2.1 Refractory castables.

Refractory castables are the type of unshaped refractories that

constitutes of fine and coarse refractory aggregates which are primarily
bonded with a binder that gives initial green strength by formation of gel
(continuous binding phase) and when heated to elevated temperatures the
bonding formed by binder is replaced by a ceramic bond that is many times
stronger than the initial green strength bonding.

Monolithic refractories now constitute around 50% of the refractories market.

Installation of refractories is easier than the shaped ones which reduces the
furnace downtime which in turn becomes cost efficient [6]. Refractory
castables are installed on to the surfaces or through the spaces by pouring or
pumping [7]. Refractory castables can be classified on the basis of its
constituents and binders, based on the amount of CaO they are classified in to
CAC castables, Low cement castables, Ultra low cement castables and no
cement castables [6, 12]. CAC was most opted binder for the refractory
castables but recent trends in reduction of cement contents gave rise to new
batch of castables [6]. castables can also be classified on the basis of
installation as self-flow castables, Shotcrete castables and vibration
castables[8].The application of new class of castables is gaining momentum
because of its properties like elevated corrosion and deformation resistance.
Which is obtained due to reduction of CaO content in the castables [9].

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

0
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.

Fig2. Binary phase diagram of CaO-Al2O3 in wt%.

2.2 Binders for refractories.

1
 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 classification of different binders based on the continuous binding matrix

developed is hydraulic binders, chemical binders, organic binders and
coagulation binders.

2.2.1 Hydraulic binders.

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

2
Hydratable alumina they have observed good thermo mechanical properties
[14].

R. Roy, S. Ghosh and P. K. Das Poddar in their work “Development of

Activated Alumina and its effect on the properties of cement free Castable
Refractories”, Activated alumina has been prepared by thermal dehydration
(300oC-600oC) of chemically pure Aluminium Hydroxide. The prepared alumina
was incorporated in cement free castables batch, after that various tests like
bulk density, apparent porosity, cold compressive strength etc. were done.
And it was found that, Activated alumina developed by thermal dehydration of
chemically pure aluminium hydroxide have hive surface area and contribute to
green strength of cement free castables. Activated alumina prepared at 400 oC
acts as better bond material in cement free castables, as it exhibits a
consolidated flexible matrix resulting in high bulk density, low porosity, good
compressive strength and better thermal shock resistance [15].

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].

3
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].

2.2.2 Chemical binders

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.

A P Luz, D T Gomes and V C Pandolfelli in their work “High-alumina

phosphate- bonded refractory castables: Al(OH)3 sources and their effects ” in
this work they have taken two Al(OH)3 sources added to refractory
formulations of H3PO4 (with distinct concentrations) in order to highlight their
influence on the phase evolution and thermos-mechanical properties of the
prepared samples. As a result the most promising binding system that they
have obtained is by mixing H3PO4 solution with 48 wt% of concentration +
Al(OH)3 prior to preparing the castables. The generation of this mono-
aluminium phosphate proved to be a an alternative and effective route,
leading to the generation of high-alumina castables with improved cold and

4
hot mechanical performance when compared to commercial phosphate-
bonded refractory material [18].

2.2.3 Organic binders

C N A Jaafar, I Zainol, S Sulaiman and M I Ayub in their work “Effects of PVA-

PEG binders system on microstructure and properties of sintered Alumina”
they have taken three different formulations of alumina samples which were
prepared by mixing alumina with 3% of Poly ethylene glycol (PEG) with 1 to 3
wt% of poly vinyl alcohol (PVA) binders. The degradation temperature of
binder was investigated by TGA, Diametral Compressive strength test, SEM to
charecterize microstructure was done. And the result they got is that the PVA
binder plays important role in sintering of alumina. The relative density and
tensile strength increase as the percentage of PVA increases for each sintering
temperature, without affecting the binder composition. The results inferred
that alumina samples which have 3%wt PVA-3%wtPEG binder sintered at
1600oC shows the highest tensile strength (129MPa) compared to other
formulations [19].

2.3 Effects of CaO in refractories.

Castable refractories containing CAC are used everywhere in the furnace-lining

applications in the iron, steel, cement, glass and ceramic industry.

M W Vance and K J Moody in their work “Steelplant Refractories containing

Alphabond hydratable alumina binders” have shown the following studies.

5
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].

2.4 Synthesis of Alumina Sol.

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

6
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].

Fig4. Flow diagram for sol making.

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

7
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].

