Page | 1

Effect of Filler Material Replacement on the

Properties of the High Alumina Conventional
Castables


A thesis submitted in the partial fulfillment of the
requirements for the degree of Bachelor of Technology


By
Subhojeet Ghose
Roll No: 109CR0496


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Effect of Filler Material Replacement on the
Properties of the High Alumina Conventional
Castables


A thesis submitted in the partial fulfillment of the
requirements for the degree of Bachelor of Technology


By
Subhojeet Ghose
Roll No: 109CR0496
Supervisor: Santanu Bhattacharyya



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CERTIFICATE


This is to certify that the thesis entitled, Effect of Filler Material Replacement on the
Properties of the High Alumina Conventional Castables submitted by Subhojeet Ghose
(109CR0496) for partial fulfillments of the requirements for the award of Bachelor of
Technology degree in Ceramic Engineering at National Institute of Technology, Rourkela is an
authentic work carried out by him under my supervision and guidance. To the best of my
knowledge, the matter embodied in this thesis has not been submitted to any other
University/Institute for the award of any Degree or Diploma.



Date:






Page | 4

ACKNOWLEDGEMENT


With deep respect, I avail this opportunity to express my gratitude to Santanu Bhattacharyya,
Professor, National Institute of Technology, Rourkela for his inspiration and guidance and
valuable suggestion throughout this research work. His vast knowledge in the field of Science
and Technology helped to enlighten me. It would have been impossible on my part to come up
with this project report without him. I would like to express my gratitude to Dr. S.K Pratihar,
HOD, Ceramic Engineering, Prof. Ritwik Sarkar, Prof. Sumit Pal and all other faculties for their
constant support and valuable suggestions. I would also take this opportunity to express my
gratitude to the non-teaching staff for their help and kind support. I would also like to thank TRL
Krosaki Limited and IFGL Refractories for providing me with the Raw Materials. I am also
thankful to the Research Scholar in the Department of Ceramic Engineering for helping out in
labs and analysis. And lastly I am thankful to my parents and friends for their constant support







Subhojeet Ghose
109CR0496



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CONTENTS

ABSTRACT 6
1. INTRODUCTION 10
2. LITERATURE REVIEW 12
2.1 REFRACTORIES 13
2.2 CLASSIFICATION OF REFRACTORIES 14
2.3 MONOLITHICS 15
2.4 CASTABLES 16
2.5 HIGH ALUMINA BASED CASTABLES 19
2.6 LOW CEMENT CASTABLES 20
2.7 MULLITE 20
2.8 TABULAR ALUMINA 22
2.9 BAUXITE 22
2.10 WHITE FUSED ALUMINA 24
2.11 CALCIUM ALUMINATE CEMENT 25
2.12 REACTIVE ALUMINA 27
2.13 FUMED SILICA 27
3. EXPERIMENTAL PROCEDURE 28
3.1 MATERIALS AND METHODS 29
3.2 CASTING AND SAMPLE PREPARATION 31
4. TESTING AND CHARACTERIZATION 35
4.1 DETERMINATION OF CCS 36
4.2 DETERMINATION OF BD 36
4.3 DETERMINATION OF FLOWABILITY 37
4.4 DETERMINATION OF HMOR 37
4.5 PHASE ANALYSIS 38
4.6 MICROSTRUCTURE ANALYSIS 38
5. RESULTS AND DISCUSSIONS 39
5.1 VARIATION OF BD AND CCS WITH CURING TIME 40
5.2 STUDY OF FIRED STRENGTH OF CASTABLES 44
5.3 STUDY OF FLOWABILITY OF CASTABLES 46
5.4 STUDY OF HMOR OF CASTABLES 47
5.5 PHASE ANALYSIS BY XRD 48
5.6 MICROSTRUCTURAL ANALYSIS BY SEM 49
6. SUMMARY 50
7. REFERENCES 52

Page | 6

ABSTRACT

The demand for the monolithic refractories as compared to their shaped counterparts have been
increasing over the years due to their distinct advantages like comparable durability, low cost
and relatively easy installation procedure. Several attempts are being made in the optimization
of the properties of these products. Among monolithics, refractory castables are the major ones
which have replaced significant fraction of shaped refractories in the furnace lining. Among the
castables, high alumina based castables are the most important type. This work focuses on the
study of the properties of the conventional high alumina based refractory castables, firstly due to
the reduction in the percentage of cement by reactive alumina and secondly due to the
replacement of cement by micro-silica in the composition. The reduction in the percentage of
cement improved the thermo-mechanical property which was indicated by the HMOR values and
the incorporation of the micro-silica in the composition resulted in the development of good
mechanical strength to the castables and also improved their thermo-mechanical properties. The
improvement in mechanical properties and HMOR values for microsilica castables was
definitely due to mullite formation. However as the microsilica content was only 4%, the fraction
of mullite that formed on firing was also less. Therefore, though the enhancement was distinct
but it was only by about 25%.



Page | 7


LIST OF TABLE USED
Serial no. Table Page No.
1 Physical Properties of Almatis Tabular alumina 23
2 Composition of the castables 29
3 Chemical Composition of the Batch 30
4 Chemical composition of the Castable 34


LIST OF FIGURES USED
Serail No. Name of the figure Page No.
1 Application of Refractories 13
2 Crystallographic morphology of hydraulic cement
phases
17
3 SEM pictures of needle shaped mullite synthesized
hydrothermally in small drusses of volcanic rock in
Eifel Mountains,Germany
22
4 SEM pictures of Almatis Tabular Alumina 25
5 White Fused Alumina 25
6 CaO-Al
2
O
3
Phase diagram 26
Page | 8

