LADLE REFRACTORIES FOR CLEAN STEEL PRODUCTION

Kunz Gunnar, RHI Asia-Pacific

SUMMARY:
The development of sophisticated metallurgical processes in the secondary metallurgy nowadays allows
the production of ‘Clean Steels’ with lowest levels of oxygen, sulfur, nitrogen, hydrogen and carbon.
Clean Steel refers first of all to metallurgical processes, but refractories have to keep up with these
demands and not reverse the results of metallurgical work.
This article deals with the interactions between steel/ slag and refractories, shows the reasons for the
increase of unwanted elements in steel and explains the proper choice of refractories to achieve at the
same time best metallurgical results and maximum refractory life times.

INTRODUCTION
In recent years the demand for clean steel in critical applications had been steadily rising. Typical
applications are aerospace, bearings, automotive, SBQ, steel cord and spring & rail steel.
Clean steel can be defined simply as ‘steel in which the inclusions do not have an adverse effect on
manufacturing performance and or on final product behavior’ [1]. This is a result-oriented definition
reflecting the combined needs of the steel producers and their customers.
Clean Steel is commonly referred to as fully deoxidized Al-killed steel, because then a high degree of
oxidic & sulfuric cleanliness can be achieved. But also for Si-killed steel metallurgical processes have
been developed to achieve similar cleanliness levels. However for lowest sulfur levels it would be easier
to have it adjusted at an earlier stage (hot iron de-S, low-S scrap).
The main objective of clean steel is inclusions control during the steel making process, especially in
secondary metallurgy, then to avoid putting them back during casting.
The requirements in clean steel are rising steadily, specifications are getting tighter. Key aggregate for
inclusion control is the ladle, fine adjustments are possible in the tundish.
This article offers refractory solutions for clean steel production in the ladle.

CLEAN STEEL FACTORS:

There are countless influences to clean steel production during steel Melting, Tapping and Ladle
Refining/Degassing (table 1).
Major factors to steel cleanliness are process &
Operational Stage Factor
metallurgy related. Understanding and
controlling each of these factors is vital for an Melting Oxygen Blowing Practise
effective operation and significant for a Carbon Injection to Bath/Slag
successful metallurgy.
Refractories (incl. purging) are one factor that Tapping Slag Carry Over
Deoxidation Methode & Timing
becomes important, when all other factors had
been already optimized. Ladle Refining & Deoxidation & Inclusion Engineering
The adjustment of steel cleanliness usually Vacuum Degassing Desulphurization Practise
happens during secondary metallurgy in the Slag Type & Conditioning
Treatment Time & Temperature
ladle, whether it is in the LF, VD, VAD, VOD Ladle Refractories
and/or RH. Thus, the refractory choice for the Purging Intensity & Plug Location
ladle lining is crucial for the achievement of a
high degree of steel cleanliness. Table 1: Key Factors for Steel Cleanliness

OXIDIC STABILITY OF REFRACTORIES

High oxidic and sulfuric cleanliness can be achieved, when reoxidation of the steel by the refractory
lining can be avoided. Out of that reason the oxidic potential of the refractory lining has to be as low as
possible. In addition the refractory lining has to be resistant against basic slags during desulphurization.
1
For fully deoxidized steel the typical oxygen partial pressure is ~10-15bar (The oxygen partial pressure
can be directly calculated from the remaining dissolved oxygen in steel).
To avoid any re-supply of oxygen from the refractory lining into the steel, the refractory oxide’s partial
pressure must be below the steel melt’s partial pressure [2].

The Richardson – Jefferson diagram [3,4]

illustrates this basic rule (picture 1). The temperature
dependence of the free Gibb’s Enthalpy for reaction
to oxides is shown. Also the refractory oxide’s partial

Free Gibbs Enthalpy [kcal/mol O2]

pressure can be found at steel operating temperature 2Fe+O 2
Æ 2Fe
O

of 1,600ºC (highlighted in red).

