DEVELOPMENT OF SLAG-RESISTANT REFRACTORY LININGS

By

DIPANKAR/SARKAR

B.Tech., Indian Institute of Technology, Kharagpur, 1

A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF

THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF APPLIED SCIENCE

in
THE FACULTY OF GRADUATE STUDIES
Department of Metallurgical Engineering

We accept this thesis as conforming

to the required standard

THE UNIVERSITY OF BRITISH COLUMBIA

.July 1984

(T) Dipankar Sarkar, 1984

6
f
 In p r e s e n t i n g this thesis in partial f u l f i l m e n t of the
r e q u i r e m e n t s f o r an advanced degree a t the University
of British Columbia, I agree that the Library s h a l l make
it freely available for reference and study. I further
agree t h a t permission for extensive copying of this thesis
for s c h o l a r l y p u r p o s e s may be g r a n t e d by the head o f my
department or by h i s or her representatives. It is
understood that copying or p u b l i c a t i o n of this thesis
for f i n a n c i a l gain s h a l l not be a l l o w e d w i t h o u t my written
permission.

Department of

The U n i v e r s i t y o f B r i t i s h Columbia
1956 Main Mall
V a n c o u v e r , Canada
V6T 1Y3

DE-6 (3/81)
 ii
ABSTRACT

A t t e m p t s have been made t o d e v e l o p slag resistant

r e f r a c t o r y l i n i n g f o r Dore f u r n a c e s , which a r e p r i m a r i l y
used f o r s m e l t i n g Pb-anodes i n o r d e r t o e x t r a c t precious
metals. A l l t h e p h y s i c a l p r o p e r t i e s o f Dore s l a g (PbO-
b a s e d ) such a s , m e l t i n g t e m p e r a t u r e , m e l t d e n s i t y , v i s c o s -
i t y , s u r f a c e t e n s i o n and w e t t i n g b e h a v i o u r over the tempera-
t u r e range o f f u r n a c e o p e r a t i o n s ( 6 0 0 - 1 1 0 0 ° C ) were d e t e r -
mined. These s t u d i e s i n d i c a t e d t h a t Dore s l a g s ( i ) m e l t
at t e m p e r a t u r e s between 550 and 6 0 0 ° C ; ( i i ) have
3
the m e l t d e n s i t i e s 5.0 t o 7.0 g/cm i n t h e t e m p e r a t u r e
range 7 5 0 - 1 0 5 0 ° C , m e l t d e n s i t y p r i m a r i l y b e i n g c o n t r o l l e d
3
by t h e c o n c e n t r a t i o n o f Pb0(P2QOQ-8.0 g/cm ) and B.i'^O^
3

(P QO -8.9 g/cm ) ; ( i i i ) a r e h i g h l y f l u i d i n t h e t e m p e r a -
2 C

t u r e range 7 5 0 - 1 0 5 0 ° C , h a v i n g t h e v i s c o s i t y o f 0.4 t o 0.8

N.S.m ; ( i v ) have low s u r f a c e t e n s i o n v a l u e s 450 t o 325
dyne.cm -1
a t 750°C and ( v ) have low c o n t a c t a n g l e s between 15
and 30° on a l u m i n a s u b s t r a t e s . These s l a g p r o p e r t i e s indi-
c a t e t h a t t h e s l a g s would s p r e a d v e r y e a s i l y on a l u m i n a r e -
f r a c t o r i e s and most p o s s i b l y on o t h e r refractories.

Coating compositions were then d e v e l o p e d by s t u d y i n g

the a v a i l a b l e phase e q u i l i b r i u m diagraim/s, w i t h t h e c o n s i d e r a -
t i o n t h a t a g l a s s y component would be n e c e s s a r y i n the
coating to seal-up the pores. S l a g p i l l t e s t s on c o a t e d
bricks revealed that only a p p l i c a t i o n of a coating could
not p r e v e n t s i g n i f i c a n t s l a g p r e n e t r a t i o n . T h i s i s so i n
s p i t e of the f a c t that the coating compositions contained
60-70 s i l i c a t o form a l a r g e amount o f g l a s s y phase i n
the c o a t i n g . To r e d u c e t h e h a r m f u l e f f e c t o f s l a g con-
s t i t u e n t s , CaO was found t o be t h e b e s t o x i d e t o p r o d u c e
h i g h t e m p e r a t u r e m e l t i n g compounds by r e a c t i n g w i t h oxide
constituents in slags.

F u r t h e r s t u d i e s on i m p r e g n a t i n g the b r i c k s with
CaO and C a C ^ show t h a t an optimum i m p r e g n a t i o n of bricks
w i t h i> 2 wt.% C a C ^ , and a c o a t i n g o f a m i x t u r e o f 30%
CaO, 60% S i 0 2 and 10% s l a g on t h e i m p r e g n a t e d b r i c k s , have
been a b l e t o s t o p s l a g p e n e t r a t i o n i n t o t h e r e f r a c t o r y
bricks.
 iv
TABLE OF CONTENTS
Page

Abstract ii
Table of Contents iv
L i s t of Tables viii
L i s t of Figures . ix

Acknowledgement x
iii

Chapter
1 INTRODUCTION .' 1

1.1 Refractory Usage ... 1

1.2 Refractory Failure 2

1.3 Refractory Lining Repair 3

1.4 Remedies f o r Refractory Failure 4

1.5 Problems Associated with Conventional Remedies .. 5

1.5.1 Dense Refractories . 5
1.5.2 Water Cooling 9

1.5.3 Water-cooled Panels 1,0

1.5.4 Refractory Impregnation .. 10

1.6 Refractories i n Ferrous Metallurgy ^ 2

1.7 Refractories i n Non-Ferrous Metallurgy 13

1.7.1 Lead Metallurgy 14

1.7.2 Possible Approaches Towards Solving the

Problem of Refractory Corrosion i n Dore
Furnaces ^
24
1.7.3 Dore Furnace Slags
 V

Chapter Page

1.8 Objectives of this Investigation 26

2 EXPERIMENTAL PROCEDURES AND RESULTS . 2 8

2.1 Materials Studied 2 8

2.2 Slag Properties 2 8

2.2.1 Chemical Properties 2 8

2.2.2 Chemical Composition 29

2.2.3 Slag Structure 29

2.2.4 Physical Properties 30

2.2.4.1 Melting Point Determination 30
2.2.4.2 Viscosity of Slags 36
2.2.4.3 Surface Tension and Melt Density 50
2.2.4.4 Melt Density 56

2.2.4.5 Experimental Procedure 60

2.2.4.6 Results and Analysis 66

2.2.4.7 Contact Angle 69

2.2.4.8 Conclusion . 81

3 DEVELOPMENT OF COATINGS 8 8

3.1 Coating Composition 0:7

3.1.1 Properties Required 89

3.1.2 Choice of Brick and Slag 91

no
3.1.3 Basis of Coating Development
94
3.1.4 Coating Composition
 vi

Chapter Page

3.1.4.1 Phase Diagrams Relevant to

Coating Composition Development.. 94
3.1.4.2 Coating Development Experiments.. 98
3.1.5 Coating A4. 104
3.1.5.1 Coating Materials 104
3.1.5.2 Coating Preparation 104
3.1.5.3 Coating Applications 104
3.1.5.4 Testing of Coating A4 .. 105
3.1.5.5 Determination of Slag-Penetration >
,;,

Depth 105
3.1.5.6 Results and Discussion 107
3.2 Ca0-Si0 -Slag Coatings
2 1° 7

3.2.1 Coating Composition 1° 7

3.2.2 Low Ca0-Si0 Coatings ...

2
109

3.2.3 High S i 0 Coatings

2
113

3.2.3.1 X-ray Diffractometer Studies of .'

the Coatings H 3

3.2.3.2 Coating Preparation ] 1 4

3.2.3.3 Slag Penetration Tests ]15

3.3 Results and Discussion 115

4 IMPREGNATION OF REFRACTORY BRICKS BY OXIDES AND SALTS 1 1 8

4.1 Introduction 1 1 8

119
4.2 Impregnation
 vii
Chapter Page

4.2.1 Calculation of Brick Porosity 119

4.2.2 Oxide Impregnation 120
4.2.2.1 Vacuum Suction 122
4.2.2.2 B o i l i n g 125

4.2.3 S a l t Impregnation 126

4.2.4 Slag Penetration Tests on C a C l 2

Impregnated Bricks I 2 9

4.2.5 E f f e c t of Different wt.% C a C l 2 '

Impregnation on Slag Penetration ^ 2

4.2.6 Impregnation and Coating ^ 37

4.3 Reactions Between Coatings, C a C l and Slag

2 144
4.4 SEM Studies on Slag Penetration 147
4.5 Coatings and Impregnation on Magnecon Bricks .... 153

