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BASIC
CALCINED MAG C (93%)
It is basically reuse of the MagC bricks that have been used once in the lining. After their service
they are calcined at around 13001400oC which results in complete oxidation of remaining C in
the bricks. The resulting product can once again be used as aggregates in brick manufacturing.
Advantage
It is used as a source of MgO in basic burnt and un-burnt bricks.
Disadvantage
Any unreacted antioxidant present such as aluminum can react to form its respective
hydroxide and cause volume expansion.
CHROME ORE
The general chemical formula of natural chrome ore is FeO.Cr2O3. Part of the FeO in chrome ore
is replaced by MgO and parts of Cr2O3 are replaced by Al2O3 and Fe2O3. This is all in complex
solid solution .Therefore it is represented by the general formula of RO.R2O3. The most common
variety of chrome bearing refractory is magnesia chrome and chrome magnesia. The former
quality consists of more than 50% magnesia and the later variety consists of more than 50%
chrome ore.
Typical composition of chrome ore:-
Cr2O3- 48-55%min)
SiO2- 1%-2%(max)
Fe2O3- 18 24 %
MgO- 10 %
Al2O3- 7 8 %
Disadvantage
One main disadvantage of natural chome ore is the presence of silica which is highly
detrimental because it reacts with it to form low melting phase fyalite(F2S). On firing it
forms spinel due to the interaction between oxides of type RO and R2O3 and hence this
causes volume instability (usually expansion due to the lower sp. gravity of
spinel),chrome is neutral in nature and hence has a lower corrosion resistance against
basic slag than the variety incorporating magnesia and chrome or magnesia alone
Advantage
Chromite itself has high refractoriness 21350C unlike magnesia.
Neither magnesia nor chrome are self sufficient because magnesia is superior to chrome in
terms of corrosion resistance but has poor thermal shock resistance, so the best way is to
incorporate chrome in magnesia which increases the spalling resistance of magnesia as the
thermal expansion coefficient of chrome is less than that of magnesia., and since its neutral in
nature its withstanding capacity to acidic slag is good and even chrome silica briks had been
developd to increase the spalling resistance of silica.
FUSED MAG CR
This is basically a synthetic raw material which is prepared by a way in which chrome
ore and magnesia are mixed, fused in an electric arc furnace ,solidified and ground into
required size fractions.
Advantage
Excellent volume stability since spinelization has already occurred, since its fused it has
superior corrosion resistance but not as good as fused magnesia, higher purity.
Disadvantage
Higher cost, poor thermal shock resistance than sintered variety though spinel inside it
helps to increase thermal shock resistance to some extent.
FUSED MAGNESIA
Fused magnesia is prepared by melting sintered magnesia clinker in an electric arc furnace,
solidified and ground into required size fractions.
Advantage
Higher corrosion resistance than sintered variety due to fusion & slow cooling involved
forming crystals of larger sizes. This indicates smaller no. of crystals per unit area and
grain boundary. As corrosion gets facilitated in presences of grain boundary only it
shows the better resistance.
higher purity, higher density, larger crystal size.
Disadvantage
Poor thermal shock resistance than sintered magnesia, as due to lesser porosity the
grain hardly finds any space to accommodate volume change.
higher cost because higher temperature require melting magnesia.
GRAPHITE
Carbon has several allotropic forms such as diamond, graphite and amorphous carbon (coal,
coke, resin, pitch)
Structure of graphite
The structure of graphite is layered with huge hexagonal network consisting of carbon atoms
and the bond length within the hexagonal networks is 0.142 nm, indicating a strong covalent
bond but the distance between layers are large close to 0.3354 nm revealing that the layers are
bonded by weak van der waal forces. Therefore graphite shows a large anisotropy in properties.
These layers can slide over on another and hence it has a greasy touch.
Advantages: -
It is the only refractory material which has both high corrosion resistance due to non
wetability as well as high spalling resistance due to high thermal conductivity as well as
high refractoriness
Disadvantage:-
poor oxidation resistance, achieving an oxidation proof condition is a common need for
all carbon based products,
It is of 2 types: flaky and powdery. These 2 are distinguished on the basis of their aspect
(length: width) ratio, usually flaky variety consists a higher % of fixed carbon.
Due to higher thermal conductivity of graphite, if its used in greater quantities, they may
transfer heat from liq. Steel from ladle thereby reducing steel temp. Consequently steel
density & quality.