7 Reaction mechanism of hydration of Calcium
Aluminate phases
27
8. Flow chart for Conventional Cement Castable 31
9 Flow chart for Low Cement Castable 32
10 Mixing Sequence of Castable 3(Low cement Type) 33
11 Variation of BD with curing time of castable 1 41
12 Variation of BD with curing time of castable 2 41
13 Variation of BD with curing time of castable 3 42
14 Variation of CCS with curing time of castable 1 42
15 Variation of CCS with curing time of castable 2 43
16 Variation of CCS with curing time of castable 3 43
17 Variation of CCS with respect to curing time of the
three different castables
44
18 Fired strength of the castables 45
19 Flowability of the castables 46
20 Compressive study of HMOR of samples 47
21 XRD Analysis of Castable 3 48
22 SEM Analysis of castable 3 49



Page | 9

LISTS OF ABBREVIATIONS USED
Sl.No. Abbreviations used Full Form
1 CAC Calcium Aluminate
Cement
2 XRD X-Ray Diffraction
3 WTA White Tabular Alumina
4 BD Bulk Density
5 CCS Cold Crushing Strength
6 CA CaO.Al
2
O
3

7 CA
2
CaO.2Al
2
O
3

8 CAH
10
CaO.Al
2
O
3
.10 H
2
O
9 C
2
AH
8
2 CaO.Al
2
O
3
.8H
2
O
10 C
3
AH
6
3 CaO.Al
2
O
3
.6 H
2
O
11 C
12
A
7
12 CaO.7Al
2
O
3

12 C
3
A 3CaO.Al
2
O
3

13 CA
6
CaO.Al
2
O
3

14 SEM Scanning Electron
Microscopy







Page | 10



CHAPTER 1

INTRODUCTION




Page | 11

With the increase in the demand for refractories, several methods are being
adapted so as to optimize the properties of the refractory materials. One such step is the
advancement being made in the field of monolithics. Refractory castables are used as a
replacement of the conventional refractory bricks for the furnace linings [1-2]. They are
continuous mass and are free from corners and joints. The corners and the joints are usually the
sites for maximum amount of corrosion, erosion and slag penetration. So, the life and durability
of the refractory bricks are usually very poor. So, castables are mostly used in the furnace lining.
Refractory castables are a homogenous mixture of the refractory aggregates and the binders.
Mostly cement is being used as a binder phase for the castables. The addition of
cement also provides flow properties and leads to easy installation of the cement bonded
castables usually reducing skilled labour. So, cement bonded castables are getting very popular
these days. The present day practice is the reduction in the percentage of cement for increasing
life and durability of the castables. The enhancement in properties is due to the reduction in the
amount of the low melting phases in the castable which are mostly Anorthite and Gehlenite with
reduction in the percentage of cement. This also improves the creep resistance and other thermo-
mechanical properties of the castables. Since the replacement of cement is done through addition
of purer and refractory grade raw material, the composition of the aggregate affects the
properties of the castable especially their chemical resistance. Also the particle size distribution
also affects the packing and the ultimate strength of the castables [3].
Present day trend is to use High Alumina based castables as it has extremely good
chemical resistance against any corrosive medium. The incorporation of fumed silica in the
composition improves the flowability and also leads to the formation of the mullite phase after
sintering. The presence of these phases leads to improved mechanical strength, higher thermal
shock resistance and better corrosion resistance as well.
.




Page | 12





CHAPTER 2

LITERATURE REVIEW





Page | 13

2.1 REFRACTORIES:
Refractories are used to withstand very high temperatures. Refractories are inorganic, nonmetallic,
and heterogeneous materials composed of thermally stable mineral aggregates, a binder phase and
additives. ASTM C71 defines refractories as "non-metallic materials having those chemical and
physical properties that make them applicable for structures, or as components of systems, that
are exposed to environments above 1,000F (811 K; 538C) [4].The main requirements of a
refractory materials are
High temperature stability
High load bearing capacity
Abrasion and wear resistance
Erosion and corrosion resistance
High thermal shock resistance



Fig 2.1: Application of Refractories [5].
Refractories
Steel Industry
(70%)
Incinerators
(8%)
Refineries/
Petrochemicals
/others(7%)l
Glass Industry
(15%)
Page | 14

2.2 CLASSIFICATION OF REFRACTORIES
1. On basis of chemical nature
Acidic Refractories: These are those refractories which are used in the presence
of any acidic slags. The Cao/SiO
2
ratio (C/S ratio) for acidic refractories is < 1.
Some examples of acidic refractories are Silica refractories, Fire Clay
refractories etc. They are used in coke oven, glass tank furnace etc [6].
Basic Refractories: These are those refractories which are used in presence of
basic slags. The Cao/SiO
2
ratio (C/S ratio) for basic refractories is >1. Ex:
Magnesia refractories, Magnesia carbon refractories, Magnesia-chromite,
dolomite refractories etc. They are used in the Blast Furnace, BOF, EAF, VOD
etc. [6].
Neutral Refractories: These are those refractories which can withstand both
acidic and basic slags. Ex: high alumina refractories. [6].
2. On basis of Shape:
Shaped refractories: They have fixed size and shapes. They are further classified
into standard shapes and special shapes. Standard shapes are those which have a
specific dimension that are conformed by most refractory manufacturers and are
generally applicable to kilns or furnaces of the same types. Special shapes are those
that are specifically made for applications in particular kilns or furnaces. Shaping
processes include pressing, casting etc. [6].
Unshaped Refractories: These are without definite form and are only given shape
upon application. These types are better known as monolithic refractories. The
common examples are plastic masses, Ramming masses, castables, gunning masses,
fettling mix, mortars etc. [6].
3. On basis of porosity:
Porous refractories: Contain air pores which act as insulators. They are used in the
backup lining. [6].
Dense Refractories: They are used in the working lining of the furnaces. [6].