5 SUMMARY AND CONCLUSIONS I 5 6

SUGGESTIONS FOR FUTURE WORK ]59

BIBLIOGRAPHY I 6 1

APPENDICES
1 V i s c o s i t y of Slags 165

la V i s c o s i t y Measurements 1f
>9
2 Surface Tension and Density of Slags 172

3 Correction f o r the E f f e c t of Gravitational Force '

on the Shape of a S e s s i l e Drop 175

4 Contact Angles of Dore Slags 180

 vi i i

LIST OF TABLES

Table P a
9 e

I Composition o f Magnecon B r i c k s 16

II S e r v i c e L i f e of Magnesia R e f r a c t o r i e s 20

III Composition of Dore" Slags

IV Phases I d e n t i f i e d i n Dore Slags . 31

V M e l t i n g P o i n t of Dore Slags 35

VI PbO-Oxide E u t e c t i c s ... 36

87
VII P h y s i c a l P r o p e r t i e s o f Dore Slags.
no

VIII Phase Diagrams f o r Magnecon-Dore Slag Systems

IX Phases I d e n t i f i e d i n CaO + Slag C4 Mixtures 103

X Composition o f Coatings ^
XI P o r o s i t y o f Alumina B r i c k s 120

124

XII CaO Impregnation i n Alumina B r i c k s

XIII Wt. % CaO Impregnation i n Alumina B r i c k s 126

XIV CaO Impregnation i n Alumina B r i c k s I 2 8

Ala.l V i s c o s i t y o f DorS Slags 170

Ala.2 V i s c o s i t i e s o f CaO and Slag Mixtures 171

A2.1 Surface Tension 173

A2.2 Density o f Slags 174

A4.1 Contact Angles o f D i f f e r e n t Slags 181

182
A4.2 I n t e r f a c i a l Tension o f D i f f e r e n t Slags
 ix

LIST OF FIGURES
Figure Page

1 S t a b i l i t y and Propagation Behaviour of Cracks 8

2 Flow-Chart for the Dore Process 17

3 Simplified Flow-Chart f o r the Dore Process .. ^ 8

4 Elevation View of a Dore Furnace 19

5 Photograph of Corroded Magnecon Refractories 22

6 Melting Temperature of Dore Slags 33

7 Schematic View of the Viscosity-Measuring Apparatus .. 39

8 Schematic View of the Vertical-Furnace 4 2

9 Calibration Plot f o r the Modified Spindle 4 4

10a Viscosity of Dore Slags 4 7

.10b Normalized Viscosity Plot of Dore Slags ..

11 Viscosity of Dore Slags 49

12 Capillary Rise i n a Tube 53

13 D i f f e r e n t i a l Capillary Rise in Tubes 53

14 Increase of Capillary Rise of Slags i n Alumina Tubes

With Time. Time from 1 to r ( i ) 30 sees , ( i i ) 60
sees and ( i i i ) 2 mins. ^
15 Apparatus Used for the Maximum Bubble Pressure Method. 61
16 Dependence of the Maximum Manometric Height on
Bubbling Interval 64
17 Surface Tension of Dore Slags 67
18 Density of Dore" Slags 70
 X

Figure Page

19(a) Elevation View of a S e s s i l e Drop 71

19(b) Surface Tensions Associated with a S e s s i l e Drop 7

1
20(a) S e s s i l e Drop 76

20(b) Incorporation of the Drop in (a) into a

Representative C i r c l e — 7
^
21 S e s s i l e Drop Picture of a Slag Pellet on an
on
Alumina Substrate u

22 Contact Angles of Dore Slags on Alumina 82

, oo

23 Interfacial Tension of Dore Slags with Alumina

24 Density and Viscosity of Dore Slags vs Wt.%Pb Content
of the Slags 85

25 Surface Tension and Content Angle of Slags vs

Wt.% Pb Content 86

26 Normalized Viscosity Plot for CaO Slag C4 Mixtures 100

27 DTA Plot for a 20 Wt.% CaO + Slag C4 Mixture 101
28(a) Picture of a Slag-Penetrated Alumina Brick 106
28(b) Schematic View of the Brick in 28(a) .. 106
29 Slag Penetration in A 1 0 Bricks
2 3 108
30 Ca0-Si0 Phase Diagram
2 :... 110
31 DTA Plot for Coating C8 112
32(a) Slag Penetration in A l , ^ Bricks with Coatings 1:

A8, C7 and C8 116

32(b) Slag Penetration in Alumina Bricks with Coatings
C6, DI and D2 H 7
 xi
Figure Page

33 Apparatus Used f o r Vacuum Suction 123

34 Shows Alumina Bricks after Slag-button Tests 130
35 Bricks with Varying Amounts o f C a C l Impregnation
2 133
36 Photograph o f Cracks in Bricks Due to Excessive ^
C a C l Impregnation
2 135
37 SEM Photomicrograph of such a Crack 136
38 Slag Penetration Distance vs Wt.% C a C l 2 Impregnation
for Coatings A6, C8 and DI 1 3 9

39 Slag Penetration Distance vs Wt. % CaCl 2 Impregnation

for Coatings A4, D2 and C6 1 4 0

40 Slag Penetration i n Alumina Bricks with Coating

A4 and C a C l Impregnation
2
141

41 Slag Penetration i n Alumina Bricks with Coating

i no

DI and C a C l Impregnation
2

42 Slag Penetration in Alumina Bricks with Coatings

14?

and C a C l Impregnation
2

43 Slag Spreading on Alumina Bricks — 145

44 SEM-EDX Plot for a Slag Attacked Alumina Brick 1 4 8

45 SEM-EDX Plot f o r a Slag Penetrated C a C l Impregnated

2

149
Alumina Brick
46 SEM-EDX Plot for a Slag Penetrated Alumina Brick
with Coating D2 ,ou

47 SEM-EDXImpregnation
Plot f o r a and
Slag.Coating
Penetrated 152
CaCl~ D2 Alumina Brick with
 xii
Figure Page

48 SEM-EDX Plot f o r a Slag Penetrated Magnecon

Brick with CaCl Impregnation and Coating D2 —
2 155
A3.1 S e s s i l e Drop 176

A3.2 S e s s i l e Drop Under the Influence of Gravity I 7 6

A3.3 Plot Used f o r Contact; Angle Corrections I 7 9

 xiii

ACKNOWLEDGEMENT

I w o u l d l i k e t o t h a n k P r o f . A.C.D. C h a k l a d e r for his

a s s i s t a n c e and guidance, and t h e t e c h n i c i a n s and t h e
graduate students o f the department f o r t h e i r help.
T h a n k s a r e a l s o due t o C o m i n c o , L t d . , f o r t h e i r k i n d
cooperation and a l s o f o r s u p p l y i n g the slags along with
t h e i r a n a l y s i s and t h e b r i c k s used f o r t h i s i n v e s t i g a t i o n .

Financial support f r o m NSERC i s g r a t e f u l l y a c k n o w l e d g e d .

 Chapter 1

V. INTRODUCTION

1• 1 Refractory Usage

A l a r g e number o f i n d u s t r i e s , b o t h metallurgical
and n o n - m e t a l l u r g i c a l , use r e f r a c t o r i e s f o r v a r i o u s pur-
poses. In the m e t a l l u r g i c a l i n d u s t r i e s , r e f r a c t o r i e s are
u s e d m a i n l y f o r metal p r o d u c t i o n by pyrometallurgical
processes. The f o l l o w i n g i n d u s t r i e s a r e the p r i m e c o n -
sumers o f r e f r a c t o r y bricks:^
Iron and S t e e l Industries 60% o f t h e t o t a l )
Non-ferrous metals
Cement
Glass
P e t r o l e u m and o i l
Cerami c
Power g e n e r a t i o n

In t h e m e t a l l u r g i c a l industry, the major areas

where r e f r a c t o r i e s a r e used can be i d e n t i f i e d a s :
Smelting
R o a s t i ng
Heat Treatment
 2

Soaking P i t
Coke Oven
Ladle Lining
T u n d i sh

1-2 Refractory Fai1ure

The m a j o r c a u s e s o f r e f r a c t o r y f a i l u r e can be
b r o a d l y c l a s s i f i e d under the f o l l o w i n g categories:

(a) C o r r o s i o n and Erosion

The m a j o r c a u s e o f r e f r a c t o r y f a i l u r e i n any metal-
l u r g i c a l f u r n a c e i s due to the c o r r o s i o n and e r o s i o n o f the
refractory lining materials by the m o l t e n s l a g . In s l a g
c o r r o s i o n , the s o l u t i o n a t the s l a g - r e f r a c t o r y interface
and the d i f f u s i o n o f the d i s s o l v e d r e f r a c t o r y constituents
from the i n t e r f a c e t h r o u g h a b o u n d a r y l a y e r i n t o the slag,
2

i s the m a j o r r a t e c o n t r o l l i n g f a c t o r . Hence, i t can be

e n v i s a g e d t h a t both c o r r o s i o n and e r o s i o n l e a d to r e f r a c -
t o r y d i s s o l u t i o n which l e a d s to t h e i r f a i l u r e .
(b) Spalling
S p a l l i n g i s u s u a l l y d e f i n e d as the f r a c t u r e o f r e -
f r a c t o r y b r i c k s due to t h e r m a l s t r e s s e s s e t up i n the brick
d u r i n g t h e i r use. Thermal s t r e s s e s ean be s e t up by uneven
h e a t i n g o r c o o l i n g of the b r i c k due to t e m p e r a t u r e
fluctuations in service. In the l a t t e r c a s e , the expansion
 3

c o u l d be l a r g e enough to p r o d u c e s h e a r f a i l u r e s . Refrac-
tory materials (metal o x i d e s ) n o r m a l l y have low thermal
c o n d u c t i v i t y and so when t h e y are s u b j e c t e d to h i g h heating
or c o o l i n g r a t e s , t h e r m a l s t r e s s e s can e a s i l y c a u s e f a i l u r e .

(c) Slag Penetration and Spalling

T h i s s p e c i a l but common c a u s e f o r r e f r a c t o r y
3

f a i l u r e has been c a l l e d s p a l l i n g by some, but i t would

be b e t t e r not to c l a s s i f y i t under s p a l l i n g . In t h i s c a s e ,
the s l a g : i ) penetrates the s u r f a c e l a y e r s o f the brick,
i i ) r e a c t s w i t h the b r i c k m a t e r i a l , and i i i ) forms various
compounds and g l a s s y p h a s e s . The s l a g - p e n e t r a t e d layer,
so f o r m e d , has a d i f f e r e n t t h e r m a l e x p a n s i o n c o e f f i c i e n t
as compared to the r e s t o f the b r i c k , and the s u r f a c e layer
cracks, p e e l s or s h e a r s o f f d u r i n g thermal c y c l i n g .

1.3 Refractory Lining Repair

The c o s t o f r e p l a c i n g or r e p a i r i n g refractory
l i n i n g s i s a r e c u r r i n g e x p e n s e and problem.

In c e r t a i n o p e r a t i o n s , where r e f r a c t o r y bricks
have to be r e p l a c e d two or t h r e e t i m e s a y e a r , the cost
involved in r e f r a c t o r y repair contributes a significant
p a r t t o the t o t a l c o s t o f metal p r o d u c t i o n . To g i v e an
example, one of the l a r g e s t i r o n and s t e e l p r o d u c e r s i n
 4
Canada s p e n t a b o u t 40 m i l l i o n d o l l a r s t o p u r c h a s e r e f r a c -
t o r i e s i n 1980. It i s very l i k e l y that they spent almost
the same amount i n s t a l l i n g them. The c o s t o f down-time
( s h u t - d o w n ) o f metal p r o d u c i n g u n i t s i s not i n c l u d e d i n
the above estimate.

The t o t a l c o s t i n v o l v e d i n r e f r a c t o r y l i n i n g r e p a i r
can be g r o u p e d under the f o l l o w i n g categories:

(a) Cost of purchasing r e f r a c t o r i e s .

(b) The down-time c o s t o f the m e t a l p r o d u c i n g units.
(c) The l a b o u r c o s t o f i n s t a l l i n g the r e f r a c t o r i e s .

1.4 Remedies f o r R e f r a c t o r y F a i l u r e

Due to many f a c t o r s , t h e p r o b l e m o f r e f r a c t o r y b r i c k
d i s s o l u t i o n by s l a g s c a n n o t be p r e v e n t e d i n p r a c t i c e , but
r e c e n t d e v e l o p m e n t s have i n d i c a t e d t h a t r e f r a c t o r y f a i l u r e ,
due t o s p a l l i n g o r s l a g a t t a c k , can be r e d u c e d s i g n i f i c a n t l y .
In the f o l l o w i n g s u b s e c t i o n s , r e f r a c t o r y f a i l u r e by s l a g
a t t a c k w i l l be e m p h a s i z e d more i n c o m p a r i s o n to thermal
f a i l u r e as ( i ) t h i s k i n d o f f a i l u r e i s more common and
( i i ) the p r e s e n t work i s d i r e c t e d towards the s t u d y o f s l a g
a t t a c k on r e f r a c t o r i e s .

The s l a g c o r r o s i o n p r o b l e m i s c o n v e n t i o n a l l y
handled by the f o l l o w i n g methods:
 5
(a) Use o f dense r e f r a c t o r i e s whenever a v a i l a b l e
(b) C h e m i c a l c o m p o s i t i o n mani pul a t i o n - e s ' s e n t i a l l y i n -
v o l v i n g the s e a r c h f o r a c h e m i c a l l y i n e r t r e f r a c t o r y
material
(c) Water c o o l i n g o f r e f r a c t o r y linings
(d) Replacement o f r e f r a c t o r i e s o r f u r n a c e w a l l s en-
t i r e l y by t h e use o f w a t e r - c o o l e d metal panels
(e) F i l l i n g the p o r e s i n r e f r a c t o r i e s w i t h c a r b o n
(f) The use o f s p e c i a l r e f r a c t o r i e s l i k e s i l i c o n c a r b i d e ,
silicon nitride, etc.

1. 5 Problems A s s o c i a t e d w i t h C o n v e n t i o n a l Remedies

]. 5 . -j Dense R e f r a c t o r i e s
Dense r e f r a c t o r i e s have two main drawbacks: (a)
4-8
poor t h e r m a l shock p r o p e r t i e s ~ ••(b) the h i g h c o s t and
d i f f i c u l t y involved in their fabrication. As a m a t t e r o f
f a c t , v e r y few such r e f r a c t o r i e s a r e c o m m e r c i a l l y available.

The b a s i c r e q u i r e m e n t s o f a r e f r a c t o r y b r i c k a r e
h i g h t h e r m a l shock r e s i s t a n c e c o u p l e d w i t h low t h e r m a l
conductivity. The l a t t e r p r o p e r t y i s n e c e s s a r y and impor-
t a n t , as r e f r a c t o r i e s s h o u l d a l s o p o s s e s s i n s u l a t i n g p r o -
p e r t i e s . K i n g e r y 8 and Hasselman 9 showed t h a t good t h e r m a l
shock r e s i s t a n c e r e q u i r e s h i g h t h e r m a l c o n d u c t i v i t y , but
high thermal c o n d u c t i v i t y in r e f r a c t o r i e s o b v i o u s l y leads
 6

to poor i n s u l a t i n g p r o p e r t i e s . T h i s means good t h e r m a l

shock r e s i s t a n c e and low t h e r m a l c o n d u c t i v i t y are mutually
incompati b l e .

I t has been shown by HasseTman, Smith and co-

w o r k e r s , 5 and G a r v i e and N i c h o l s o n 4 t h a t i n h e r e n t p o r o s i t y
or induced p o r o s i t y i n r e f r a c t o r i e s up t o a c e r t a i n d e g r e e
h e l p s t o i n c r e a s e the t h e r m a l shock p r o p e r t i e s . Their
work was done p r i m a r i l y on a l u m i n a (Al2^3) and partially
s t a b i l i z e d z i r c o n i a ( P S Z ) , but t h e i r c o n c l u s i o n s can be
extrapolated to o t h e r r e f r a c t o r i e s as w e l l . Pores i n
5
b r i c k s can a c t both as c r a c k i n i t i a t o r s and a r r e s t o r s .
So,, i n the l a t t e r c a s e an i n c r e a s e d p o r o s i t y l e a d s to a
decrease in crack length. The shape and d i s t r i b u t i o n o f
5 10
the p o r e s ' a l s o seem': to have a b e a r i n g on the t h e r m a l
shock p r o p e r t i e s . In the above d i s c u s s i o n , the term
' t h e r m a l s h o c k ' i s d i r e c t l y r e l a t e d t o the s t r e n g t h re-
t a i n e d i n a r e f r a c t o r y b r i c k a f t e r a t h e r m a l shock t e s t . ' ' 6 1 1 1 2

T h i s term can be f u r t h e r e l a b o r a t e d quantitatively. Hassel-

man d e v e l o p e d an e q u a t i o n to p r e d i c t the c r i t i c a l temperature
d i f f e r e n c e (&T ) c r e q u i r e d f o r the i n i t i a t i o n o f c r a c k pro-
pagation which i s :
HT c = x (1+2TTN£ ) 2

•na EZ

where the symbols a, E and G r e f e r t o the c o e f f i c i e n t o f

t h e r m a l e x p a n s i o n , Young's modulus o f e l a s t i c i t y and the
 7

f r a c t u r e surface energy, r e s p e c t i v e l y . F i g u r e 1 shows AT c

as a f u n c t i o n o f c r a c k length.