When compared with the typical oxygen partial

pressure (PP) of below 10-15 bar at 1,600ºC:
- MnO, SiO2, FeOx, Cr2O3: PP ≥ 10-15 bar
SiO 2
Æ causing steel re-oxidation Si+
O2
Æ
Æ
TiO 2

- Al2O3, MgO, CaO, TiO2: PP < 10-15 bar

O2
Ti+
10-15
Æ providing oxidic stability O 2
Æ
l O3
2A 2
l+3
4A
gO
2M
As a result we can classify refractory types suitable 2M
g+O 2
Æ
Æ
2CaO

for clean steel production: 2C

a+
O2

- high in Al2O3, MgO and CaO

- low in MnO, SiO2, FeOx, Cr2O3
Which are: high purity Alumina, Magnesia, Doloma
Refractories
Picture 1: Richardson – Jeffs Diagram
OXIDIC CLEANLINESS:
In laboratory trials [5] the re-oxidation potential of
refractory materials on Al-killed steel was analyzed,
measured by the loss of dissolved [Al] in steel (picture 2)
When re-oxidation from the refractory material occurs, the
oxygen reacts with free [Al] under formation of (Al2O3)
that partly floats to the slag, partly remains in steel as
Al-loss in %

inclusion. As a result the oxygen content of steel increases

plus [Al] loss ‘burn-out’ can be noticed.
Refractory materials with the lowest oxygen potential
results in the lowest [Al]-loss (picture 2).
Synthetic materials, such as pure Lime, Corundum and
Magnesia do result in no or very little [Al]-loss.
High purity refractories, such as Al-spinel, MgO-C and Dol-
C show also low [Al]-loss.
Low purity refractories, such as bauxite, MgO-Cr2O3 and Time in min
Zirconia result in high [Al]-loss. The high oxidic potential Synthetic Materials: Refractories:
of SiO2, Cr2O3 and ZrO2 are responsible for that. 1 … Lime 4 … Al-Spinel brick
2 … Corundum 5 … MgO-C brick
3 … Magnesia 6 … Dol-C brick
Conclusion: 7 … Bauxite brick HQ
To achieve high oxidic cleanliness, the oxidic potential [6,7] 8 … Bauxite brick SQ
9 … MgO-Cr2O3 brick
of the refractory lining must be lower compare to steel, so 10 … Zirconia brick
that re-oxidation is prevented. Picture 2: Al-loss to steel re-oxidation [4]

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SULFURIC CLEANLINESS
A high sulfuric cleanliness is the same as good Desulfurization Reaction:
desulphurization result. Table 3 shows the metal-slag (CaO) + [S] Æ (CaS) + [O]
reactions during steel desulphurization. [O] + [De] Æ (DeOx)
The summarized reaction shows, that CaO from the slag ------------------------------------------
reacts with sulfur in steel in the presence of a strong (CaO) + [S] + [De] Æ (CaS) + (DeOx)
deoxidant to CaS and the oxide of the deoxidant.
To achieve good desulphurization, the CaO activity in the De … Deoxidant (Al, Ca, C)
slag has to be high, i.e. lime saturated basic slags have to be
used. Further the oxygen in steel has to be low, i.e. reducing Conditions for good de-S:
conditions are required by the use of a strong deoxidant. 1) CaO-Activity high
High sulfuric cleanliness can be easily achieved in fully Al- Æ highly basic ladle slag
killed steel, where Al acts as deoxidant. In case of Si-killed 2) [O] content low
steel, it is beneficial if tapping sulfur is already low. It is Æ reducing conditions
advisable to remove S already in the hot iron (from BF) or Æ strong De-Ox of steel/slag
use low-S scrap/ DRI. Satisfactory desulphurization results Æ low Re-Ox by refractory lining
can be then achieved in the ladle through CaSi/CaFe wire-
injection/ top-blowing or deep deoxidation in VD/RH.

To achieve high sulfuric cleanliness, reoxidation of the S-pickup from slag due to
S-pickup from slag in ppm
steel by the refractory lining has to be avoided. So the steel re-oxidation
oxygen potential of the refractory lining must be as low
as possible.
Furthermore a slag zone lining is required that has
minimal wear and does not reduce the CaO activity in the
slag, in order not to disturb the balance (table 3).