SEA WATER MAGNESIA
Sea water magnesia is the purer variety than the one produced by sea water. The procedure of
obtaining sea water magnesia is addition of dolomite or limestone to sea water which already
contains magnesite salts(MgCl2, MgSO4). This dissolved salt reacts with the added dolomite or
limestone and magnesium hydroxide is precipitated. This precipitate is dehydrated and
calcined to obtain sea water magnesia.
Advantage
Since this variety is precipitated variety so its MgO content is on the higher side and
impurities are on the lower side.
Good spalling resistance.
Disadvantage
Poor corrosion resistance
Though impurities are on the lower side and care is taken to remove B2O3 but its still
contaminated with B2O3 which forms glassy phase(MgO.2B2O3) at high temp and
reduce hot properties at application temperature.
DEAD BURNED MAGNESIA
Magnesite is calcined in a rotary kiln whereby magnesite loses its structural water and carbon
dioxide and crystal size grows and changes from tetragonal to cubic. After being calcined at
about 1650 1700 degree C , its hydration resistance is improved drastically.
Advantage
It has superior spalling resistance than fused variety because its porosity being on the
higher side it can accommodate the expansion occurring.
Disadvantage
It has poor corrosion resistance against basic slag than the fused variety.
Again main impurities are CaO and SiO2 whose ratio should be ideally >2 because lower
ratio results in the formation of low melting phases like montecellite and merwinite.
The rate of formation of the glassy will mainly depend on the size of aggregates. Smaller
the size of impurities greater will be the rate of glassy phase formation.
DOLOMITE
Advantages
1. More basic in nature than magnesite, thereby being more resistant to basic slags than
that of magnesite refractories.
2. Dolomite bricks have better RUL than Magnesite refractories.
3. Lower melting phases of monticellite and merwenite are not formed in dolomite bricks,
unlike of magnesite.
Disadvantages
Fair spalling resistance which in turn depends on % of silica and consequent C2S phases
formed, which have 3 polymorphs which are stable at <675 deg C, 675-1410 deg C and
at > 1410 deg C. Formation of gamma phase at less than 675 derg C is associated with
considerable vol expansion , which in turn decreases the spalling resistance.
FIRECLAY
Fireclay has a disordered kaolinite structure and unlike pure kaolin, are not white burning primarily
due to the presence of iron oxide and titania as impurity. In fireclay [SiO4]-4 tetrahedra and AlO(OH)2
octrahedra are linked together to from two dimensional sheets of tetrahedra and octrahedra. It occur in
well define beds associated with coal seams or lenticular beds associated with coarser segments.
Fireclay chemical compositions have a range of 23-34 wt% Al2O3, 50-60 wt% SiO2, and 9-12 wt%
L.O.I. Fire clays usually contain Fe2O3 (maximum 25 wt%), along with CaO, MgO, K2O, Na2O, and
TiO2.
Depending upon their capacity to withstand high temperatures before melting, the fireclays are graded
into the following:
ADVANTAGES
Fireclay is classified under acid refractories i.e., it is not attacked by acidic slag. In blast furnaces, the
lining is done with fireclay bricks. Because of the abundant supply of fireclay, its comparative
cheapness and resistant to high temperatures, having fusion points higher than 1,600C; the refractory
bricks made out of it are the most common and extensively used in all places of heat generation, like:
Boiler furnaces
Chimney linings
Pottery kilns
Blast furnaces
Reheating furnace
DISADVANTAGE
Fireclay during firing shrinks and leaves pores and cavities around the chamotte grains. Its
contain appreciable amount of impurity like quartz, feldspars, micas, iron and titanium bearing
minerals, limestone, megnesite, gypsum which acts as a flux except quartz and reduce the PCE.
During firing, there is development of glass, by the combination of silica from clay
decomposition, other oxides and impurities. So fireclay bricks will tend to deform under load.
PYROPHILITE
ADVANTAGE
It has excellent thermal stability and is added to clay to reduced thermal expansion when firing.
DISADVANTAGE
High alkali content, precalcination is required to remove structural water to eliminate shrinkage.
CALCINED BAUXITE
ADVANTAGE
Its higher alumina content (nearly 85%) is its prime advantage as high alumina content improves
the strength, higher thermal conductivity because of iron oxide and titania and higher corrosion
resistance. It gives mullite and corundum after firing and thus have superior properties than lower
alumina containing bricks.