From t h i s f i g u r e i t can be seen t h a t when i < i' ,

m

AT c decreases w i t h i n c r e a s i n g c r a c k l e n g t h and i s indepen-

dent o f c r a c k d e n s i t y . When % > & , 'AT m -increases r a p i d l y
w i t h both t h e c r a c k l e n g t h and the c r a c k d e n s i t y . The
reason f o r t h i s i s t h a t the p r e s e n c e o f the c r a c k s reduces
the e f f e c t i v e v a l u e o f Young's modulus ( E ) . For crack
lengths > £ , t h e value of AT
m £ can be i n c r e a s e d s i m p l y by
i n c r e a s i n g the c r a c k d e n s i t y 'N'.

7 4
R o s s i , G a r v i e and N i c h o l s o n who worked on m i c r o -
c r a c k e d MgO-W c o m p o s i t e s and p a r t i a l l y s t a b i l i z e d z i r c o n i a
(PSZ) r e s p e c t i v e l y , v e r i f i e d t h a t m i c r o c r a c k i n g and p o r o s i t y
i n c r e a s e d the thermal shock p r o p e r t i e s o f c e r a m i c s . So i t
can be c o n c l u d e d t h a t the use o f dense ( a l m o s t 100%) r e -
f r a c t o r i e s may not be a s u i t a b l e remedy f o r s l a g a t t a c k .

Dense r e f r a c t o r i e s c o u l d be used to p r e v e n t slag

13
p e n e t r a t i o n but i t has been shown t h a t s l a g s can also
penetrate along grain boundaries. So c o n s i d e r i n g the c o s t
and e f f o r t s needed i n d e v e l o p i n g such b r i c k s and a t the
expense of thermal p r o p e r t i e s , i t may not be an e f f e c t i v e
way in preventing s l a g p e n e t r a t i o n and corrosion.
F i g . 1: S t a b i 1 i t y and P r o p a g a t i o n B e h a v i o u r of Cracks.
C Ref. 9 )
 9

Developing a new r e f r a c t o r y f o r a s p e c i f i c k i n d o f
a f u r n a c e and s l a g i s n o t v e r y f e a s i b l e due t o t h e l a c k o f
i n f o r m a t i o n ( e s s e n t i a l l y phase d i a g r a m s ) i n the f i e l d of
ceramics. Although t h e r e a r e q u i t e a number o f phase
d i a g r a m s on b i n a r y and t e r n a r y o x i d e s y s t e m s , t h e s e aren't
o f much h e l p when c o n s i d e r i n g complex r e f r a c t o r y - s l a g prob-
1 ems.

Developing a c h e m i c a l l y i n e r t b r i c k with a l l the

r e q u i r e d p h y s i c a l ( c r u s h i n g s t r e n g t h and modulus o f r u p t u r e )
and t h e r m a l (thermal shock and i n s u l a t i o n ) p r o p e r t i e s may
not be p o s s i b l e , even i f c h e m i c a l l y i n e r t m a t e r i a l s c a n be
found o r developed.

1.5.2 Mater C o o l i n g

Water c o o l i n g o f r e f r a c t o r i e s i s a p o s s i b i l i t y b u t
here t h e f u r n a c e and t h e r e f r a c t o r y l i n i n g d e s i g n would
have t o be c h a n g e d , w h i c h would i n v o l v e e l a b o r a t e re-design-
ing. T h i s method would o b v i o u s l y r e q u i r e a l a r g e c a p i t a l
investment.

This approach i s followed s p e c i a l l y i n t h e f e r r o u s -

extractive industry. In t h e b l a s t f u r n a c e , t h e temperature
i n the lower zone ( h e a r t h , b o t t o m , bosh and t u y e r e region)
i s i n t h e o r d e r o f 1 3 0 0 - 1 8 0 0 C ; here the r e f r a c t o r i e s
o

( c a r b o n , f i r e b r i c k , f u s e d a l u m i n a and z i r c o n i a ^ a l u m i n a ) a r e
water c o o l e d . Water c o o l e d c a r b o n l i n i n g s a r e a l s o used
in the c a s e o f c a s t i r o n C u p o l a s i n the lower p a r t s o f
the s h a f t r e g i o n . In the n o n - f e r r o u s i n d u s t r y , where t h e
operating temperatures a r e n o t v e r y h i g h compared to b l a s t
f u r n a c e s and s t e e l - m e l t i n g f u r n a c e s , t h e use o f c o o l i n g o f
r e f r a c t o r i e s (by a i r o r w a t e r ) i s somewhat l e s s p r e v a l e n t .
To c i t e some e x a m p l e s : the b o t t o m s o f c o p p e r anode r e f i n -
ing f u r n a c e s a r e c o o l e d by a i r or a t t i m e s by water*, w a t e r
c o o l i n g i s used i n e l e c t r i c s t e e l making e x t e n s i v e l y .

1.5.3 Water-cooled Panels

Removing r e f r a c t o r i e s a l t o g e t h e r and r e p l a c i n g them

by w a t e r - c o o l e d metal panels (or w a l l s ) i s a p o s s i b i 1 i t y
N

but t h i s a g a i n , as i n the p r e v i o u s e a s e , i n v o l v e s a l a r g e
c a p i t a l investment an.d a. re-design "of the f u r n a c e . In t h i s
e a s e , t h e p r o t e c t i v e c o a t i n g on the w a l l s i s o b t a i n e d by
the s l a g i t s e l f , as the s l a g s o l i d i f i e s when i t comes i n
c o n t a c t w i t h the c o l d , w a t e r - c o o l e d walls.

1.5.4 Refractory Impregnation

F i l l i n g r e f r a c t o r y p o r e s w i t h c a r b o n has been
p r a c t i c e d from as e a r l y as t h e l a t e 1800s. These early
r e f r a c t o r i e s were made from m i x t u r e s o f d e a d - b u r n t d o l o m i t e
and p i t c h ( t a r ) , and were used p r i m a r i l y i n b a s i c - b e s s e m e r
furnaces. A t p r e s e n t , r e f r a c t o r y b r i c k s , used i n t h e i r o n
and s t e e l i n d u s t r y , and s p e c i a l l y i n B a s i c Oxygen P r o c e s s
14
(BOP), a r e a l m o s t always P i t c h - B e a r i n g MgO-CaO r e f r a c t o r i e s .
When t h e s e p i t c h b e a r i n g r e f r a c t o r i e s a r e i n i t i a l l y h e a t e d ,
by c h a r g i n g h o t coke i n t h e c o l d BOP f u r n a c e , t h e r a p i d
h e a t i n g ( 3 8 ° C / m i n ) t o about T095°C i g n i t e s t h e p i t c h i n t h e
refractory lining. The v a p o u r s p r o d u c e d by t h i s ignition,
moves away from t h e h o t f a c e and d e p o s i t s carbon i n the
c o n s t r i c t e d ends o f p o r e s a t a p o s i t i o n where t h e c a r b o n i z a -
tion temperature i s reached. The c a r b o n i n t h e s e b r i c k s
15
c o u l d be a b o u t 3-4% by w e i g h t . These b r i c k s a r e more
c o r r o s i o n r e s i s t a n t , as s u g g e s t e d by t h e i r use i n t h e BOP.
Carbon p r e v e n t s t h e c o r r o s i o n o f t h i s r e f r a c t o r y b r i c k
( m a i n l y M a g n e s i a and M a g n e s i a - C a l c i a ) by t h e methods p r o -
p o s e d by Park and B a r r e t t , 15 Kappmeyer and H u b b l e , 16 Howe
and McGee, 17 B r e z n y and Landy 18 and o t h e r s :
(a) The c a r b o n p h y s i c a l l y p r e v e n t s t h e e n t r y o f t h e
s l a g i n t o t h e b r i c k as t h e s l a g - c a r b o n c o n t a c t a n g l e i s
q u i t e l a r g e ( g r e a t e r than 9 0 ° ) . 1 6

19
(b) Robinson proposed that the pressure of the carbon
monoxide gas p r o d u c e d by t h e r e d u c t i o n o f MgO i n t h e b r i c k
by t h e c a r b o n ( a l s o p r e s e n t i n t h e b r i c k ) a c c o r d i n g t o t h e
reaction:
 12

MgO(s) + C(s) •+ Mg(gr) + CO(g) 1.2

prevents or r a t h e r delays the penetration of slag i n t o the

brick.
20

(c) Chesters proposed t h a t t h a t carbon i n the r e -

f r a c t o r y b r i c k reduces the f e r r i c oxide (or calcium f e r -
r i t e ) i n t o FeO o r even m e t a l l i c i r o n , b o t h o f which a r e
v i r t u a l l y non-corrosive to m a g n e s i a (MgO) and l i m e (CaO) i n
the b r i c k .
15 18

Recently, * i t has been shown t h a t t h e c a r b o n

i n t h e r e f r a c t o r y b r i c k s used i n BOP's has c e r t a i n d r a w b a c k s .