In laboratory trials the influence of different refractory

linings on the desulphurization result was analyzed [5].
For that steel with already deep sulfur content of 10ppm
was exposed to a high sulfur containing slag. The sulfur
content development of the steel was measured as a
function of the sulfur reversal from slag to steel
depending to the type of refractory material. Increasing Time in min
sulfur content has to be explained by a reoxidation of
Synthetic Materials: Refractories:
steel by the refractory lining that disturbs the sulfur
1 … Lime 4 … Al-Spinel brick
balance between steel & slag. 2 … Corundum 5 … MgO-C brick
As can be seen in Picture 3 best results are achieved with 3 … Magnesia 6 … Dol-C brick
basic linings no matter whether synthetic lime, magnesia 7 … Bauxite brick HQ
8 … Bauxite brick SQ
or Dol-C, MgO-C. A good result can be also achieved by 9 … MgO-Cr2O3 brick
Al-spinel, improved compare to synthetic corundum. All 10 … Zirconia brick
other materials do result in substantial sulfur reversal and Picture 3: sulfur reversal from slag to steel [5]
are not suitable for deep desulphurization.

Conclusion:
To achieve high sulfuric cleanliness, the oxygen potential of the refractory lining has to be low.

PHOSPORIC CLEANLINESS:
Phosphorus has to be removed from steel early during primary metallurgy.
In case low P-content in steel is required, phosphate bonded refractories (i.e. bauxite) must not be used.
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NITROGEN PICKUP
A direct pickup of nitrogen from refractories in contact with
steel is not the case, while steel can pick up in contact with
air. Modern metallurgy demands low air-exposure of steel
during tapping and more important during casting.
Refractories can help to achieve low nitrogen levels by
protecting steel from air-exposure.

The amount of N-pickup during tapping of EAF/BOF is

influenced by the oxygen content of steel (Picture 4). ULC
steel is therefore most prone to N-pickup. In conventional
cylindrical tap holes the steel stream develops turbulences,
Picture 4: N-pickup during tapping depending
which continue afterwards and mixes with air. The resulting to oxygen content of steel [8]
nitrogen pickup can be enormous. Nitrogen can be removed
satisfactory by vacuum treatment only, so high initial levels

turbulet kin.energy [m2/s2]

result in higher metallurgical efforts and longer treatment
times for removal.
Conical tap holes that are wider in the entry area result in
much less steel turbulences, less air exposure and less
nitrogen pickup (picture 5).
The most inconvenient nitrogen pickup may happen during
casting of steel from ladle to tundish. After secondary
treatment nitrogen levels may be already low, so contact with
air has to be avoided. Common tool used is the ladle shroud.
However, simple use of the ladle shroud does not completely
solve the problem, Ar purging at the collector nozzle / ladle Picture 5: cylindrical vs. conical tap hole [9]
shroud connection effectively reduces the air ingress and
consequently nitrogen pickup. Picture 6 compares
N-pickup in ppm

nitrogen pickup for open casting and closed casting (ladle

shroud) without/with Ar-purging.
There is also a strong influence of the steel’s sulfur
content on the ability to pickup nitrogen [10].
Picture 7 shows that the lower the sulfur content, the
higher the proneness to nitrogen pickup, the higher the
susceptibility to nitrogen pickup. Low sulphur steel Open Closed Casting Middle
Casting without Ar with Ar Chamber
therefore requires closed casting with Ar-purging to
Picture 6: nitrogen pickup for different casting
minimize N-pickup. methods for thin sheet [10]

HYDROGEN PICKUP
N-pickup in ppm

There is usually no hydrogen from the ladle refractory

lining, especially brick linings. Ladles with monolithic
lining have to be properly cured and preheated for quite a
long time, so all crystal water can be removed.
The biggest danger of hydrogen pickup is in the tundish,
when low hydrogen steel (after RH ~1ppm) contacts the
lining made of slurry gunning mix in combination with S-Content in ppm
cold tundish practice. Then a hydrogen pickup of 2ppm is Picture 7: nitrogen pickup depending on
possible. To avoid this, waterless dry setting or self sulfur content in steel
hardening mixes can be used.