Page | 15


4. On basis of carbon content:
Carbon containing refractories: They have some carbon content in their composition
for imparting corrosion and thermal shock resistance. They are again classified on
the basis of their oxidation resistance. Ex: Magnesia carbon refractories. [6].
The Alumino Silicate refractories are further classified on the basis of their alumina content as:
[6].
Low Heat Duty (25%-30% Al
2
O
3
)
Medium Heat duty (30%-35% Al
2
O
3
)
High heat duty (35%-40% Al
2
O
3
)
Super heat duty (40%-45% Al
2
O
3
)
The heat withstanding capacity is directly proportional to the alumina content in the composition.
2.3 MONOLITHICS
The use of monolithic refractories has become very wide spread looking back at the last 20 years
[1-2].These refractories do not have any specific shape and come in form of loose powders. They
are called as monolithics which comes from the word mono-lithus meaning Single stone.
[6].These are the materials which are installed as some form of suspension/plastic mass that
ultimately harden to form a solid mass. They contain some refractory grains as aggregates along
with binder as the minor phase. The main properties of these materials are their respective high
chemical inertness, better mechanical integrity, higher abrasion resistance and high thermal
shock resistance at high temperatures.
ADVANTAGES OF MONOLITHIC REFRACTORIES [6].:
Easy installation
Less skill requirement during installation
These unlike the shaped refractories are joint-less which leads to higher corrosion and
abrasion resistance.
Any desired shape can be made.
Page | 16

Cheaper as no firing are required
They help in repairing of the furnaces even in the working conditions.
They are easy for transportation.

2.4 CASTABLES:
These are those types of monolithic products which can act as a substitution for the conventional
refractory bricks used in the lining of the furnaces for high temperature applications. They
consist of an aggregate phase and a binder phase which at the installation site is mixed with a
liquid preferably water after which they set and hardens and develop a suitable amount of green
strength in the system. Then they are subjected to firing after which they develop ceramic bond
formation during sintering and the strength further increases. The majority of refractory castables
use calcium aluminate cement as the bonding agent though in recent years other bonding systems
have been employed. The ultimate properties of the refractory castables are affected by the
particle size distribution, packing and the sintering temperature. Initial strength in the castable
system is mostly developed due to the presence of binder which gets activated by the addition of
liquid at the installation site. For instance the cement bonded castables show the following type
of reaction mechanism at the installation site [7]:
CA + H
2
0 = CAH
10
(Temperature <21C)
CA+H
2
0=C
2
AH
8
+AH
3
(21C < Temperature<40C)
CA + H
2
O =C
3
AH
6
+AH
3
(Temperature is > 40C)
The crystal morphology of these calcium aluminate phases shown below:
Page | 17


CAH
10
C
2
AH
8


C
4
AH
13
C
3
AH
6

Fig: 2.2 : Crystallographic morphology of different hydraulic cement phases.[8]
C
3
AH
6
phase is the thermodynamically most stable phase and is formed eventually. It has a cubic
crystal structure. When the castable is heated the hydrated cement phase will undergo a
dehydration process due to the loss of water in the form of water vapor over a temperature range.
Dehydration occurs over a temperature range from 210C to 370C, with the peak dehydration
being at 230C and 315C for AH
3
and C
3
AH
6
respectively [9-10]. If the evolved vapors are
not allowed to get released out then outward pressure will develop in the castable systems and
this will result in spalling. CAC bonded castables also require careful drying for the escape of the
Page | 18

moisture as well as prevent the internal pressures of the water vapors [11]. Presence of unreacted
water molecules in the castable system can also result in generation of porosity upon firing the
castable due to the evaporation of the unbonded water molecules. This will result in spalling and
reduction in strength of the castable. Therefore the usual practice is to cure the castables for
longer duration for achieving maximum green density before firing is carried out. [12].
Cement bonded castables can be further classified on the basis of the percentage of cement used
in the castable. They are: [6]
Conventional Cement Castable (15% cement)
Low Cement Castable (4-6% cement)
Ultralow Cement Castable (1-3% cement)
No Cement Castable
On basis of type of binders, Castables can be further classified as [6]
Sol Bonded Castables
Cement Bonded Castables
Hydratable Alumina Bonded Castables
Phosphate bonded Castables
Castables can also be classified on basis of flow as [6]:
Self-flow castables
Vibratable Castables
Most of the refractory castables also show the heterogeneous microstructure which consist of
different type of phases .These can have different coefficient of thermal expansion and this can
result in the development of stresses internally within the system and this can influence the
thermo-mechanical properties [13-14].
On basis of chemical composition the castables can be further classified as :
Alumina Castables
Silica Based Castables
Page | 19

Magnesia Castables
2.5 HIGH ALUMINA BASED CASTABLES:
High Alumina based castables are those type of castables in which the percentage of alumina in
the composition varies from 45%-99%.These type of castables have a tendency to show very
high refractoriness and good high temperature properties. Further the properties can be improved
by incorporating new phases like mullite and spinel in these castable systems. The typical
properties of the high Alumina refractory castables are [6]:
High Mechanical Strength
High Corrosion Resistance
High Abrasion Resistance
High Thermal Shock Resistance
High Thermal Conductivity
High Refractoriness
The presence of the alumina in the composition of the refractory aggregates in the range of 45-
99% decides whether the refractory is a high alumina refractory or not. Some typical type of
aggregates to be used in the composition of the refractory aggregate composition for the high
alumina castables are [6]:
White fused alumina
Reactive alumina
Tabular alumina
Bauxite
Brown fused alumina
Calcined Alumina
On basis of the percentage of cement in the castables, the High Alumina based castables can be
further classified as [6]:
Conventional Cement Castable (10% Cement)
Low Cement Castable (4-6% Cement)
Page | 20