I t seems t h a t t h e c a r b o n i n the b r i c k reduces the

m a g n e s i a and t h e magnesi um vapour thus- p r o d u c e d l e a v e s that
particular region. T h i s i n c r e a s e s b r i c k p o r o s i t y and
leads, e v e n t u a l l y , to a decrease i n the strength of the
brick.

When c a r b o n i m p r e g n a t e d a l u m i n a b r i c k s were used

1 5

i n a sodium t e t r a b o r a t e m e l t and a sodium v a n a d a t e melt,

the c a r b o n was r a p i d l y o x i d i z e d t o CO2 g a s . The e v o l u t i o n
o f gas from the i n n e r p o r e s o f a r e f r a c t o r y c o u l d give
r i s e t o m i c r o - and m a o r o - c r a c k i n g .

1.6 R e f r a c t o r i e s i n Ferrous Metallurgy

As m e n t i o n e d b e f o r e , t h e F e r r o u s Metallurgy
 13
i n d u s t r y i s t h e m a j o r consumer (A, 60%) o f a l l r e f r a c t o r i e s .
So, i t i s q u i t e u n d e r s t a n d a b l e t h a t most o f the r e f r a c t o r y
d e v e l o p m e n t has been done i n t h i s f i e l d . Some r e c e n t
developments i n t h i s f i e l d i n c l u d e t h e use o f :

(a) g r a p h i t e - S i C b r i c k s i n t h e bosh r e g i o n o f t h e
b l a s t f u r n a c e by the Japanese.
(b) S i C and S i N 3 4 b r i c k s i n t h e m i d d l e and upper
sections of b l a s t furnaces. Servere abrasion occurs in
t h e s e s e c t i o n s , due to the passage o f l i m e s t o n e , coke and
iron ore s i n t e r s .
(e) a i r and water c o o l e d g r a p h i t e b r i c k s i n t h e h e a r t h
r e g i o n o f b l a s t f u r n a c e s , where the o p e r a t i n g temperatures
are very high.
(d) carbon impregnated b r i c k s i n t h e B a s i c Oxygen
Furnace (section 1.5.5 ) and a l s o i n t h e LD p r o c e s s o f
s t e e l making.
S l a g a t t a c k on r e f r a c t o r i e s i s v e r y s e v e r e i n t h e s e p r o -
c e s s e s , due t o h i g h t e m p e r a t u r e s employed. Such b r i c k s
can be used f o r about 300 h e a t s i n the BOF and f o r a b o u t
3000 h e a t s i n the QB0P. 1

1. 7 R e f r a c t o r i e s in Non-Ferrous Metallurgy

In the f i e l d o f n o n - f e r r o u s m e t a l l u r g y , v e r y
l i t t l e work has been done towards the d e v e l o p m e n t o f
r e f r a c t o r i e s as compared to f e r r o u s m e t a l l u r g y . The
 14
development o f r e f r a c t o r i e s i n t h i s f i e l d i s very dif-
f i c u l t , due t o t h e l a c k o f phase e q u i l i b r i a f o r s y s t e m s
involving non-ferrous s l a g s and o x i d e s .

The o n l y d e v e l o p m e n t has been an i n c r e a s e d u s e o f

3

basic refractories i n non-ferrous metallurgy. Most o f

the r e f r a c t o r i e s a r e s e l e c t e d on a t r i a l and e r r o r b a s i s ; 1

the f a c t o r s f o r c h o o s i n g the best r e f r a c t o r y being i t s

c o s t , a v a i l a b i l i t y and r e s i s t a n c e t o s l a g attack.

No a p p a r e n t a t t e m p t has e v e r been made t o d e v e l o p

new r e f r a c t o r i e s f o r s p e c i a l i z e d a p p l i c a t i o n s i n non-
ferrous metallurgical furnaces. This i s true f o r the
C o p p e r , N i c k e l , Lead and o t h e r n o n - f e r r o u s metallurgical
industries. I t ean be s a i d t h a t t h e major d e v e l o p m e n t s
and improvements t h a t can be made i n t h e f i e l d o f r e f r a c -
t o r i e s l i e i n non-ferrous metallurgical applications.

1.7.1 Lead M e t a l 1urgy

In t h e p r o c e s s of lead e x t r a c t i o n , the valuable

e l e m e n t s l i k e g o l d and s i l v e r a r e c o n c e n t r a t e d i n the
lead anodes. When t h e s e l e a d anodes ( b u l l i o n ) a r e f u r t h e r
p u r i f i e d , t h e p r e c i o u s m e t a l s ( g o l d and s i l v e r ) a l o n g with
b i s m u t h , a n t i m o n y , c o p p e r , a r s e n i c , s i l i c o n and z i n c pass
i n t o t h e anode s l i m e . This slime i s melted y i e l d i n g
' B l a c k M e t a l ' (26 o z / t o n Au, 7000 o z / t o n Ag, 20 wt.% Pb,
40 w t . ! Sb, 15 wt. % A s , 5 wt.% Bi. and 3 wt.% C u ) . The
B l a c k M e t a l i s b u r n t down i n Dore f u r n a c e s i n d i f f e r e n t
s t a g e s and e v e n t u a l l y s i l v e r and g o l d a r e r e c o v e r e d and
f u r t h e r p u r i f i e d by e l e c t r o l y s i s ( F i g s . 2 and 3 ) .

The r e f r a c t o r y b r i c k s used i n t h e s e Dore f u r n a c e s

are e s s e n t i a l l y Magneeon ( T a b l e I ) . The s l a g s t h a t a r e
g e n e r a t e d i n t h e s e d i f f e r e n t 'Dore burndowns' ( f i g . 3 ) ,
have d i f f e r e n t c o m p o s i t i o n s which a r e l i s t e d i n T a b l e I I .
I t can be seen t h a t t h e s l a g s have h i g h l e a d , a r s e n i c ,
b i s m u t h and a n t i m o n y concentrations.

The Dore f u r n a c e i s ' e s s e n t i a l l y an o v a l - s h a p e d

domed f u r n a c e i n t h e p l a n view. From F i g . 2, i t c a n be
n o t e d t h a t t h e maximum t e m p e r a t u r e i n any o f t h e s e
f u r n a c e s i s l e s s than 1100°C. Temperature here i s n o t as
s e v e r e as i n t h e ease o f most f u r n a c e s used i n t h e f e r r o u s
metallurgical industry.

Most o f t h e r e f r a c t o r y d i s s o l u t i o n t a k e s p l a c e
a t t h e s l a g l e v e l and a t t h e r o o f l e v e l . F i g . 4 shows an
e l e v a t i o n view o f t h e f u r n a c e . I t can be seen t h a t h i g h
duty f i r e c l a y b r i c k s a r e used on t h e bottom and c o r r o s i o n
here i s n o t so s e v e r e . T h i s i s due t o t h e f a c t t h a t a t
the b o t t o m , most o f t h e m e l t i s i n t h e m e t a l l i c s t a t e and
 16

Table I Composition o f Magnecon B r i c k s

Consti tuents wt. %

Si0 2 9.0

CaO 18.3

F e
2°3 7.6

A 1
2°3 3.9

C r
2°3 7.9

MgO 53. 3
 Slag "A" 700 C
o

Slimes Melting

Metal Metal

Bumdown Burndown
No. 4 Dore No. 5 Dore
Mild Oxidation M i l d Oxidation

Metal Metal
Plus Plus
Slag "D" Slag "D"
840°C 840°C

Slag "B" No. 1 Dore No. 2 Dor£

1080°C Strong Oxidation Strong Oxidation

Slag "B"
1080°C
Metal Metal

Parting C e l l s

Drum-Shaped
No. 3 Furnace
Mild Reduction
Gold/Silver

B1/Pb A l l o y

Slag "C" 1040 C

e

2 Flow-Chart f o r the Dore Process.

Impure Lead Anode Slime Slime Block Metal (Au,

Bullion (Anodes) (Ag,Au,Bi,Sb,As) Melting Ag.Pb.Sb, As, Bi.Cu)

Burn-down Furnace
removes Sb 8 As
at ~ 8 0 0 C B

Burn-down
Metal
I
Dore Furnoce (~IIOO°C)
removes Pb,Bi, Cu as
Litharge Slog
1
Dore Furnoce Metal

99 % A g a ~ 0 5 % Au

Ag. 1
Electrorefining
Au

3 S i m p l i f i e d F l o w - C h a r t f o r the Dore P r o c e s s .
Fig. 4 E l e v a t i o n View o f a Dore F u r n a c e .
 20

T a b l e II S e r v i c e L i f e of Magnesia Refractories.