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CARBON PICKUP
Nowadays Ultra Low Carbon Steels are getting more important. Decarburization Reaction:
They obtain their strength not from carbon in the steel structure, [C] + [O] Æ {CO}
but secondary precipitations during annealing process. [%C] · [%O] = 2.5 ·10-3 · pCO (T=1600ºC)
For such steel grades usually carbon is effectively removed
during primary metallurgy (EAF/BOF) by oxygen blowing. Conditions for low C-content:
During secondary metallurgy the carbon content can be further 1) CO-pressure low
removed by vacuum treatment, down to 20ppm. Æ vacuum treatment (RH)
2) [O] content high
Table 4 shows the reaction of oxygen & carbon in steel to CO-gas Æ not or partly de-Ox steel
with conditions for low carbon content in steel. Optimal 3) low C-pickup from lining
conditions are under vacuum, when the CO-gas is removed, so Æ fired or low-C bricks
more CO-gas can be formed. Furthermore an oversupply of
Table 4: Conditions for low carbon in steel
oxygen will speed up the reaction. Vacuum treatments where the
steel is just partly deoxidized were developed. Preheating of MgO-C bricks
The refractory lining should not supply fresh carbon leading to an 10min at 1,200ºC, vacuum
Æ strong C-pickup
unwanted C-pickup. Fired or low-C bricks are the best solution. 14%C

10%C
In laboratory trials the influence of the C-content and the length of
preheating on C-pickup were tested. [5]
Picture 8 shows the different C-pickup of a 10min and 120mins 5%C
preheated MgO-C brick lining. Short preheating does not prevent C-
pickup: a higher C-content of the brick also results in higher C-pickup.
The situation changes when the brick is preheated for 120 min. Then
the surface is decarburized, C-pickup is less and independent from the Preheating of MgO-C bricks
original C-content. 120min at 1,200ºC, air
Æ surface decarburization
Æ little C-pickup
The conclusion could be that MgO-C bricks in the ladle are for ULC 5%C 10%C 14%C
steel production not suitable. However, in the slag zone MgO-C bricks
usually provide the highest life time result. The best compromise is
then to use MgO-C bricks in the slag zone only and low-C or C-free
bricks in the metal zone plus proper preheating.
It will also help to avoid production of ULC steel in the first 3-5 heats,
after that the ladle is ‘ready’.
Picture 8: C-pickup by MgO-C bricks
depending to preheating [5]
Just for permanent vacuum treatment and highly oxidizing conditions
(i.e.VOD process), fired Dol or Mag-Dol bricks will result in better
metallurgical results (lowest C levels) plus satisfactory refractory
lives.

5
GASPURGING IN THE LADLE
Interactions between steel/ slag and refractories had been discussed.
These reactions slow down considerably when higher concentrations
are reached in the reaction zone. To improve this, a kind of ‘motor’
is necessary to bring movement into the steel bath. This can be done
CO
by electromagnetic stirring, or - more effective - is the use of gas
purging through the ladle bottom.
Ar-bubbles are injected into the steel bath. By moving upwards, they C O
cause a stirring effect of the steel melt. This improves steel
Picture 9: Heterogenous Nucleation at the
homogenization in terms of temperature & chemical composition, surface of Ar-bubbles
but also steel cleanliness. Non-metal inclusions - steel impurities,
chemical reaction products or refractory wear products – are
Linear Bubbling Turbulent
transported much faster to the top-slag than just waiting for flotation Bubbling
/ buoyancy to do its work.
Equally important, chemical reactions can happen much faster at the
surface of Ar-bubbles as the most effective way of heterogeneous
nucleation (Picture 9). The larger the collective Ar bubble surface,
the faster chemical reactions can process. Many fine bubbles are
more effective than a few big bubbles. Initially the number of fine
bubbles grows with the gas pressure (picture 10). After a certain bubble number

limit is reached, the number of bubbles remains the same, but just
the bubble volume increases. Then the growth of the collective
bubble surface slows down. This continues until a critical point,
above that linear bubbling changes into turbulent bubbling. Bubbles Gas pressure

