Refrac 2
Refrac 2
The properties of the refractory castables are mainly governed by the type of
binder and additives that are added for setting purposes. Varying bonding
matrix and additives can gives rise to different properties. To obtain improved
properties of the refractory castables the amount of cement content is to be
reduced and ultra-dispersive additives are to be added so that the water
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requirement during setting phase is reduced [11]. With time the bonding
system of the castables is also developed significantly, from hydraulic binders
such as CAC and HAC to colloidal binders like colloidal alumina and colloidal
silica. But the presence of CaO in the castables leads to a drawback that is it
reacts with the oxides present in the castables and forming a low melting point
phase at high temperatures [12]. So there is active research going on so that
castables are made without CaO, which is by using colloids, hydaratable
alumina, spinel etc.
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Binder is the main constituent for unshaped refractories. Binder is
responsible to provide a continuous binding matrix which holds the precision
graded coarse and fine refractory particles helping them to set by giving
strength at green stage. Which later is replaced by a ceramic bond, which is
many more times stronger than when it was in green stage [13].
The binders that react with water to form a continuous bonding matrix
that holds the aggregate together giving them green strength while setting are
called as hydraulic binders. Examples for such binders are calcium aluminate
cement (CAC), hydratable alumina (-alumina) etc. hydraulic binder when
mixed with water forms hydrates that provide with cohesive bonds holding
particles together until ceramic bonds are formed [13].
Rafael Salomao, Marina Rojas Ismael, Victor Carlos Pandolfelli in their work
“Hydraulic binders for refractory castables: mixing curing and drying” they
have studied the properties, when CAC and two different grades of Hydratable
alumina are used as binders in castables. From experimenting and testing they
have found that due to presence of CaO and aluimina they have observed
reduced refractoriness in the castables, especiallty those containing microsilica
and magnesia. But when they have used the calcium free binders such as
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Hydratable alumina they have observed good thermo mechanical properties
[14].
I.R. Oliviera, F.S. Ortega, V.C Pandolfelli in their work “Hydration of CAC
cement in a castable refractory matrix containing processing additives” a
study has been made, where High alumina refractories along with CAC binder
and additives, also with an accelerator (Li2CO3) added, was studied for its
setting behaviour. And the result was that the additives presented a retarding
effect on the hydration process which was more significant for citric acid and
diammonium citrate [16].
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I.R. Oliviera, V.C Pandolfelli in their work “Dispersants and their effects on
Hydratable Alumina containing castables”. A study has been made on
explosive spalling nature of hydratable alumina containing castables. The
explosive Spalling nature is due to permeability reduction, which increases the
difficulty of the migration of vapours from inside to outside. To overcome this
limitation additives (Dispersants) were used. And it was found that use of citric
acid resulted in retarding of hydration mechanism that in turn loses higher
amount of water but this generate large pores and flaws in the sample. But
polymeric additives present a high steric effect due to their ion-gel-chain
molecule. In the presence of this molecule formation of AH and AH3 was
favoured. Resulting in better mechanical properties and less likelihood of
explosive spalling on drying [17].
The binders that are non-hydraulic, inorganic and cold setting are called
as chemical binders. The most important binders that come under chemical
binding system are Phosphates, Water Glass, and Magnesia cement.
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hot mechanical performance when compared to commercial phosphate-
bonded refractory material [18].
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Fig3. In the first picture Injection lance is tapered due to corrosion where as in
second picture where it is lined with Alphabond 300, tapering due to corrosion
is eliminated.
Injection lances must withstand being plunged through basic slag into liquid
steel superheated to 1649oC and remain immersed in the steel while solid
agents or gases are injected into the metal. Then the lance is removed and the
refractory rapidly cools down while on stand by for next cycle.
Here when CAC was used as binder it would react with the basic slag at high
temperatures corroding itself. This effect was eliminated when Alphabond 300
Hydratable alumina was used [20].
Akhilesh Kumar singh and Ritwik Sarkar in their work “Synthesis and
Charecterization of Alumina Sol and Its Use as Binder in No Cement High-
Alumina Refractory Castables” they have prepared Alumina Sol by using
aluminium nitrate nonahydrate and liquor ammonia as precursor material.
aluminium nitrate solution 1M was also prepared. And liquor ammonia was
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slowly added to the aluminium nitrate solution in the ratio of 1:3. Addition of
ammonia was found to increase the viscosity and pH of the solution. The highly
viscous liquid thus obtained was washed to make it free from any unreacted
precursors and by products. To get a stable suspension of colloidal alumina a
small amount of dilute nitric acid was added a small amount of the suspension
was taken out in a petri dish and dried at 60oC, which gives a thin transparent
gel like film [21].
Ramalingam Manivannan, Anil Kumar and Rajnish Kumar Jai in their work
“Toxic-Free Aqueous Gelcasting of Alumina Ceramics Using Alumina Sol
Binder” they have prepared Alumina sol by using Aluminium Isopropoxide as a
precursor by hydrolysing under acidic medium using nitric acid, HNO 3 as
catalyst. The reaction starting materials aluminium isopropoxide, deionized
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water and HNO3 were taken in the Molar ratio of 1:100:0.01, respectively. And
the reaction was carried out at 90oC for 24Hrs. and hydrolysed aqueous
Alumina sol was obtained [22].