Slag A v e r a g e L i f e o f 9"
Magnesia R e f r a c t o r i e s

A 9-12 months
B 3 - 5
C 9-12
D 6-12

Composition and s e r v i c e t e m p e r a t u r e o f above s l a g s .

Slag Temp °C % Cu % Pb % Zn % Sb % As % Bi % Si0 2

1

A 700 9.2 26.0 0.2 39.0 7.0 0.3 10.0

B 1080 10.0 47.0 0.2 7.0 3.0 18.0 1.5
C 1040 2.7 42.0 4.0 17.0 3.0 2.0 5.0
D 840 10.0 47.0 0..2 7.0 3.0 18.0 1.5
 21

i t d o e s n o t wet the r e f r a c t o r i e s and c o n s e q u e n t l y does not

corrode.

Magnecon b r i c k s (Table I) seem t o o p e r a t e b e s t in

Dore' f u r n a c e s as c o m p a r e d t o t h e o t h e r s t a n d a r d commerci a l l y
available bricks. The average l i f e of high magnesia-chrome
r e f r a c t o r i e s i n the s l a g - l i n e and roof i n d i f f e r e n t Dore'
furnaces is listed i n T a b l e II ( s u p p l i e d by C o m i n c o ) . It
can be s e e n t h a t s l a g 'B' (Table II) i s the most corrosive
of a l l s l a g s .

The s e v e r i t y of s l a g attack can be s e e n i n F i g . 5,

w h e r e a 9 i n c h m a g n e c o n b r i c k was reduced to about 1.75
inches i n j u s t 72 d a y s by s l a g B a t a b o u t 1 0 8 0 ° C . The
c o s t o f t h e s e b r i c k s and that of r e p l a c i n g them i s quite
1arge.

Slag 'B' and slag 'D' have s i m i l a r compositions

but the o p e r a t i n g t e m p e r a t u r e i n the case of s l a g 'B' is
much h i g h e r (by a b o u t 2 4 0 ° C ) t h a n i n t h e c a s e o f s l a g 'D'.
So i t can be s a i d t h a t t h e r e f r a c t o r y d i s s o l u t i o n rate
(in r e l a t i v e t e r m s ) d e p e n d s p r i m a r i l y on t h e operating
temperature of the furnace.

1.7.2 Possible Approaches Towards S o l v i n g the Problem

of Refractory Corrosion i n Dore Furnaces

The s o l u t i o n to the problem in t h i s s p e c i f i c case

 22

Fig. 5 Photograph of Corroded Magnecon R e f r a c t o r i es.

 23

i s t o d e v e l o p a r e f r a c t o r y l i n i n g m a t e r i a l f o r Dore furnaces
which can r e s i s t t h e a t t a c k o f h i g h l y c o r r o s i v e l e a d - b e a r i n g
slags. The p r o b l e m ean.be a p p r o a c h e d i n two ways:

(i) Development o f an e n t i r e l y new r e f r a c t o r y body

composition b a s e d on s l a g - o x i d e c h e m i s t r y . T h i s would
e s s e n t i a l l y i n v o l v e the tedious procedure o f making s u i t a b l e
phase d i a g r a m s b e c a u s e most o f the d i a g r a m s needed f o r
developing s p e c i a l i z e d r e f r a c t o r i e s do n o t e x i s t . This
would c e r t a i n l y be a v e r y l a r g e r e s e a r c h p r o j e c t c o n s i d e r i n g
a l l t h e work t o be done. F u r t h e r m o r e even i f a new r e f r a c -
t o r y b r i c k c a n be d e v e l o p e d i n t h i s manner, a s u i t a b l e and
w i l l i n g manufacturer f o r such a b r i c k may n o t be easy to find.

(ii) Development o f a r e f r a c t o r y c o a t i n g f o r c o m m e r c i a l l y
available refractory materials. T h i s seemed t o be t h e b e s t
p o s s i b l e approach to the problem f o r t h i s study. When t h i s
i n v e s t i g a t i o n was s t a r t e d , i t was soon r e a l i z e d t h a t no
work had been done i n t h i s f i e l d b e f o r e , s o , t h e r e wasn't
much r e f e r e n c e i n f o r m a t i o n a v a i l a b l e . However i t can be
s a i d t h a t t h i s l a t t e r a p p r o a c h a p p e a r s t o be more v i a b l e
and l e s s t i m e c o n s u m i n g as compared t o t h e p r e v i o u s one.
Moreover, i f a s l a g - r e s i s t a n t coating f o r conventional
r e f r a c t o r i e s can be developed.,: any Dore f u r n a c e user
s h o u l d be a b l e t o make t h i s c o a t i n g m a t e r i a l i n - p l a n t and
apply i t to the b r i c k s .
 24

I t s h o u l d be m e n t i o n e d h e r e , t h a t no c o a t i n g can
r e s i s t the a t t a c k o f m o l t e n s l a g s , but a good c o a t i n g
s h o u l d s l o w down the s l a g a t t a c k .

1.7.3 Dore" F u r n a c e Slags

The o n l y i n f o r m a t i o n a v a i l a b l e on the Dore' f u r n a c e

slags i s t h e i r composition (Table I I I ) . The important slag
p r o p e r t i e s r e q u i r e d to s t u d y the i n t e r a c t i o n s between
r e f r a c t o r y o x i d e s and the s l a g s a r e p h y s i c a l p r o p e r t i e s such
as:

(i) s u r f a c e t e n s i o n and m e l t density

(i i) v i scos i t y
(iii) melting points
(iv) w e t t i n g c h a r a c t e r i s t i c s and
(v) w e i g h t l o s s on heating.

None o f the above p h y s i c a l p r o p e r t i e s o f the s l a g s were

known when the work was started. Even to d e v e l o p a refrac-
t o r y c o a t i n g as d e s c r i b e d i n s e c t i o n (1..7...2), i t i s h e l p f u l
to know the phase r e l a t i o n s between the s l a g c o n s t i t u e n t s
and the o x i d e s i n the b r i c k . However, some phase e q u i l i -
b r i a d i a g r a m s r e l e v a n t to t h i s s t u d y are a v a i l a b l e o n l y as
binary diagrams. These are l i s t e d l a t e r along with t h e i r
l o w e s t e u t e c t i c t e m p e r a t u r e s and t h e i r numbers as they
a p p e a r i n Ref. (21). On the b a s i s o f the l i t e r a t u r e s u r v e y
Table III Composition o f Dore S l a g s i n wt.%.

Slag Temp °C % Cu % Pb % Zn % Sb % As % Bi % Si0 2

A 700 9.2 26.0 0.2 39.0 7.0 0.3 10.0

B 1080 10.0 47.0 0.2 7.0 3.0 18.0 1.5
C 1040 2.7 42.0 4.0 17.0 3.0 2.0 5.0
D 840 10.0 47.0 0.2 7.0 3.0 18.0 1.5
CI - 2.0 48. 7 - 22.0 5.1 0.8 -
C2 - 4.5 49.0 - 16.5 3.4 6.7 -
C3 - 2.6 76.8 - 2.0 0.7 1. 7 -
C4 - 10.4 31 .6 0.3 2.5 0.2 41 .2 0.4

The c o m p o s i t i o n s o f t h e s l a g s were s u p p l i e d by Cominco.

ro
cn
 26
above, an e x p e r i m e n t a l programme was f o r m u l a t e d to study
the s l a g p r o p e r t i e s and then t o d e v e l o p a slag resistant
refractory coating, i f possible.

1.8 Objectives of this Investigation

The o b j e c t i v e o f t h i s s t u d y i s t o d e v e l o p a slag-
r e s i s t a n t r e f r a c t o r y m a t e r i a l t o i n c r e a s e t h e l i f e o f the
l i n i n g c u r r e n t l y b e i n g used i n Dore f u r n a c e s .