Ultra Low Cement Castable (1-3% Cement)
No cement castable
2.6 LOW CEMENT CASTABLES:
These type of castables have an aggregate and a binder phase just like any other monolithic
product. The only difference is in the percentage of the cement used as binder which is 4-6% in
this case. This type of castable technology had developed in the 1970s.[6]
Some important characteristics of the low Cement Castables are [15-16]:
Low Value of initial strength due to inadequate formation of hydraulic bonds due to
lower percentage of cement in the composition
Lesser faller in strength due to the loss of water in the form of water vapor from the
castable
Better amount of strength developed upon firing
Better thermo-mechanical properties
Lower percentage of low melting phases developed within the system after sintering
The properties of the low cement castables are further influenced by the addition of ultrafine
components to the castable mixture. Also addition of deflocculants can also influence the
flowability of the castables. The particle size distribution in the castable system also influences
the packing of the castable and its ultimate strength [17].
The flowability of the low cement castables are usually expected to be lower because of the
presence of lesser amount of cement and hence lesser amount of water which is very responsible
for the flowability. So, usually we add a chemical compound called the deflocculant which will
prevent the coagulation in the system and improve the flowabilty [6].
2.7 MULLITE:
Mullite is a solid solution of Alumina and silica. Theoretically, mullite has 72% Alumina and
28% silica in the composition. Mullite has several advantages of being a refractory material. It
has extremely good thermal shock resistance and high refractoriness and good mechanical
Page | 21

strength. This is always a desired phase in the alumino-silicate systems for refractory
applications. Sintering behaviour of mullite-containing powders has been studied over a range of
chemical compositions (Al
2
O
3
/SiO
2
ratio). It has been found that the observed lattice parameters
of mullite samples are highly influenced by minor compositional changes and different thermal
conditions such as temperature of synthesis and both heating and cooling rate. The properties of
mullite are highly influenced by the nature of the starting raw materials. Mostly alumino silicate
based materials are used as the starting raw materials. It has been reported that among the
naturally occurring raw materials, silimanite group of minerals mostly leads to the formation of
equi axed mullite grains and kaolinite leads to needle-like grains.[18]
Some of the typical properties of mullite are [19]:
Good thermal shock resistance
Low thermal conductivity
Good strength
Wear resistant
Usable to high temperatures
Mullite phase is highly desirable for the following types of applications
Protection tubes
Furnace liners
Electrical insulators

Page | 22


Fig 2.3 SEM Pictures of needle shaped mullite synthesized hydrothermally in small druses
of volcanic rocks of the Eifel mountains, Germany [20]


2.8 BAUXITE:
Bauxite (Al
2
O
3
.2H
2
O) is a naturally occurring source of aluminum and alumina and is a mixture
of Gibbsite [Al(OH)
3
], Bohemite [AlO(OH)] and diaspore [-AlO(OH] along with impurities
like TiO
2
, Gohetite ((FeO(OH)) and Haematite (Fe
2
O
3
). Bauxite owing to its low cost is used as
an aggregate in the refractory castable and can act as an important source of Alumina.
Commercially two different grades of bauxite are available. They are Chinese Bauxite and Indian
Bauxite. Chinese Bauxite is of a purer grade having 94% Alumina whereas Indian Bauxite has
88% Alumina in the composition. [21]
2.9 TABULAR ALUMINA:
It is obtained by pressing the calcined alumina obtained from Baeyers process in the shape of
balls and then firing them to a temperature of 1800-1900 C. It undergoes densification and
Page | 23

sintering upon firing and we get a nearly pore free structure which shows the following types of
properties [6]:
high refractoriness
high bulk density,
High thermal shock resistance,
High wear-resistance
high purity
High chemical resistance,
complete crystal tabularization
low porosity.
It is called as tabular Alumina because the crystals are arranged in a tabular manner. Due to the
manufacturing process the Tabular Alumina is a very costly material. Tabular Alumina is further
subdivided into [6].
White Tabular Alumina(WTA)
Brown Tabular Alumina(BTA)
Tabular Alumina is a highly dense material. It is mostly sintered through the solid state sintering
route to achieve maximum possible density. Almatis is a leading producer of Tabular Alumina in
the world [22]. The Tabular Alumina is also available in the form of WTA and BTA fines. It is
an important component of the aggregate phase of the castable and impart very high mechanical
strength and high abrasion resistance and very high thermal shock resistance owing to its high
thermal conductivity due to its narrow porosity and low coefficient of thermal expansion.
Table 2.1 Physical Properties of Almatis Tabular Alumina [22]

Bulk Density

3.5

Apparent Porosity(%)

5

Water Absorption(%)

1.5
Page | 24



Fig 2.4 : SEM Pictures of Almatis Tabular Alumina [22]

2.10 WHITE FUSED ALUMINA:
White fused Alumina is obtained by arc melting the Baeyers Alumina and then cooling it. It is
of very pure grade and free from iron impurities. Due to its massive and large grain size white
fused alumina has very high chemical resistance. Some of the other characteristics properties of
the White fused Alumina are [6]:
higher hardness
light lower toughness comparing with brown fused alumina
high purity
ability of self-sharpening
better cutting,
higher efficiency
good thermal stability
Page | 25


Fig 2.5 White Fused Alumina [5]
2.11 CALCIUM ALUMINATE CEMENT (BINDER):
Calcium Aluminate Cement or High Alumina Cement or simply Aluminous Cement is a
hydraulic binder used as a binder for the refractory castables and other monolithic products.
They set and harden at the installation site upon mixing with water and provides strength to the
system. It is based on the Calcium Aluminate phases unlike the Calcium Silicate Cement in the
Ordinary Portland Cement. There are several phases in the CaO-Al
2
O
3
phase diagram. They are
C
3
A, CA, CA
2
, CA
6
. In the Calcium Aluminate Cement the phases that are mostly maintained
are CA and CA
2
. The rate of hydration of each of the phases is determined by the percentage of
CaO content in it. Higher the percentage of CaO in the phase composition, higher will be the rate
of hydration which gives C
3
A a flash setting property due to its rapid hydration. It rapidly sets
and hardens upon water addition. While the most hydraulic phase is CA, CA
6
is the non-
hydraulic phase and has the highest amount of refractoriness due to very high percentage of
alumina in the composition. The different phases in the CaO-Al
2
O
3
system is as shown
Page | 26