coagulate into bigger bubbles, the number of bubbles gets reduced

Effective Ineffective
Purging Purging

drastically. As a result purging efficiency in the turbulent area is

Picture 10: Bubble-size & -volume depending
ineffective and leads to unnecessary cooling of steel and higher to gas pressure
refractory wear.
Steel Desulfurization [11]:
Another important function of Ar-purging is the mixing of steel &
slag, required for effective steel desulphurization (Table 2 & 5). The
de-S speed is equivalent to the slag/metal interface area, which is
ks ... de-S speed
equivalent to the stirring power and gas-flow rate by Ar-purging ms … mass transfer coefficient
(picture 11). A … slag/metal interface area
Until a certain gas-flow rate there is little slag-metal mixing, hence V … steel volume
the rate of desulphurization is slow. For higher stirring rates better έ … stirring power, n= 0.25-0.3
mixing slag-metal happens, so de-S speed increases accordingly. The
Table 5: Influence of Purging to steel De-S
transition point depends to the slag type & viscosity.

Picture 11: De-S speed depending to Ar gas

6
 REFRACTORIES FOR CLEAN STEEL
While MgO-C bricks are standard for the ladle slag zone (exception: VOD ladle), for the metal zone
there is a big variety of brick types, which have to be chosen according to their features (table 4).

MgO-C Dol-C Dol Mg-Cr AMC Bauxite Monolithic Al-Spinel

Purity (max. 100%) 97-98% 98% 98% 85% 95% 88% 98% 99.2%
Bonding Resin Resin Ceramic Ceramic Resin Ceramic Hydraulic Ceramic
Thermal Expansion at 1,600*C 2.0-2.5% 1.8% 2.0% 1.5% 2.3% 0.9% 1.2-2.3% 1.6%
Thermal Expansion after cooling 0-0.5% -0.8% -1.0% 0.0% 0.7% 0.0% 0.5-1.5% 0.5%
Thermal Shock Resistance - - -- + ++ +++ ++ ++
Hydration Resistance + - -- - ++ ++ +++ +++
Decarburisation Resistance - +/- +++ +++ - +++ +++ +++
Oxidic Stability +++ +++ +++ -- + --- +++ +++
Chemical Stability - acidic slag +/- ++ +++ -- - +/- +/- +/-
Chemical Stability - basic slag ++ +/- - +/- +++ + +++ +++
Abrasion Resistance Stirring + - - +/- ++ + +++ +++

Table 4: Refractory Types for the Ladle Metal Zone and their features during application

CARBON CONTAINING REFRACTORIES

MGO-C BRICKS The ‘MgO-room’

MgO is chemically very stable (picture 1) and in
contact with basic slags the MgO-solubility is very low,
higher in contact with acidic slags (picture 12). Wear
resistance against slag attack increases with the
periclase (MgO crystal) size due to decreasing grain
boundaries area (picture 13)

Fired MgO bricks have too high thermal expansion and Optimum Point (4%MgO)
too little thermal flexibility to be suitable for the ladle
wear lining with its permanent temperature changes. In Picture 12: Theoretical MgO solubility in
addition fired MgO bricks don’t provide a barrier CaO-SiO2-Al2O3 slags
against slag infiltration, slag would infiltrate deeply
until it reaches solidification temperature.
To make MgO bricks useable for practical ladle
application, graphite is added, usually between 5 –
14%, brining with it carbon (resin or pitch) bonding
technology.

Sinter Magnesia Large Crystal Magnesia Fused Magnesia

[30-120μm) [150-200μm] [500-10,000μm]
Corrosion Resistance

Picture 13: crystal size of Magnesia grade

7
Graphite has two decisive advantages that explain its application into ladle refractories:
1) Chemical Influence:
Reduction of FeOx in infiltrating slags following a (CaO-FexSiO2)liquid Æ [Ca2SiO4]solid + Femet
eutectic ~1300°C eutectic >1650°C
Redox reaction (table 5)
Table 5: chemical influence of graphite
2) Physical Influence:
Non-wetting effect of graphite on infiltrating slag. As
a result slag infiltration depth is reduced. Picture 14
shows the difference of the wetting angle of a slag
drop on MgO and on Graphite.
Graphite also fundamentally changes the brick properties,
such as Thermal Conductivity and Modulus of Rapture Picture 14: non-wetting effect of graphite
(Picture 15)
Disadvantage of graphite addition and carbon bonding are Reduction of FeOx

at 1000°C
the proneness to C-pickup of steel and the temperature Thermal Conductivity

Modulus of Rupture [kg/mm2x103]

Thermal Conductivity [kcal/mh°C]

loss through thermal conduction.