DISADVANTAGE
Bauxite has to be calcined to facilitate concentration of alumina and prevent structural spalling
during firing or usage by removing structural water and also convert the clay contained as
impurity into mullite and bring volume stability. Actually bauxite contains clay impurities which
inherently contain alumina and silica havin sp gravities of 3.98 and 2.65, which during firing
converts to spinel with chemical formula 2Al2O3.SiO2 having sp gravity 3.15, so , due to density
decreament volume expansion occurs, called as burting expansion of bauxite. Iron oxide and
titania though helps to increase spalling resistance due to high thermal conductivity to some
extent but at some point they form iron spot and low melting phases which detoriates high
temperature property.
DIASPORE
ADVANTAGE
DISADVANTAGE
For use in refractory purpose, precalcination is needed to remove structural water. It contains less
amount of alumina than bauxite and concurrently higher on impurities.
CALCINED ALUMINA
In the bayers process bauxite is treated with caustic soda to precipitate aluminium hydroxide
which is calcined at 1000 1200oC in a rotary kiln to produce calcined alumina.
ADVANTAGE
Good spalling resistance, corrosion resistance is good due to low impurity content but less than
that of tabular alumina and sintered alumina, available at a reasonable price and used for the
manufacturing of tabular and fused alumina.
DISADVANTAGE
Since it is only calcined at comparatively lower temperature hence its crystal sizes are smaller
and porosity on higher side to have low corrosion resistance.
ADVANTAGE
It shows high chemical purity, high chemical inertness, excellent abrasion resistance, good
corrosion resistance due to very high alumina content (nearly 99.5%), better than calcined
alumina due to higher crystal size than calcined alumina. It has higher thermal shock resistance
than fused alumina due to higher porosity.(5%). Its BD is 3.55 gmcc.
DISADVANTAGE
Due to higher porosity its corrosion resistance is lesser than fused alumina, higher cost so its
presence in the composition imparts better properties to the brick very much will depend on how
much the customer pays.
WFA
This variety is prepared by fusion route. Here calcined alumina which is obtained by bayer
process is fed to an electric arc furnace where it is melted beyond its fusion point where by the
impurities are removed and hence result in a fused high purity product.
ADVANTAGE
High purity suitable for critical application, larger crystal size compared to WTA and hence
greater corrosion and erosions resistance.
DISADVANTAGE
It shows low thermal shock resistance, because of lower porosity(<1%) and higher BD of 3.7
gm/cc.. It is costly.
BFA
It is produced by electro-fusion of bauxite in EAF and has relatively low alumina content
(95.1%).
ADVANTAGE
Good corrosion resistance than WTA because of larger grain size but less than that of WFA
because at higher temperature iron oxide forms low melting phases. It shows better spalling
resistance than WFA because of higher thermal conductivity of iron oxide and titania.
DISADVANTAGE
The sillimanite groups of mineral consist of Sillimanite, Kyanite and Andalusite, which have the
same chemical composition (Al2O3.SiO2) but are different in crystal structure and properties.
In all these three structures half of the Al ions are 6 coordinated and rest half are 4,5, and 6
coordinated in sillimanite, andalusite and kyanite respectively.
ADVANTAGE
They are used to manufacture bricks whose alumina content varies from 55% to 65%. They are
readily converted to mullite and silica (crystobalite and amorphous silica) when they are heated in
between 1200oC 1500oC. Among them kyanite give mullite at lower temperature(1300 deg C)
compared to other and sillimanite give mullite at higher temperature. Andalusite readily
converted to mullite at 1350-1400oC with no significant change in volume. Raw kynite can be
used in finer fractions in the brick to reduce porosity via volume expansion and fill up the pores.
SILLIMANITE:
ADVANTAGES:
1. Provide good spalling resistance because of small value of thermal expansion coefficient.
DISADVANTAGES:
Sillimaanite can only be obtained in fine fractions so in coarse or middle fractions they
cannot be used.
ANDALUSITE: andalusite acts as a better refractory than sillimanite as it involves only
1-2% voliume expansion during conversion of mullite.
KYANITE
Advantages:
Raw kynite can be used in finer fractions in the brick to reduce porosity via volume expansion
and fill up the pores.