Fig 2.6 CaO-Al
2
O
3
phase diagram [23]

Some of the major properties of the Calcium aluminate Cement are:
Higher refractoriness
Provides high strength to the matrix
High Corrosion Resistance
Lower Initial Setting Time but shorter final setting time compared to Portland cement
Improved Thermal shock resistance


Upon addition of water the Calcium Aluminate phases gets hydrated as per the following
reaction scheme [23]
Page | 27


Fig:2.7: Reaction Mechanism of hydration of the Calcium Aluminate Phases [23]
FILLER MATERIALS
2.12 REACTIVE ALUMINA:
Reactive Alumina is obtained through extensive grinding of the calcined alumina obtained from
Baeyers process in a ceramic lined ball mill for more than 24 hours [24]. The final crystal size is
nearly less than 1m.Due to its finer particle size they have high sintering, densification and
reactivity rates. They also readily react with other components like microsilica to form mullite a
material of strategic importance in refractory. They also undergo spinel formation upon sintering
with MgO.
2.13 FUMED SILICA
Fumed Silica or microsilica is also used as a filler material for the castable. It is also known as
pyrogenic silica because it produced in a flame. It consists of microscopic droplets of amorphous
silica which are fused into branched, chainlike and three-dimensional secondary particles which
then agglomerate into the tertiary particles [25]. It has extremely low bulk density and high
surface area. It has the tendency to undergo sintering with reactive alumina and form mullite and
this phase is highly advantageous for refractory applications.
Page | 28







CHAPTER 3

EXPERIMENTAL PROCEDURE





Page | 29

3.1 MATERIALS AND METHODS
The raw materials that were used were:
Aggregate: White Fused Alumina, Reactive Alumina, Tabular Alumina, Bauxite,
Binder: Calcium Aluminate Cement (Polychem, CA 14)
Filler: Microsilica, Reactive Alumina
The Reactive alumina (A-16 SG) of grain size (<1 m) and Tabular Alumina of size (1-3mm)
were used. The chemical composition is given in the Table 3.2 below. The white fused Alumina
which had an average particle size of 0.5-1 mm was collected from Hindalco India, and the
Bauxite of 75 mesh grain size was obtained from M/S Tata Krosaki Refractories, Belpahar
Orissa. Calcium aluminate cement (CAC) was used as a binder. Two commercial varieties of
CAC were used i.e CA 14 (Almatis) and Polychem (Polychem Rourkela). The weight percentage
of CAC, white fused alumina, tabular alumina, reactive alumina and bauxite used in the castables
are shown below:
Table 3.1 Composition of the castable
WEIGHT PERCENTAGE IN THE BATCH
Castable 1

Castable2 Castable 3

WFA(0.5mm-
1mm)
15 15 15
Reactive
Alumina
30 34 30
Tabular
Alumina
(1-3 mm)
30 30 30
Bauxite
(75 mesh)
15 15 15
Fumed Silica - - 4
HAC 10 6 6
Water 12.5 7 7
Page | 30

The chemical composition of the several aggregates is as shown in the Table below:

Table 3.2 Chemical Composition of the Batch
CHEMICAL COMPOSITION OF THE BATCH

Tabular
Alumina


Bauxite

Calcined
Alumina


Reactive
Alumina


WFA
(0.5mm-
1mm)

CAC
(%)
Polychem

CAC
(%)
CA 14
Al
2
O
3
99.5 90 97.56 99.8 99 71.48 71.42
Fe
2
O
3
- 1.40 0.11 0.02 0.2 - 0.11
TiO
2
- 2.50 Traces - - - -
B
2
O
3
- - - <0.01 - - -
CaO - - 0.51 0.03 - 24.6 26.91
SiO
2
<0.09 - Traces 0.02 - 0.4 0.20
Na
2
O <0.4 0.25 0.49 0.07 0.2 0.05 0.14
K
2
O - 0.25 0.08 - 0.2 0.05 0.14
MgO - - 0.61 0.04 - 0.2 0.31
LOI - - 0.37 - - - -







Page | 31

3.2 CASTING AND SPECIMEN PREPARATION
Three different types of castables were prepared according to batch composition given in table
2.1.The castables were shaped as per the following flowcharts.
FLOW CHART FOR CONVENTIONAL CEMENT CASTABLE
Tabular Alumina + White fused Alumina + Bauxite
(Mixed for 15 minutes)

Reactive Alumina (30%)
(Mixed for 10 minutes)

Aggregate Mixer
+ CAC (10%) + Water (12%)
(Mixed for 5 minutes)
Castable
N.B All mixing were done in Hobart Mixer (5 kg capacity)
Fig 3.1: Flow chart for Conventional Cement Castable



Page | 32

FLOW CHART FOR LOW CEMENT CASTABLE

Tabular Alumina + White fused Alumina + Bauxite
(Mixed for 15 minutes)

Reactive Alumina (34%)
(Mixed for 10 minutes)

Aggregate Mixer
+ CAC (6%)+ Water (7%)
(Mixed for 5 minutes)
Castable

N.B All mixing were done in Hobart Mixer (5 kg capacity)

Fig 3.2: Flow chart for Low Cement Castable

Page | 33

FLOW CHART FOR LOW CEMENT CASTABLE
Tabular Alumina + White fused Alumina + Bauxite
(Mixed in for 15 minutes)

Reactive Alumina (30%)
(Mixed for 10 minutes)