Slag Infiltration Depth [mm]

Modulus of
Al2O3-MGO-C BRICKS Rupture
AMC bricks are similar to MgO-C bricks, with the
difference that the main raw material used is Alumina Slag Infiltration Depth
plus some Magnesia. While AMC bricks are just for use
in the ladle metal zone, they are polular due to their in- Graphite Content [%]
situ formation of MA-spinel in connection with volume Picture 15: influence of graphite addition
expansion (picture 16), that closes surface porosity & on MgO-C brick properties
brick joints, avoiding slag/steel infiltration.
Remarkable is their resistance to abrasion, which makes
them particularly suitable for the bottom impact.
They are an excellent solution for Al-killed steel grades
when the slag has Al2O3-content >15% [12] and no
threat to steel cleanliness as long fused corundum with
low oxygen potential is used. Due to the MA-spinel
formation less graphite addition is required to achieve the
same slag-stop effect as MgO-C bricks.

DOL/ DOL-C BRICKS

Dolomite is the chemically most stable refractory
material (picture 1) and the best lining type for deep
Picture 16: Thermal expansion of AMC bricks with
desulphurization. Main problem is however the proneness in-situ MA-spinel formation
to hydration when cooled <600ºC and the negative
thermal expansion of dolomite when cooled after use.
Fired dolomite is therefore most suitable for non-stop
operation with minimum thermal changes (f.i. VOD
ladle). In order to provide a better brick flexibility and avoid slag infiltration, graphite is added and the
brick carbon (pitch or resin) bonded. Brick property development is similar to MgO-C bricks (picture
15). Due to the lower porosity of dolomite, less graphite (usually 2% only) is required compare to MgO-
C & AMC bricks. As a result Dol-C bricks are less thermal conductive and cause less C-pickup in ULC
steel grades. After proper preheating, Dol-C bricks can be even used in VOD ladles for stainless steel
production.
Dolomite performs best in contact with acidic slags due to its ability to form a dense C2S/C3S layer with
infiltrating slag. In contact with basic slags it is important the slag is CaO-saturated, which can’t be
8
guaranteed for all stages. Infiltrating Al2O3-rich slag forms low-melting CA-phases in the surface layer.
Out of that reason for basic slags usually MgO-C or Alumina/AMC linings are more suitable.
CARBON FREE REFRACTORIES

MGO-CHROME BRICKS
In the past fired Mg-Cr bricks were often used for ladle linings. Cr-ore addition to MgO solved the
problems of MgO thermal inflexibility. The relatively heterogeneous distribution of magnesia, Cr-ore
and chromite spinel results in an improved thermal shock resistance [13].
But unfortunately Cr2O3 has a high oxygen potential (picture 1), that is why Mg-Cr bricks can’t be used
for clean steel production. In contact with acidic slags they can’t prevent deep infiltration; the resulting
chemical wear is high. That is why they were also replaced by dolomite in VOD ladle linings. In recent
years Cr-ore got very expensive, so the use of Mg-Cr bricks for ladles is not common any longer.