ROdica Rogojan, Ecaterina Andronescu, Cristina Ghitulica and Bogdan Stefan

Vasile in their work “Synthesis and characterization of Alumina Nano-powder
obtained by sol-gel method“ they have prepared Alumina sol by using two
different precursors. First being, AlCl3 as precursor, the sol-gel synthesis
consisted of the preparation of a 0.1 M AlCl3 ethanolic solution. By adding a
28% NH3 solution a gel was formed. this gel was let to mature for 30 hours at
room temperature and then dried at 100oC for 24 Hrs. Second being, organic
triisopropylate (C3H7O)3Al, for C9H21AlO3 used as precursor, the sol-gel
synthesis consisted in the preparation of a 0.1M (C3H7O)3Al ethanolic solution.
A 28% NH3 solution was added in order to form a gel. Mild shaking at 90 oC for
10 Hrs was utilized. The gel was let to maturate at room temperature for 24
Hrs, and then dried at 100oC for 24 hrs [23].

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

8
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].

2.5 Synthesis of Hydratable alumina

S D Vaidya and N V Thakur in their work “Effect of temperature, pH and

ageing time on hydration of -alumina by studying phase composition and
surface properties of transition alumina obtained after thermal dehydration”
have synthesised -alumina by heating micro fine gibbisite from room
temperature to 250o C for 12 hours under constant vaccum of 0.01 Torr. The
rate of heating was around 20oC per hour [25].

Taichi SATO in his work “Preparation of Rho Alumina” has synthesised

hydratable alumina by taking hydragiliite-I and II and bayerite I and II in which I
and II consist of coarse and fine particles as starting materials. H-I and H-II
were precipitated from sodium aluminate solution (molar ratio
Na2O/Al2O3=1.70 in 3.5mol dm-3 NaOH) by seeding decomposition at 30oC with
H-I and B-II, respectively (H-I by seeding decomposition at 50oC). B-I and B-II
were precipitated from sodium aluminate solution of the same concentration
for the preparation of hydragillite by interaction with a stream of carbon
dioxide at the rate of 1 and 4 litre min-1, respectively. These products obtained
are heated to stated temperature that is 250-300 oC at the rate of 1.25 to 5 oC
min-1 which takes around 1.5 hours obtaining rho alumina [26].
9
S D VAIDYA and N V Thakur in their work “Study of phase transformations
during hydration of rho alumina by combined loss on ignition and X-ray
diffraction technique” have synthesised rho alumina by heating NSPH20 grade
micro fine gibbisite from room temperature to 250oC with heating rate of
20oC/hr for 12 hours under constant vacuum of less than 0.01mmHg. The
sample was cooled under vacuum and immediately placed in an air tight dry
container. This obtained sample is rho alumina [27].

2.6 Particle size distribution.

To make any refractory we need the constituent material in various sizes to

enable a better packed and dense condition. As particles that are to be
combined are usually of different shapes for them size cannot be defined, for
this different irregular shapes to represent size, term like equivalent diameter
of a sphere is used. Below table shows the different equivalent diameter to be
used [28].

Table 3 Description on diameters of an equivalent sized sphere for an

irregularly shaped particles.

10
 Fig5. Representation of diameter of an equivalent-sized sphere for an
irregularly shaped particle.

Density packing for castables is different from shaped refractories. Shaped

refractories require high density and compact packing but for castables we
require flowability along with density and strength. Flowability is a unique
requirement of the castables as it is required for its application as to cast into
any intricate shape. A different packing model is required for castables and
that is continuous particle size distribution. In this distribution, particle sizes
are there in continuous manner, not in discrete manner. Different particle sizes
are used for such a pattern. Each size fractions used for this type of distribution
has a maximum and minimum size value. Where each maximum size of particle
fraction is minimum for earlier coarser fraction and the minimum size of the
earlier coarser fraction is the maximum for next finer fraction. Thus, the whole
range of particles is present within the system in continuous manner.
Continuous size distribution gives very good rheological properties such as
flowability [28].

Dinger and Funk Model of particle size distribution:

Experimenting with the packing of particles using Andreason’s equation one

can fill a certain fixed volume with particles of different size fractions going

11
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]

CPFT/100 = (Dn – Dsn)/(DLn - Dsn)

Where:

CPFT - Cumulative percent finer than.

D - Particle size in diameter.

DL - The largest particle size.

Ds - The smallest particle size.

12
Chapter 3 Objectives.

Objectives of this project are:

 To study the effect of CAC, Hydratable Alumina and Alumina Sol as

binder in the high alumina refractories.
 To Study the use of Hydratable Alumina as a binder for steel industry
refractories, and its effectiveness against the corrosion of the
refractories due to slag.
 To study the changes in mechanical and refractory properties when
different composition of binders are used.