Disadvantages:
MULLITE
Here calcined alumina and silica sand are mixed and fired in a rotary kiln for sintered variety and
fused in an electric arc furnace for fused variety. Like WFA and WTA sintered variety has a
better spalling resistance and fused variety has a better corrosion resistance.
ADVANTAGE
In mullite based bricks synthetic aggregates of mullite are only used in various size fractions and
thus those bricks have superior properties than sillimanite or fireclay bricks that contain
crystobalite and glass(reaction of alumina with soda, potash and iron oxide) along with mullite
that hamper the high temperature properties and corrosion resistance of the brick against basic
slag.
DISADVANTAGE
Since mullite consists of 30 weight % SiO2 so its corrosion resistance against basic slag is lower
than that of corundum based refractories.
REACTIVE ALUMINA
Reactive alumina is a key components and performance enhancers for modern refractory bricks.
They have a major impact on the strength, porosity, and slag and wear resistance of the
refractories.
The name "reactive alumina" initially comes from the ceramic industry, where it refers to the
sintering reactivity of alumina powders.
Reactive aluminas are fully ground powders, which are significantly finer than ground aggregate
minerals. They are practically agglomerate free when compared to ground calcined aluminas and
therefore do not absorb water. This reduces the liquid requirement of refractory formulations and
results in enhanced performance. Reactive alumina is typically combined with ground aggregate
fines (e.g. tabular alumina) to fill out the matrix particle distribution of a refractory formulation
and achieve optimized particle packing. Almost all modern high performance alumina refractories
contain significant amounts of reactive alumina.
Reactive alumina is produced dry milling in ceramic lined batch ball mills using ceramic
media. The grinding
process eliminates the porous agglomerates formed during the calcination process
resulting in optimal
products for achieving the targeted ceramic application properties
Reduced water demand
Low open porosity
Excellent sinter reactivity
Excellent wear resistance and mechanical strength
Excellent high temperature mechanical performance
RESIN
The most commonly used resin is PFR phenol formaldehyde resin which consists of a
cyclic chain consisting of phenol (OH) and formaldehyde (CHO) groups.
Again the resin can be classified as resol and novalak types
Advantage :-
Disadvantage:-
Resol:-It has to be stored under 25 degree C or otherwise it polymerises itself and becomes
useless for mixing.
Novalak:-it requires hexamine addition which provides extra CH2O group that helps in
polymerization.
If resin is used in higher proportions, then due to its high viscosity of approximately 7000
cps, agitation problem may occur during mixing. As well as, green shaped body strength
may also get reduced. Whereas, if used in larger quantities, during application, say mag
carbon bricks in ladle operations, all resin may get converted to carbon only, thereby
making the whole shape completely disintegrated.
Also, as resin contains volatile matter too, during operation it may crate substantial amount
of porosity, thius reducing strength of the body.
While resin doesnt need preheating like that of pitch which has a much higher viscocity, the
C content of resin is comparatively low but pitch is carcinogenic.
Chemical binders
The role of chemical binders is of upmost importance in chemically bonded and unfired
bricks, mortars, gunning masses and ramming masses.
The chemically bonded refractories are not fired and hence when they are installed they
dont have as hih strength as fired variety. So addition of chemical binders is necessary.
Advantages
In gunning masses during hot gunning there is a sudden and very high temperature change
and thus the water is quickly removed before it can impart strength to the gunning mass on
drying. So the presence pf chemical binder helps as it reacts to form phosphate, chromate or
sulphate bonding and impart strength to the gunning mass and hence the structure. If the
binder would have absent then the gunned material wouldnt have patched properly.
Disadvantage
The chemical binders especially silicates and phosphates should be used to achieve
optimum results as they reduce the hot properties and abrasion resistance due to formation
of low melting phases.
Hexamine
Hexamine is used in carbon based refractories to aid in polymerization of resin (resol type).
Powder resin is the phenol formaldehyde resin in powder form. It is used along with liquid
resin.
Advantage
Liquid resin is added to bring the wokability in the graphite mixed mixture. But if all liquid
resin is used to bring the desired amount of C addition through it then the mixture becomes
over workable i.e the workability is lost and purpose is not served. Hence powder resin has
to add to some extent.
Disadvantage
Powder resin cannot be used singly because firstly it has no liquid content and hence cannot
provide any kind of workability and secondly its very costly
Role of binders
SHMP its use in the ramming mass helps in the setting of ramming mass by the formation
of a gel like structure upon curing and later on during firing it forms phosphate bond to give
strength at high temperature prior to sintering.