MONOLITHIC LINING
Monolithic casting lining of the metal zone is one of the
latest type of refractories for the ladle (for slag zone
commonly MgO-C is used)
Castables are alumina based, typically based on fused
alumina, under use of a hydraulic cement binder. This
makes them most suitable for ultra low carbon steel
production. In case white fused alumina is used, they also
have excellent oxidic & good sulfuric stability (when
MA-spinel forming/added). For lower purity alumina
types (brown fused alumina, bauxite), oxidic & sulfuric
stability is less (pictures 2 & 3). Because there is a need
to precisely preheat the ladle for 50 hrs, all crystal water
can be removed from the cement binder, so there is also
no risk of hydrogen-pickup.
Picture 17: Monolithic lining casting procedure
Monolithic linings perform best in steel plants for flat
steel production (usually Al-killed & basic slag), while
Heat up Graph
resulting in shorter lifes in steel plants for long product 1.000
Working Temperature
production (usually Si or Al/Si mixed killed & acidic
slags). 55-60 °C/h
T em p eratu re [°C ]

States of the art are thixotropic castables, which liquefy 600

under exposure to vibrations, but solidify when the

30-35 °C/h
vibrations are stopped. Templates are therefore required 400

to be equipped with vibrators at the inside (picture 17). 10-15 °C/h

Though monolithic lining of ladles appears easy and the 200

10 °C/h
‘joint-less’ result tempting, it requires investment into
new machinery and the precise following of complex 15 20 Hours 35 40 46 50 60

installation & drying procedures: These include

positioning the template into the ladle, centering and Picture 18: Monolithic lining heat up graph
casting of the gap behind the vibrating template by a
rotating conveyor belt placed on top of the template
(picture 17). After 4-6 hrs drying the template is removed and the bottom can be cast. Finally the metal
zone lining goes to 50 hrs preheating to remove the crystal water. The exact preheating curve has to be
followed (picture 18) with 2 holding points for crystal water removal.
Main advantage of the monolithic lining lies in the option to ‘reline’ the metal zone. For that the worn
out slag zone is removed and the metal zone cleaned from slag/steel-infiltrations with a specific chisel
driller. After that the template can be inserted again and the remaining gap casted. Then preheating
9
schedule to be repeated. The more often the relining is repeated, the lower the cost of monolithic lining
and the less refractory waste material.
ALUMINA-SPINEL BRICKS
These bricks combine the advantages of brick lining &
monolithic lining in terms of easy brick lining, high oxidic
& sulfuric cleanliness, no C-pickup and good thermal
insulation. From raw material base (fused alumina, spinel)
most similar to monolithic lining, a brick lining of course
can’t be relined. However, due to the low wear-speed and
high strength of the brick lining, metal zone thickness can
be minimized, so that steel content is maximized. Because
no joint-wear happens, it can be used until 20-30mm
residual thickness. As a result the specific consumption is
close to monolithic lining. And that without any investment
in new machinery!
Fired high alumina bricks show excellent results for the Picture 19: thermal expansion of alumina
production of Al-killed steel, especially in cases where the refractories with addition of MgO
slag has >15%Al2O3. However, the life is reduced in and pre-reacted MA-spinel [14]
contact with highly basic slags due to their ability to pick-
up Al2O3. This problem is addressed by the addition of
MgO with in-situ formation of MA-spinel, forming a dense
MA-layer at the brick surface. This concept works well for
AMC bricks. But in fired bricks without the presence of
graphite, capable to relieve tensions, this can lead to
uncontrolled irreversible expansion. Under addition of pre-
reacted MA-spinel the surface barrier function remains
intact, but also thermal expansion can be controlled to
minimized remaining expansion (picture 19). MA-spinel is
available in different MgO & Al2O3 compositions. The
Picture 20: Phase diagram MgO-Al2O3 [13]
stoichiometric MA-spinel with ~78%Al2O3 was found
most suitable [16] (picture 20).

10
REFRACTORY WEAR MECHANISMS:
The chemical interactions between steel and refractories was discussed influencing steel cleanliness and
causing pickup of unwanted elements (O,S,N,H,C,…).
But how does the refractory wear happens that sets free unwanted elements? Picture 21 illustrates
schematically the different stages of refractory wear in contact with slag/steel:

1.Stage: Coating
Slag coats the brick surface through direct contact during casting,
when the bath level sinks along the barrel height.

2.Stage: Infiltration
Slag infiltrates into the brick surface, after a new heat is tapped into
the ladle that melts the coating slag. Because of the ferrostatic
pressure, the slag-layer is pressed on the refractory surface.