Zhixian Hao, Hui Liu, Bin Guo, Hong Li, Jiawei Zhang, Lihua Gan, Zijie Xu,
Longwu Chen in their work “Sol-Gel Synthesis of Alumina using Inorganic salt
precursor” the procedure for preparation of Alumina sol was as follows, 8.04 g
of Al(NO3)3.9H2O was added to 40.0 ml of anhydrous ethanol in a 250ml beaker
with constant stirring at room temperature. After the aluminium nitrate was
fully dissolved, propylene oxide was added and stirred constantly until the
mixture is converted into a homogeneous liquid phase. The beaker was then
sealed with a piece of polyethylene film and kept under static conditions.
Several minutes later the transparent solution was gradually transformed into
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a kind of cloudy gel, meanwhile a large amount of heat was released with a
remarkable rise in temperature. After two days of aging at room temperature
[24].
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Fig5. Representation of diameter of an equivalent-sized sphere for an
irregularly shaped particle.
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from coarse particle to finer. To get fully packed condition if we consider the
volume of the space to be filled to be 100% then the volume of spheres to be
packed should also be 100%. To obtain such filling, one can simply count the
number of spheres required for each different particle size used in the
andreason distribution with a particle distribution co efficient. To fill a fixed
volume using this pattern first the coarsest particles are filled the volume and
their number is counted and then the second coarser particle is used to fill the
volume and the numbers are counted, this way the size of the particles go
down to finer particles. So for any practical work the finest particle is fixed and
one cannot go beyond that size. So packing is stopped at some finite minimum
size Ds. And Dinger and Funk worked exactly this way and defined the D s for
calculation of particle size distribution. And the equation is as follows [28]
Where:
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Chapter 3 Objectives.
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Chapter 4 Plan of work.
Synthesis of Binders
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Experimental procedure
1) Synthesis of Alumina sol:
1M aluminium nitrate solution was prepared.
In a beaker 1M aluminium nitrate and in a burette liquor ammonia is
taken. In the ratio of 3:1
Liquor ammonia is added to the beaker containing 1M aluminium nitrate
solution with constant stirring. Addition of ammonia was found to
increase pH of the solution.
Then there will be a formation of highly viscous liquid which is later
washed to remove unreacted precursors and by-products.
A small amount of dilute nitric acid should be added to obtain a stable
suspension of colloidal alumina.
A small amount of the suspension is taken in a petri dish and dried at
60oC, which gives a thin semi-transparent gel-like film.
This gel is then dried and grinded to obtain fine powder.
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And the sample is let to cool in the vacuum itself. After it reaches room
temperature pressure is released and the sample is taken out and
placed in an air tight container.
3) After the synthesis of the binders it will be sent for SEM and XRD to study
the phase transformations and constituents.
4) After that high alumina castable will be prepared using White tabular
alumina (WTA) grains and White fused alumina (WFA) grains and the particle
size distribution will be based on Dinger and Funk model. Along with this 3%,
5% and 8% (Vol to wt%) of Alumina Sol and Hydratable alumina will be added
separately.
5) Using prepared castables 5cmx5cm cubic casts are made which are then set,
dried and fired.
6) The formed Cubic refractories are tested for their Modulus of rigidity (MOR),
hot modulus of rigidity (Hot MOR), Refractoriness and cold crushing strength.
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REFERENCES
[1] “Refractory technology: fundamentals and applications” by Ritwik Sarkar,
published by CRC press, Taylor and Francis group.
[5] R Manivannam, Anil kumar, Rajnish kumar jain and Challa Subhramanyam;
“Toxic free aqueous Gelcasting of Alumina ceramics using Alumina Sol Binder”;
Int. J. Appl. Ceram. Technol., 1–6 (2014) DOI:10.1111/ijac.12352.
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bodies- A review”; All-union institute of refractories; plenun publishing
corporation.
[14] Rafael Salomao, Marina Rojas Ismael, Victor Carlos Pandolfelli; “Hydraulic
binders for refractory castables: mixing curing and drying”;
[16] I.R. Oliviera, F.S. Ortega, V.C Pandolfelli; “Hydration of CAC cement in a
castable refractory matrix containing processing additives”;
[17] I.R. Oliviera, V.C Pandolfelli; “Dispersants and their effects on Hydratable
Alumina containing castables”;
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[21] Akhilesh Kumar singh and Ritwik Sarkar; “Synthesis and Charecterization
of Alumina Sol and Its Use as Binder in No Cement High-Alumina Refractory
Castables”;
[22] Ramalingam Manivannan, Anil Kumar and Rajnish Kumar Jai; “Toxic-Free
Aqueous Gelcasting of Alumina Ceramics Using Alumina Sol Binder”;
[24] Zhixian Hao, Hui Liu, Bin Guo, Hong Li, Jiawei Zhang, Lihua Gan, Zijie Xu,
Longwu Chen; “Sol-Gel Synthesis of Alumina using Inorganic salt precursor”;
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