Fumed Silica


Aggregate Mixer
+ CAC (6%)+ Water (7%)
(Mixed for 5 minutes)
Castable
N.B All mixing were done in Hobart Mixer (5 kg capacity)

Fig 3.3 Flow chart for Low Cement Castable
Page | 34

The required amount of CAC was weighed separately and kept away in an evacuated desiccator
because of its hygroscopic nature. The mixing sequence is as shown in the fig 3.1, 3.2, 3.3. The
coarser components were taken first and mixed thoroughly in a Hobart mixer for 15 minutes
followed by the addition of the finer particles and thoroughly mixed for about 10 minutes.
During the final stage of casting, the CAC was added to the batch followed by thorough mixing.
Required amount of water (12% for Castable 1 and 7% for Castable 2 and Castable 3) was added
during the final mixing stage. The resultant mixture was then rapidly poured into the steel mould
(dimension 50mm x 50 mm x 50mm) for setting and hardening. The mould was covered with a
wet cloth and kept in air atmosphere for about 24 hours for humidity drying. After 24 hours the
cubes were demolded and the blocks were subsequently kept in cool water for curing at a room
temperature for different time periods viz 1 day, 3days, 7 days, 14 days, 28 days .The batch
composition of the castables is shown in Table 3.3. This is calculated using the data mentioned in
the Table 3.2.
Table 3.3 Chemical Composition of the Castable
Weight Percentage in Castable
Castable 1 Castable 2 Castable 3
Al
2
O
3
87.41 88.58 84.59
Fe
2
O
3
0.51 0.50 0.51
TiO
2
0.26 0.26 0.26
B
2
O
3
0.001 0.002 0.002
CaO 3.15 1.93 1.93
SiO
2
8.17 8.15 12.12
Na
2
O 0.21 0.21 0.21
K
2
O 0.02 0.02 0.03
MgO 0.26 0.26 0.26
LOI 0.09 0.09 0.09

Page | 35







CHAPTER 4

TESTING AND CHARACTERIZATION








Page | 36

4.1 DETERMINATION OF COLD CRUSHING STRENGTH (CCS):
The cured samples were removed from water and oven dried for about 24 hours at 110 C and
then analyzed for its strength. The CCS of the castables was determined by the following
equation:
CCS = L/A ...eqn (4. 1)

where, CCS= Cold Crushing Strength (kg/cm
2
), L=Load at which fracture occurs (kg) and
A= Area of the sample (cm
2
). The CCS was determined for 3 specimens and the mean of the 3
values were reported.
The fired CCS of the castables was determined after firing the green samples at 1650 C for 2
hours. The initial heating rate was 5
O
C/min up to 1000
O
C followed by heating at 3
O
C/min up
to desired temperature. The castable blocks were furnace cooled and then CCS was determined
as described above.
4.2 DETERMINATION OF BULK DENSITY OF AS CURED AND AS FIRED
CASTABLES:
After the desired curing time was over, the samples were removed from water and oven dried for
about 24 hour at 110 C and then analyzed for its bulk density. The bulk density of the samples
was calculated by taking the weight of each of the castable sample and then dividing the weight
by the volume. It is calculated by the formula:
BD= Mass/Volume eqn. (4.2)
To determine the fired BD of the castables the samples were subjected to sintering at 1650 C
after initial curing of 7 days. Firing was done in a programed controllable furnace.During
sintering the initial heating rate is 5
O
C/min up to 1000
O
C and then reduced to 3
O
C/min up to
desired temperature. The castable blocks were then cooled and then subjected to BD
determination as described above.


Page | 37

4.3 DETERMINATION OF FLOWABILITY:
The flowability of the castables was determined by the help of flow cone. The base diameter of
the flow cone was 100 mm and the top diameter was 70 mm. The castables of desired
composition was prepared by thoroughly mixing the aggregates, fillers and binder as shown in
Fig 3.1 and was poured into the flow cone. The system was placed on the vibratable table and
vibrated for 2 minutes. The material flowed as a result of vibration and the change in the base
diameter was noted down. The difference was indicative of the flowaility of the castables. Larger
the diameter greater is the flowability of the castable.
If X is the measured diameter of the base after vibration then the flowabilty is given by:
Flowability = (X-100) mm eqn (4.3)
4.4 DETERMINATION OF HOT MODULUS OF RUPTURE (HMOR):
Hot Modulus of Rupture (HMOR) is the maximum load at which the refractory material will
break under a 3 point bending system under hot conditions. For calculating the HMOR of the
samples, the aggregates and the binder were thoroughly mixed as per the sequence shown in the
Fig 3.1.The castable was prepared and poured into the bar shaped moulds of dimensions 150mm
x 25mm x 25mm.The cast was demoulded after 24 hours and then subjected to curing for 7 days
in water. After 7 days the samples were removed from water and then subjected to drying in a
oven for 24 hours at a temperature of 110C. The dried samples were subjected to sintering at
1650 C with soaking time of 2 hours at 1650 C. During sintering the initial heating rate was 5
O
C/min up to 1000
O
C followed by heating rate of 3
O
C/min up to desired temperature. After
firing the samples were furnace cooled and then taken out of the furnace.The sintered samples
were subjected to HMOR analysis. The loading rate was 1.3 kg/sec and the heating rate of
8
O
C/min up to 1000
O
C and then reduced to 5
O
C/min up to desired temperature of 1400C. The
mean value of 3 readings for each type of castable was considered.
The HMOR was calculated as per the formula:
HMOR=(3*P*L)/2B*D
2
..eqn( 4.4)

Page | 38

Here, P=Load (kg) at which the sample failed.
L= Span length
B= Breadth of the sample
D= Height of the sample

4.5 PHASE ANALYSIS:
The phases in the fired castable was observed by XRD. The fired castable was crushed and
ground to very fine powders using a mortar pestle and then subjected to XRD analysis to identify
the phases formed after sintering. The scan was performed at a 2
O
C/min scan rate at 40 kV and
30 mA. The X- ray data was plotted using the XPert Pro software and the peaks were matched
with JCPDS files to get the phases.