3.Stage: Interaction
The infiltrated slag interacts with the refractory surface through
chemical reactions. Main attack happens along the weaker part,
binding matrix and grain boundaries, first. Graphite and Antioxidants
are added to combat this process. When the attack processes, big
grains loose their attachment to the structure. Through circulation
reaction products are swapped outside, fresh slag goes to the front.
The liquid & solid reaction products are usually transported through
steel to the top-slag. This process is accelerated under Ar-purging
through the bottom. However, interaction between the reaction
products and steel is likely and may become a critical factor of steel
cleanliness.
The reaction speed is slower compare to the slag zone, because less
slag is available. But because the process repeats every heat, still
there is some significant influence of the ladle slag on the metal zone
lining.

4.Stage: Consequences 1. Steel bath, 2. Attached slag layer, 3. Original Materia

4. Big grains, 5. Binding Matrix, 6. Penetrated Layer
The densification factor of the infiltrated surface layer is not to be 7. Big grains loosing attachment

underestimated. When the lining is cooled down after treatment, the Picture 21: Wear Mechanisms [14]
infiltrated layer behaves differently to the original refractory lining.
Because all porosity is filled up, the surface layer might not be able to shrink; even expansion effects
can take place (MA-spinel formation, C2S-decay) during cooling. As a result, the surface layer might
tend to spall, when the tensions below the surface exceed the critical material strength.

Because of all these reasons, deep infiltration of the metal zone lining has to be prevented. For every
refractory type a different technology is required plus for every kind of slag a different approach is
required. Therefore the selection of refractories for different steel/type is an important task (table 4).

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CHEMICAL STABILITY OF REFRACTORIES
Picture 21 explained how slag manages to infiltrate the refractory brick structure. What happens then in
the infiltrated zone differs whether the refractories are carbon bonded or casted/fired.

C-BONDED REFRACTORIES
To this group belong MgO-C, AMC and Dol-C bricks. Their
reaction to infiltrating slag first of all depends to the added A B C
graphite and antioxidants.
Components of the infiltrating slag (FeO, MnO, …) attack the
carbon binding matrix resulting in carbon ‘burn-out’ and loosening
of the matrix. As a result a de-carburized zone emerges (Zone B in
picture 22). In MgO-C bricks graphite and antioxidants are slowing
this process. In Dol-C bricks a dense C2S/C3S layer can form,
when the infiltrating slag is rich in SiO2. In AMC bricks the
formation of MA-spinel can form a dense barrier.
However, once the binder matrix is dissolved, remaining ceramic
bonding is low. So the grains in the de-carburized zone are quickly A B C
attacked along their grain boundaries and also soon eroded away Original De-Carb. Slag
by bath agitation. Brick matrix Zone Surface
Picture 22: Wear of C-bonded Refractories
ALUMINA REFRACTORIES
To this group belong Monolithic Lining, Bauxite and Alumina-
Spinel bricks. Slag infiltrates into the refractory, where CaO and
SiO2 from the slag form low-melting phases together with Al2O3
from the refractories [17]. A dense attack zone is formed (Zone B
in picture 23) with high & low melting CA(S) phases, prone to
cracks formation along the border to the original brick matrix (D in
picture 23).
The attack speed slows with higher purity of the alumina used:
bauxite Æ brown fused alumina Æ grey fused alumina Æ white
fused/ tabular alumina.
The reaction products can have severe effect on the steel
A B C
cleanliness through re-oxidation of steel (picture 2). Original Attack Slag
Slag infiltration can be effectively reduced/ slowed by formation of Brick matrix Zone Surface
a dense surface through in-situ MA-spinel formation under volume Picture 23: Wear of Alumina Refractories
expansion or the addition of pre-reacted MA-spinel with more (D … interface cracks)
chemical stability against CaO/ SiO2 attack.
Unfortunately MA-spinel gets attacked by FeO/ MnO. As a result spinel forming/containing refractories
perform best in Al-killed steels, where also the slag is low in FeO/ MnO. In Si-killed steels usually the
FeO/ MnO content is higher, then spinel forming/containing refractories are wearing faster.

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