Titania Its also used as sintering aid but its cost is high and it cannot be used in chrome
bearing bricks because of the complex reactions which it undergoes with various oxides
present and result in glass formation.
Chromic acid helps in formation of chromate bonding in ramming masses and gives
strength at high temperature before sintering sets in.
Sodium silicate - addition of it in ramming mass helps in bonding at room temperature due
to its adhesive forces as well as it gives strength at high temperature by formation of
chemical bonds with the base material.
Additives
Al POWDER
Metallic Al powder is used as an effective anti oxidangt in Mag C refractory which protect
graphite used there from oxidation as graphite has poor oxidation resistance.
Advantages
1. It melts at 660 deg C, and forms a liquid which covers up the graphite flakes and
protects it from further oxidation.This happen particularly at lower temperature
and in absence of oxygen.
3. Reacts with graphite and residual C ins system, producing Al4C3 at higher temp and
in absence of O2;l which increases abrasion and corrosion resistance, reduces
porosity, & increase refractoriness.
4. In rearer cases, it may form mag spinel with magnesia in the system, if the total
residual C gets oxidized and temperature is sufficiently high. This spinel increases
RUL and high temp properties.
Disadvantages
1. Al melts at high firing temp producing a liquid phase which can decrease RUL
value at high temp.
2. Costly.
Metallic Silicon
Metallic Si behaves in the same wayas thatof Al powder and having similar
advantages and disadvantages.
SiC
Advantages
DISADVANTAGES
B4C
This also have similar functions but they are not used extensively because of its very high
cost.It has poor oxidation resistance at red heat and consequently forms green fumes of
B2O3.
BENTONITE
Bentonite clay lies under montmorellonite group of minerals. Unlike kaolin, they have
actually a 2:1 structure, i.e one di or tri octahedral cenral layer is basically sandwitched
between two silica tetrahedral layer.
Advantages:
Bentonite is used as a sintering aid.also it contains certain impurities which form low
melting phases in higher temperature forming glassy layer which in turn sometimes help to
fill up the pores thereby reducing the total porosity.it gives also plasticity and greater
workability.
Disadvantages:
Low melting phases such as forsterite sometimes lowers down the refractoriness if used in
greater quantities.
QUARTZITE
Quartzite is a hard, non-foliated metamorphic rock which was originally pure quartz sandstone.
It is the primary raw material for silica refractory. It contains around 98% of silica (SiO2) and
impurities such as Fe2O3, Al2O3 , & alkalizes in minute percentage. The softening ponit of SiO2
is around 17300C.
Sources: Tata, Bhikanpali, Chiraipali, Urdana
Price : Rs 4000/-
Properties :
Chemical properties Physical properties
Advantage :
When sandstone is metamorphosized to quartzite, the individual quartz grains
recrystallize along with the former cementing material to form an interlocking mosaic of
quartz crystals. This amorphous cement type matrix prevents the silica refractory from
cracking during firing due to the lager volume change during the phase transformation of
silica by absorbing the stress.
Secondly, the presence of impurities such as lime or ferric oxide act as mineralizers ,
helping in stabilizing the desired phase in silica refractory.
Due to the presence of amorphous cemented matrix in quartzite , it has lower hardness
than the quartz , which facilitate the grinding and milling of quartzite.
Due to interlocking structure of quartz grains in quartzite, it has a sound corrosion
resistance.
Quartz grains in quartzite cement matrix when melts produces a viscous liquid,
prohibiting slags to get easily penetrate.
Disadvantage :
Silica refractory has lower thermal spalling resistance below the temp. range around
6000C.
Due to phase transformation of -quartz to tridymite and crystabolite , during firing
it has less volume stability which generates stress for crack initiation & propagation.
During conversion actually the silica tetrahedral bonds get disrupted and
completely reorientated, thereby creating substantial volume instability.
Advantage:
it acts as a mineralizer to stabilize cristobalite phase in the silica refractory by creating a
calcium silicate liquid phase.
Disadvantages:
Excess use may low melting compound such as CS or C3S with refractoriness of 1500 deg C
& 1925 deg C respectively, which reduces the hot property of refractory.
Si Metal Powder:
At a considerably elevated temperature, Si first gets converted to SiO and subsequently to
SiO2, which results in volume expansion and consequently fills up the residual pores.