4.6 MICROSTRUCTURAL ANALYSIS:
SEM analysis was carried out on a crushed powder of the sintered castable. The powder was
sprayed on an aluminium stub and gold coated. The sample were observed at 30 kV accelerating
voltage at a working distance of 10 mm.




Page | 39



CHAPTER 5

RESULTS AND DISCUSSION




Page | 40

5.1 VARIATION OF BULK DENSITY AND COLD CRUSHING STRENGTH WITH
RESPECT TO CURING PERIOD:
The variation of the Bulk Density of the castables prepared with different types of Calcium
Aluminate cements as a function of curing time is shown in the Figures 5.1-5.3. The castables
were cured in water for 1 day, 3 days, 7 days, 14 days and 28 days. It is observed that the bulk
density of the castables increases with increase in curing time. This was due to the formation of
the hydraulic bonds resulting from the hydration of the cement phases due to the reaction with
water as per the following equations [7]:
CA + H
2
0 = CAH
10
(Temperature<21C)(.5.1)
CA+H
2
0=C
2
AH
8
+AH
3
(21C<Temperature <40C).. (5.2)
CA + H
2
O =C
3
AH
6
+AH
3
(Temperature>40C )(5.3)
It has been further observed that the Bulk Density of the castables with CA 14 as the binder is
higher than the castables with Polychem as the binder. This could be because of the difference in
the quality of the two cements which gives different hydration products in both the cements and
also the difference in their particle size which in turn affects their reactivity with water. It has
also been observed that after 5-7 days of curing of the castables, the bulk density reached a
constant value and there after no significant changes were observed in the value of the bulk
density of the castables. The variation of the CCS of the castables with respect to the curing time
is also shown in the Figures 5.4-5.7.It was observed that the CCS variation with respect to the
curing time was very much similar to the variation of Bulk Density with respect to the curing
time. This was due to the increase in the degree of formation of the hydraulic bonds as a result of
hydration.
Page | 41


Fig 5.1: Variation of the Bulk Density with curing time of Castable 1

Fig 5.2: Variation of the Bulk Density with curing time of Castable 2
0 5 10 15 20 25 30
2.50
2.55
2.60
2.65
2.70
2.75


B
u
l
k

d
e
n
s
i
t
y
(
g
m
/
c
m
3
)
Curing Period(Days)
(CA 14)
(Polychem)
5 10 15 20 25 30
2.40
2.45
2.50
2.55
2.60
2.65
2.70


B
u
l
k

D
e
n
s
i
t
y
(
g
m
/
c
m
3
)
Curing Time(days)
(CA 14)
(Polychem)
Page | 42


Fig 5.3: Variation of the Bulk Density with curing time of Castable 3

Fig 5.4: Variation of the CCS with curing time of Castable 1
5 10 15 20 25 30
2.40
2.45
2.50
2.55
2.60
2.65
2.70


B
u
l
k

D
e
n
s
i
t
y
(
g
m
/
c
m
3
)
Curing Time(days)
(CA 14)
(Polychem)
5 10 15 20 25 30
200
220
240
260
280
300
320


C
C
S
(
k
g
/
c
m
2
)
Curing Time(days)
(CA 14)
(Polychem)
Page | 43


Fig 5.5: Variation of the CCS with curing time of Castable 2


Fig 5.6: Variation of the CCS with curing time of Castable 3
5 10 15 20 25 30
190
200
210
220
230
240
250

C
C
S
(
k
g
/
c
m
2
)
Curing Time(days)
(CA 14)
(Polychem)
5 10 15 20 25 30
182
184
186
188
190
192


C
C
S
(
k
g
/
c
m
2
)
Curing Time(days)
(CA 14)
(Polychem)
Page | 44


Fig 5.7: Variation of the CCS with curing time of the three different castables with CA 14
as binder
From Figure 5.7 it is seen that the Castable 1 (conventional cement type) shows a higher value of
CCS as compared to the castable 2 and castable 3.This is because the Castable 1 is a
conventional cement type of castable containing 10% cement. Higher percentage of cement in
the composition allows castables to have higher percentage of hydraulic bonds upon water
addition. This fills up the porosity and holds the aggregates strongly as compared to the castable
2 and castable 3 which are low cement type (6 % cement). This imparts more green strength to
the castable 1 as compared to the castable 3.

5.2 STUDY OF THE FIRED STRENGTH OF THE CASTABLES:
All the 3 types of castables were fired at 1650C. The graphical representation of the cold
compressive strengths of the fired castables after firing at 1650C is as shown in the Fig 5.8.


5 10 15 20 25 30
180
200
220
240
260
280
300
320


C
C
S
(
k
g
/
c
m
2
)
Curing Time(days)
(Castable 1)
(Castable 2)
(Castable 3)
Page | 45


Fig 5.8: Fired strength of the Castables
Fig 5.8 shows that the fired strength of the Castable 1 is (892.70 kg/cm
2
) is lower than the
castable 2 (1024.2 kg/cm
2
) and castable 3 (1256.6 kg/cm
2
). The lower strength of the castables is
due to the higher percentage of cement (10%) in this conventional cement castable. On firing
gradual loss of water occurs due to the dehydration of the cement. So, castable 1 develops higher
porosity resulting in the reduction of strength. However for the castable 2 and castable 3 both of
which are of low cement type have lesser amount of cement (6%).Hence the quantity of water
required for the hydration of the cement phases is also less. This leads to lower gradual loss of
water in the form of water vapor due to the dehydration of the cement phases in both castable 2
and castable 3 and consequently this result in higher density. Hence fired strength of castable 2
and 3 is higher than the Castable1. Further the compressive strength developed in the castable 3
is much higher as compared to the others. This appears to be due to the presence of 4%
microsilica which had replaced reactive alumina in castable 3 .During sintering mullite formation
occurs due to the reaction between microsilica and reactive alumina. This mullite phase is likely
to provide an interlocking grain structure which imparts higher compressive strength to the
castable.