In o r d e r t o a c c o m p l i s h t h i s , the f o l l o w i n g research
i n v e s t i g a t i o n s were c o n d u c t e d :

1. P r o p e r t i e s o f Pore* s l a g s
(i) melting temperatures
(ii) viscosity
(iii) s u r f a c e t e n s i o n and m e l t density
(iv) r e f r a c t o r y o x i d e and s l a g w e t t i n g properties
(v) w e i g h t l o s s on h e a t i n g .

2. Development of c o a t i n g compositions and p r o p e r t i e s .

3. S l a g a t t a c k t e s t s on c o a t e d r e f r a c t o r i e s .

When i t was o b s e r v e d that simply coating r e f r a c -

t o r i e s d i d not adequately prevent slag attack, the follow-
i n g a d d i t i o n a l i n v e s t i g a t i o n s were c o n d u c t e d :
Impregnation of r e f r a c t o r y b r i c k s by o x i d e s

salts.

S l a g a t t a c k t e s t s on impregnated and coated

refractories.
 28

Chapter 2

2. EXPERIMENTAL PROCEDURES AND RESULTS

2.1 Materials Studied

In t h e e x p e r i m e n t a l programme - t h e p r o p e r t i e s o f
the s l a g s were s t u d i e d f i r s t . Then coating mixtures were
developed and t e s t e d on a s u i t a b l e r e f r a c t o r y . Finally,
m o d i f i c a t i o n s o f c o a t i n g m a t e r i a l s and t e c h n i q u e s f o r
impregnation were d e v e l o p e d . In t h i s c h a p t e r o n l y s l a g
properties are discussed. B e f o r e t h i s work was s t a r t e d ,
the o n l y known s l a g p r o p e r t y was c h e m i c a l composition,
which was d e t e r m i n e d by Cominco L t d .

2.2 Slag Properties

The s l a g p r o p e r t i e s r e q u i r e d f o r d e v e l o p i n g a
c o a t i n g a r e as f o l l o w s :
(a) Chemical composition
(b) Physical Properties
(c) Slag-oxide Reactions

2.2.1 Chemical Properties

The a t o m i c c o m p o s i t i o n of the slags and t h e p h a s e s

 29

p r e s e n t i n quenched s l a g s , d e t e r m i n e d by x - r a y diffraction
a n a l y s i s , a r e o u t l i n e d below:

2.2.2 Chemical Composition

The c h e m i c a l c o m p o s i t i o n o f v a r i o u s s l a g s a r e
shown i n T a b l e L U . These s l a g s a r e r i c h i n l e a d , b i s m u t h
and a n t i m o n y . The p r e s e n t s t u d y was done on s l a g s C I , C2,
C3 and C4 which were o b t a i n e d from Cominco's Dore f u r n a c e s .
As d i s c u s s e d e a r l i e r ( s e c t i o n
: 1.2 and T a b l e I I ) , s l a g 'B'
i s the most c o r r o s i v e o f a l l s l a g s a t 1080°C. Some p r e -
l i m i n a r y t e s t s w i t h s l a g b u t t o n s ( d i s c u s s e d l a t e r ) showed
t h a t s l a g C4 was t h e most ' r e f r a c t o r y - p e n e t r a t i n g ' o f t h e
four 'C-slags'. S l a g B and s l a g C4 a r e t h e c l o s e s t i n
chemical composition. So although a l l the ' C - s l a g s '
were i n v e s t i g a t e d an added emphasis was g i v e n to s l a g C4.

2.2.3 Slag Structure

The d i f f e r e n t phases p r e s e n t i n t h e s l a g were f o u n d

by t h e x - r a y d i f f r a c t i o n method as m e n t i o n e d before. The
s t u d i e s were c o n d u c t e d on ' a s - r e c e i v e d ' s l a g s .

The s l a g s were ground t o a f i n e powder (about -325

mesh), as r e q u i r e d f o r p o w d e r - d i f f r a c t i o n p a t t e r n determina-
2 2
tion. For the d i f f r a c t i o n p a t t e r n s Cu Ka r a d i a t i o n w i t h
 30
a n i c k e l f i l t e r was used.

The phases i d e n t i f i e d i n s l a g s CI , C2, C3 and 04

a r e l i s t e d i n T a b l e IV. The o n l y ' f r e e ' o x i d e s i n the
slags are P b , ^ , PbO, B i and Cu,,0. The p r e s e n c e o f
some amorphous phases was i n d i c a t e d by the e x i s t e n c e o f a
b r o a d band (hump) between 26° and 34° (2 e a n g l e e s p e c i a l l y
i n the c a s e o f s l a g C4).

2.2.4 Physical Properties

The p h y s i c a l p r o p e r t i e s o f t h e s l a g s , t h a t were
d e t e r m i n e d , a r e l i s t e d below. The e x p e r i m e n t a l procedures
and t h e r e s u l t s a r e g i v e n i n each s e c t i o n .
(a) Melting point
(b) Viscosity
(c) S u r f a c e t e n s i o n and m e l t d e n s i t y
(d) Contact angle
(e) Weight loss at elevated temperatures.

2.2.4.1 M e l t i n g P o i n t D e t e r m i n a t i o n

(a) Experimental Procedure:

The l i q u i d u s t e m p e r a t u r e o f t h e s l a g s was d e t e r -
mined u s i n g t h e D i f f e r e n t i a l Thermal A n a l y s i s (DTA) method.
A c o m m e r c i a l l y a v a i l a b l e DuPont 1090 Thermal A n a l y z e r was
used a l o n g w i t h a 1200 (°C) DTA f u r n a c e module.
 31

T a b l e IV Phases I d e n t i f i e d i n Dore S l a g s

Slag CI: P b
2°3 a n d s o m e Pb
-y 2 - x ° 7
S b

( B i n d h e i m i t e ; 2<y*3, 0<x<l)

S l a g C2: BiAs0 4 > P b S b G" and some ( S b , A s ) 0 and

2 2 7 2 3

B i
24 P b
2 °40

S l a g C3: PbO

S l a g C4: P b
2 ° 3 ' P b S b 0 .and BT 0 (B)
2 4 2 3
 32

To e n s u r e homogeneity o f s l a g s a m p l e s , a few
chunks o f a s l a g were m i l l e d t o a f i n e powder w i t h s t e e l
balls. The powder was t h e n mixed t h o r o u g h l y f o r 24 h r s . i n
a ' t u m b l i n g - u n i t ' . T h i s w ' a s t o e n s u r e t h a t the " m i c r o
sample" used i n t h e DTA, a p p r o x i m a t e l y 0.025 grams, was
r e p r e s e n t a t i v e of the bulk s l a g .

A c o n t r o l l e d h e a t i n g r a t e o f 15°C/min. was used,

and t h e f u r n a c e was p u r g e d w i t h N i t r o g e n gas w i t h a f l o w
3
r a t e o f a b o u t 50 cm /min.

The DTA p l o t s f o r t h e f o u r s l a g s r e c o r d e d by t h e
1090 Thermal A n a l y z e r u n i t a r e shown i n F i g . 6. The
o r d i n a t e i n t h i s case i n d i c a t e s the temperature d i f f e r e n c e
( A T ) between t h e s t a n d a r d sample ( A l u m i n a powder) and
the specimen ( s l a g ) . In a t y p i c a l DTA e x p e r i m e n t t h e
s t a n d a r d cup i s p l a c e d on the r i g h t and t h e sample on the
left. With such an a r r a n g e m e n t an e n d o t h e r m i c r e a c t i o n i s
r e p r e s e n t e d by a drop on t h e DTA p l o t and an e x o t h e r m i c
r e a c t i o n by a peak. In t h e c a s e o f ' g l a s s y ' m a t e r i a l s
(amorphous) t h e peaks a r e much b r o a d e r t h a n t h e peaks
associated with c r y s t a l l i n e materials. T h i s o c c u r s because
the s o f t e n i n g and m e l t i n g i n g l a s s y m a t e r i a l s a r e q u i t e
s l u g g i s h and o c c u r o v e r a r a n g e o f t e m p e r a t u r e s . The size
o f t h e e n d o t h e r m i c o r e x o t h e r m i c peak g i v e s an a p p r o x i m a t e
 33

I i i i i i i i 1 1 i . 1

0 200 400 600 800 1000

Temperature (°C )

Fig. 6 M e l t i n g T e m p e r a t u r e s o f Dore S l a g s .
 34
i d e a r e g a r d i n g the amount o f m a t e r i a l u n d e r g o i n g the thermal
t r a n s f o r m a t i on.