13
Chapter 4 Plan of work.

Synthesis of Binders

(CAC, Hydratable Alumina,

Alumina sol)

XRD SEM study of the binders.

Preparing the Alumina aggregates

for casting

Mixing different compositions of

aggregates and binders along with
additives.

Moulding, drying and firing

Testing for different mechanical

and refractory properties.

14
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.

2) Synthesis of hydratable alumina.

 50g of Aluminium Hydroxide Al(OH)3 is taken in the boat of the vacuum

furnace.
 The time temperature graph for the furnace with requirements of 20 oC
per hour until it reaches 250oC.
 The boat filled with the sample is kept in the furnace and temperature is
set according to the time temperature graph drawn.
 The pressure is lowered for under 0.1mmHg.
 It is kept the same for 12 hours or until the temperature reaches 250 oC.

15
  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.

16
REFERENCES
[1] “Refractory technology: fundamentals and applications” by Ritwik Sarkar,
published by CRC press, Taylor and Francis group.

[2] W. E. Lee, W. Vieira, S. Zhang, K. G. Ahari, H. Sarpoolaky and C. Parr;

Castable Refractory Concrete; Intern. Mat. Rev., 46[3], pp.145-167, [2001].

[3] Z. Li, G. Ye, Bonding and Recent Progress of Monolithic Refractories,

Interceram. 41[3], pp.169-173, [1992].

[4] R Salomao, M A Kawamura, A D V Souza, J Sakihama; “Hydratable alumina-

bonded suspensions: Evolution and physical propertiesd during first heating”.

[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.

[6] F.Tomsu, S. Palco; “Refractory monolithics versus shaped refractory

products”; Interceram 66 (2017) [1-2].

[7] J Roy, Sudip Chandra, Saikat Maitra; “Nanotechnology in castable

refractory”; https://doi.org/10.1016/j.ceramint.2018.09.261

[8] W E lee, W Vieira, S Zhang, K Ghanbari Ahari, H Sarpoolaky and C Parr;

“Castable Refractory concretes”. International materials reviews 2001 vol. 46
No.3.

[9] L M Aksel rod; “Refractory castables of the new generation in the

production of cast iron and steel”; Refractories and industrial ceramics Vol 40
nos 7-8, 1999.

[10] C Parr, Ch. Wohrmeyer; “The advantages of Calcium Aluminate Cement as

a Castable Bonding System”; presented at St. Louis Meeting of America
Ceramic Society, 2006.

[11] Yu. E. Pivinskii; “Refractory concretes of a new generation: low-cement

concretes and castable vibration-treated (Vibrocast) thixotropic refractory

17
bodies- A review”; All-union institute of refractories; plenun publishing
corporation.

[12] M Nouri-Khezrabad, M A L Braulio, V C Pandolfelli, F Golestani-Fard and H

Rezaie; “Nano-bonded refractory castables”;
http://dx.doi.org/10.1016/j.ceramint.2012.11.028.

[13] Chr. Parr, J M Aurvay, M Szepizdyn, Chr. Wohrmeyer and C Zetterstrom;

“A review of bond systems for monolithic castable refractories”; Refractories
world forum 7 (2015).

[14] Rafael Salomao, Marina Rojas Ismael, Victor Carlos Pandolfelli; “Hydraulic
binders for refractory castables: mixing curing and drying”;

[15] R. Roy, S. Ghosh and P. K. Das Poddar; “Development of Activated Alumina

and its effect on the properties of cement free Castable Refractories”;

[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”;

[18] A P Luz, D T Gomes and V C Pandolfelli; “High-alumina phosphate- bonded

refractory castables: Al(OH)3 sources and their effects ”;

[19] C N A Jaafar, I Zainol, S Sulaiman and M I Ayub; “Effects of PVA-PEG

binders system on microstructure and properties of sintered Alumina”;

[20] M W Vance and K J Moody; “Steelplant Refractories containing Alphabond

hydratable alumina binders”;

18
[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”;

[23] ROdica Rogojan, Ecaterina Andronescu, Cristina Ghitulica and Bogdan

Stefan Vasile; “Synthesis and characterization of Alumina Nano-powder
obtained by sol-gel method“;

[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”;

[25] S D Vaidya and N V Thakur; “Effect of temperature, pH and ageing time on

hydration of -alumina by studying phase composition and surface properties
of transition alumina obtained after thermal dehydration”;

[26] Taichi SATO; “Preparation of Rho Alumina”;

[27] S D VAIDYA and N V Thakur; “Study of phase transformations during

hydration of rho alumina by combined loss on ignition and X-ray diffraction
technique”;

[28] R Sarkar; “Particle size distribution for refractory castables: A Review”;

published by Interceram.

19