cored wire is manufactured at Kalmeshwar Industrial Zone in Nagpur, with world-class
manufacturing facility for Cored Wires functioning within Integrated Management Systems i.e. ISO-
9001, EMS 14000 and OHSAS 18001. Manufacturing facilities include 5 cored wire drawing mills
operating at 100 metres/min speed with annual production of 10,000 MT powder weight. One of the
cored wire drawing mills is dedicated for production of high performance calcium cored wire. The
plant manufactures different types of cored wire for steel and foundry applications. The product
range includes cored wires of Ca-Fe, Ca-Al-Fe, Ca-Si, Ca, C, Fe-B, Fe-Ti, Fe-Mo,Fe-Nb, Fe-Si, Graphite,
Lead, Fe-Si-Mg etc. The details of core wire facility is given below:

• Five Production Lines with all associated equipments.

• Wire diameters from 5mm to 21mm.

• Automated powder fill control system for +/- 5grms accuracy.

• Maximum production speeds upto 100MPM.

• Powder sizing and screening facilities.

• Loading and unloading area for approximate 30 Containers per day.

• Custom Bonded Ware House.

The composition and other details of various calcium based cored wire conventionally used is listed
below. It may be noted that in cored wire parlance density of cored wire means weight of filler
material in grams per meter of cored wire.
->EXPERIMENTAL
Plant scale trial results of two such products are described in subsequent sections. Broad
specification of these are given as under:

It may be noted that both cored wires had different design features.

PLANT TRIALS WITH VARIANT “A”

Pure calcium cored wire treatment of liquid steel was done at the end of refining in Ladle Furnace ie
when the steel was fully deoxidised, desulphurised to desired sulphur levels and after the
attainment of steel chemistry. The aim was to attain calcium level in the range of 15-25 PPM after
treatment at LF. The following were the injection parameters:

Quantity of Calcium addition (Kg/t): 0.06-0.09 Speed of cored wire feeding (Meters/ Minute): 100-
150
Temperature of treatment (deg C): 1580-1610

Chemistry of steel treated with calcium is given below:

PLANT TRIALS WITH VARIANT “B”

Pure calcium cored wire treatment of liquid steel was done in another steel plant at the end of
refining in Ladle Furnace ie when the steel was fully deoxidised, desulphurised to desired sulphur
levels and after the attainment of steel chemistry. Here the aim was to attain calcium level of more
than 25 after treatment at LF. The higher Ca level in this case is as per their plant practice. Following
were the injection parameters:

Quantity of Calcium addition (Kg/t): 0.09-0.125 Speed of cored wire feeding (Meters/ Minute) : 110-
120

Temperature of treatment (deg C): 1580-1600 Chemistry of steel treated with calcium is given
below:

FREQUENCY DISTRIBUTION OF CALCIUM RECOVERY

Frequency distribution of calcium recovery is shown in . It may be noted that heats having recovery
of more than 25% was more than 40% whereas percent heats having less than 20% calcium recovery
was 25%.
 *Frequency distribution of calcium recovery

EFFECT OF WIRE FEEDING SPEED OF ON CALCIUM RECOVERY

Highest average calcium recovery of more than 25% has been attained at Wire feeding speed of 120
meters/Minute . Accordingly wire feeding speed has now been optimised at this speed. It may be
noted that speed optimization is necessary for each cored wire type and is plant specific

*Effect of wire feeding speed on average calcium recovery

TRIAL RESULTS WITH VARIANT “A”

Calcium recovery :-

Various data (Wire length fed in Mtr/t, calcium addition in Kg/t, calcium content in PPM and percent
calcium recovery) of experimental heats is shown in the following Table. Calcium content of steel
after calcium treatment ranged between 14-25 PPM and percent calcium recovery varied between
18-32%. Average Calcium recovery for these heats was 24.2%. It may be noted that calcium recovery
for steels treated with cored wires of Ca-Si, Ca-Fe and Ca-Fe-Al was in the range of 12-15% for
Aluminium killed and Al-Si killed grades of steel.

TRIAL RESULTS WITH VARIANT “B”

Calcium recovery :-

Various data (Wire length fed in Mtr/t, calcium addition in Kg/t, calcium content in PPM and percent
calcium recovery) of experimental heats is shown in the following Table. Calcium content of steel
after calcium treatment ranged between 21-50 PPM and percent calcium recovery varied between
22-49%. Average Calcium recovery for these heats was 30.8%. It may be noted that calcium recovery
for steels treated with cored wires of Ca-Si, Ca-Fe and CaFe-Al was in the range of 12-15% for
Aluminium killed and Al-Si killed grades of steel. Based on our experience with variant “A” ,The
speed of wire feeding was maintained at 110-120 Mtrs/Min.

*Experimental data of Pure Ca cored wire of Variant “B”

CONCLUSIONS
• Average Calcium recovery for heats treated with pure calcium cored wire of variant “A” was
24.2% (Range 18-32%) compared to calcium recovery of 12-15% for steels treated with
cored wires of Ca-Si, Ca-Fe and Ca-Fe-Al for Al and Al-Si killed steel.
• Trials with variant “B”cored wire resulted in still higher average Calcium recovery of 30.8% in
the range of 22-49%. The higher recovery in this case is attributed to improved design of this
cored wire compared to variant “A”.
• Feeding speed for such cored wire has been optimised at 120 meters/Minute It may be
noted that speed optimization is necessary for each cored wire type and is plant specific.
• Use of pure calcium cored wire will result in significant cost saving in Ca treatment due to
enhanced recovery and also it will facilitate reduction in inventory by keeping stock of just
one single type of cored wire for all applications of Calcium treatment of liquid steel instead
of different cored wires of Ca-Fe, Ca-Fe-Al and Ca-Si for various applications.

REFERENCES :-
• https://scholarsmine.mst.edu/cgi/viewcontent.cgi?
article=6124&context=masters_theses
• https://www.sciencedirect.com/topics/engineering
/calcium-treatment

ACKNOWLEDGEMENTS :-
I am thank full to the Sparsh sir and all my professor for
providing me knowledge on FACTORS AFFECTNG CALCIUM
WIRE RECOVERY IN LADLE FURNACE.