0
500
1000
1500
Castable 1 Castable 2 Castable 3
F
I
R
E
D

S
T
R
E
N
G
T
H

(

k
g
/
c
m
2
)

Page | 46

5.3 STUDY OF THE FLOWABILITY OF THE CASTABLES:
The flowability of the castables was determined following the procedure described in section
4.5.The comparative study is as shown in the following diagram (fig 5.9)

Fig 5.9: Flowability of the Castables

From the above Figure it is seen that the flowability of the conventional cement type of castable
(castable 1) was maximum followed by the castable 2 and castable 3.This could be due to the
fact that castable 1 is a conventional cement type of castable. It is having a greater percentage
of cement in the composition as compared to the other castables. Due to greater quantity of
cement greater amount of water addition is required for this castable which enhanced the
flowability. Castable 2 has a greater quantity of reactive alumina (34%) in the composition. This
material has a very fine particle size and hence has very high reactivity. Upon water addition in
presence of cement as a binder it results in the formation of an amorphous gel like phase of AH
3
(Al
2
O
3
.3H
2
O) [26]. This phase imparts a greater amount of gel like phase to the castable which
accounts for the lesser flowability as compared to the castable 1.Similarly in castable 3, although
the presence of micro silica is expected to enhance the flow property,but the simultaneous
presence of cement, reactive alumina and microslica probably leads to the formation of a gel like
structure which reduces its flowability.
100
120
140
Castable 1 Castable 2 Castable 3
F
L
O
W
A
B
I
L
I
T
Y

(
m
m
)

Page | 47

5.4 STUDY OF THE HMOR OF THE CASTABLES:
HMOR of the castables was measured at 1400 C. The HMOR was determined for three samples
of each castable composition. The comparative study of the HMOR of the different castable
compositions is as shown in the Figure 5.10 below:


Fig 5.10: Mean HMOR of all the three castables fired at 1650 C
It is observed that at any loading rate the HMOR of Castable 1 is much lower as compared to the
HMOR values of the castable 2 and castable 3.This is because the castable 1 is a conventional
cement type of castable with very high percentage of cement (10% cement). Table 3.3 indicates
that the percentage of CaO in the castable 1 is very high i.e. 3.152% as compared to the castable
2 and castable 3 where it is 1.9328% and 1.932% respectively. This results in the formation of
higher amount of low melting phases like anorthite (CaO.Al
2
O
3
.2H
2
O) and Gehlenite
(2CaO.Al
2
O
3
.SiO
2
) upon firing. These are low melting compounds and form a liquid phase
around 1250 C. This liquid phase coats the surface of the grains and reduces the degree of
Page | 48

atomic bonding between the grains. The presence of this liquid phase results in increased grain
boundary sliding and hence easy plastic deformation in the sample and ultimately the HMOR of
the sample is reduced. It is also further observed that the HMOR of the castable 2 is lower than
the castable 3.This is because in castable 3 a small fraction of reactive alumina was replaced with
fumed silica as the filler. This resulted in the formation of mullite phase upon sintering at
1650C.This mullite phase has better refractoriness, better mechanical strength, higher RUL and
better creep resistance. Due to this, the castable 3 shows a higher value of HMOR as compared
to the castable 2.
5.5 PHASE ANALYSIS BY XRD:
The Castable 3 was sintered at 1650C for 3 hours and then crushed and grounded in a mortar
pestle and then subjected to X Ray Analysis by the process as described in sec 2.7. The XRD
analysis shows the presence of mullite and corundum. Mullite is formed by the sintering
reactions taking place between reactive alumina and fumed silica upon sintering at 1650C.
However due to the close d spacing corundum and mullite, separate mullite peaks could be
identified as most of the prominent peaks overlapped with those of corundum.

Fig 5.11:XRD Analysis of the castable 3
Page | 49

The mullite phase was matched with the JCPDS file no. 02-1160 and the corundum phase was
matched with the JCPDS file no. 71-1124.Similarly the kyanite phase was matched with the
JCPDS file no:03-0513

5.6 MICROSTRUCTURAL ANALYSIS BY SEM:
The castable 3 samples were fired at a temperature of 1650 C for 3 hours. It was then crushed
and ground to very fine particle size. These powdered samples were subjected to microstructural
analysis using SEM (Fig 5.12) The SEM image show the development of needle shaped crystals.
Mullite phase has a needle shaped microstructure. So, the SEM analysis also supports the
development of small amount of mullite phase in the microstructure. The SEM micrograph is as
shown.


Corundum Mullite (Needle shaped)
Fig 5.12: SEM Analysis of the castable 3



Page | 50




CHAPTER 6

SUMMARY





Page | 51

This study was aimed to observe the effect of reactive alumina and micro-silica on the properties
of a high alumina cement bonded conventional refractory castable. In the first step 10% cement
was reduced to 6% with replacement with 4% reactive alumina. This replacement improved the
thermo-mechanical properties of the castables as indicated by the HMOR values. In the second
step, 4% of reactive alumina was replaced with 4% micro-silica. This second step replacement
also improved the mechanical and the thermo-mechanical properties of the refractory castable.
Upon phase analysis of the castable (with reactive alumina/micro-silica combination) revealed
the development of mullite in the composition. The presence of additional mullite phase was
responsible for the improvement in the properties of the refractory castables. These low cement
high Alumina based castables with a proper combination of reactive alumina and fumed
silica/micro-silica as the filler can be used for any variety refractory application like in the Iron
and Steel industry, glass industry, refineries, oil industries, tile industries etc.













Page | 52

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