(b) Results:
The l i q u i d u s t e m p e r a t u r e s o f s l a g s C I , C2, C3 and C4
are l i s t e d i n T a b l e V. The m e l t i n g t e m p e r a t u r e s o f s l a g s
are not t r u e m e l t i n g p o i n t s but r a t h e r l i q u i d u s t e m p e r a t u r e s
o f t h e d i f f e r e n t p h a s e s t h a t e x i s t i n a complex s l a g s y s t e m .
It i s a l s o apparent t h a t the s l a g s d o n ' t have j u s t one
l i q u i d u s t e m p e r a t u r e but two o r more d e p e n d i n g on the s y s t e m
(see F i g . 6 ) . The f r e e o x i d e s t h a t were i d e n t i f i e d i n t h e s e
s l a g s by x - r a y d i f f r a c t i o n ( T a b l e IV) d i d not m e l t as s i n g l e
o x i d e s but r a t h e r r e a c t e d i n a b i n a r y or t e r n a r y fashion
w i t h o t h e r o x i d e s ; t h i s c o u l d e x p l a i n the a b s e n c e o f f r e e -
o x i d e m e l t i n g p o i n t s as i n d i c a t e d i n the DTA plots.

From T a b l e V i t can be n o t e d t h a t s l a g C3 has the

h i g h e s t l i q u i d u s t e m p e r a t u r e ; t h i s may be due to i t s h i g h
PbO content (82.7 w t . % ) . In the case o f C I , C2 and C4
t h e r e are o t h e r low m e l t i n g p o i n t o x i d e s l i k e Bi^O^ (817°C),
Sb 2
n
3 (655°C), Sb 0 2 5 (380°C), e t c . w h i c h may produce low-
t e m p e r a t u r e l i q u i d u s and e u t e c t i c s .

As e x p e c t e d , s l a g C4 has the l o w e s t l i q u i d u s tempera-

t u r e - 525°C. T h i s e x p l a i n s t h e f l u i d i t y and r e f r a c t o r y -
p e n e t r a t i n g a b i l i t y o f t h i s s l a g at 1080°C (the Dore furnace
 35

Table V Mel t i n g P o i n t o f Dore S l a g s .

Slag Melting Point (°C)

CI 540
C2 670
C3 710
C4 515
 36
temperature - ; a. t e m p e r a t u r e a l m o s t 550°C above i t s ' m e l t i n g
point'). The b i n a r y e u t e c t i c s o f the s l a g components a r e
g i v e n i n T a b l e VI.

T a b l e VI PbO-Oxide E u t e c t i c s

System Lowest E u t e c t i c T(°C)

PbO- As 0 2 5 <800
Cu 0 2 680

" B i
2°3 ^750

" S b
2°3 540
- sb o 2 5 820
- Si0 2 715

From t h e DTA p i o t s ji n' Fej g .6 , and T a b l e V I , i t can be seen

t h a t some o f the peaks c o r r e s p o n d to the l o w e s t e u t e c t i c s
i n the b i n a r y s y s t e m s . PbO i s the major c o n s t i t u e n t i n
t h e s e s l a g s , so o n l y PbO b i n a r i e s were c o n s i d e r e d .

2.2.4.2 V i s c o s i t y of Slags

(a) Introduction
The v i s c o s i t y o f a l l l i q u i d s and most s l a g s f o l l o w
an A r r h e n i u s t y p e r e l a t i o n s h i p w i t h t e m p e r a t u r e as g i v e n by
the relation
 3 7

a s A 1 exp (En./RT) 2.1

where, n. ~ v i s c o s i t y o f the liquid,
A-j = a c o n s t a n t ,
E^ = a c t i v a t i o n e n e r g y f o r v i s c o u s f l o w ,
R = gas c o n s t a n t and
T = temperature i n K.

A d e t a i l e d d i s c u s s i o n r e g a r d i n g the development of
the above e q u a t i o n i s g i v e n i n A p p e n d i x 1.

(b) Apparatus
S e v e r a l methods a r e a v a i l a b l e f o r t h e measurement
of s l a g v i s c o s i t y . In t h e p r e s e n t i n v e s t i g a t i o n a concen-
t r i c c y l i n d e r v i s c o m e t e r was used because:

1. A c o n v e n t i o n a l B r o o k f i e l d v i s c o m e t e r was a v a i l a b l e
2'. The r e l a t i v e l y s m a l l i s o t h e r m a l zone r e q u i r e d f o r
such viscometers
3. The ease o f o p e r a t i o n
4. The h i g h l y c o r r o s i v e n a t u r e o f t h e m o l t e n slag.

O t h e r methods used f o r m e a s u r i n g viscosity include:

(i) t h e f a l l i n g body method
(ii) viscous flow in c a p i l l a r i e s
(iii) the l o g a r i t h m i c d e c r e m e n t method (.using a disc»
sphere or a c r u c i b l e ) .
(iv) the cone and p l a t e method. Most o f t h e s e methods a r e
 38

s u c c e s s f u l when used f o r l i q u i d s a t r o o m ' t e m p e r a t u r e b u t

m o l t e n s l a g s pose s e v e r a l r e s t r i c t i o n s a t high, t e m p e r a t u r e s
( > 1 0 0 0 ° C ) l i m i t i n g t h e use o f t h e above methods. The c o n -
c e n t r i c c y l i n d e r method i s t h e most w i d e l y used technique
23
for measuring slag-melt v i s c o s i t i e s . Michel, D a v i e s and
Wright, 24 Kato and Minowa, 25 and B o c k r i s and Lowe 26 have
used t h e c o n c e n t r i c c y l i n d e r v i s c o m e t r i c method f o r t h e
measurement o f m o l t e n s l a g s and g l a s s .

T h e r e a r e two v a r i a n t s o f t h e c o n c e n t r i c cylinder
method, one i n w h i c h t h e o u t e r c y l i n d e r ( t h e c r u c i b l e ) i s
s t a t i o n a r y and t h e i n n e r c y l i n d e r (.-the s p i n d l e ) rotates,
and t h e o t h e r where t h e o u t e r c y l i n d e r r o t a t e s and t h e i n n e r
one r e m a i n s s t a t i o n a r y . The f o r m e r method i s used i n com-
mercial viscometers and t h e l a t t e r i s used i n s p e c i a l c a s e s
where a l a r g e r a n g e o f s h e a r r a t e s a r e r e q u i r e d .

An a p p a r a t u s was d e s i g n e d and f a b r i c a t e d t o measure

the s l a g v i s c o s i t y i n t h i s i n v e s t i g a t i o n . The a p p a r a t u s can
be d i v i d e d i n t o t h e f o l l o w i n g p a r t s : ( i ) Viscometer, ( i i )
C r u c i b l e and s p i n d l e , ( i i i ) F u r n a c e , and ( i v ) C r u c i b l e
r a i s i n g device. A schematic diagram o f the apparatus i s ;
shown i n F i g . 7. The i m p o r t a n t design aspects of the four
parts are discussed briefly:
(i) A Brookfield Synchro-Lectric viscometer was u s e d .
However, t h e m e t a l l i c s p i n d l e s o f t h i s v i s c o m e t e r could not
 Brookfield Viscometer

Fig. 7 S c h e m a t i c View o f t h e Viscosity-Measuring

Apparatus.
 40

be used f o r t h e p r e s e n t p u r p o s e as t h e s l a g e a s i l y a t t a c k e d
them.
(ii) The b i g g e s t p r o b l e m f a c e d i n m e a s u r i n g t h e v i s c o s i t y
o f Dore s l a g s was t h e s e l e c t i o n o f a p r o p e r r e f r a c t o r y
m a t e r i a l f o r t h e c r u c i b l e and t h e s p i n d l e . Platinum or
molybdenum c r u c i b l e s a r e used f o r most p u r p o s e s ( C a F 2 melts,
CaO-Al 0 -Si0
2 3 2 s l a g s , and g l a s s ) b u t t h e s e can n o t be used
i n t h i s s t u d y as t h e s l a g " a t t a c k e d " b o t h m e t a l s . Refrac-
t o r y o x i d e s were c h o s e n as c r u c i b l e and s p i n d l e m a t e r i a l s .
M u T l i t e showed p r o m i s i n g s 1 a g - r e s i s t a n t q u a l i t i e s b u t dense
a l u m i n a was f o u n d t o be t h e b e s t m a t e r i a l . The c r u c i b l e s
1

were made by s l i p - c a s t i n g a c o m m e r c i a l , c a s t a b l e a l u m i n a
powder ( A l c o a - A 1 7 ) and t h e n s u b s e q u e n t l y f i r i n g t h e g r e e n
c r u c i b l e s i n a gas f i r e d f u r n a c e a t 1700°C f o r 5 h r s . These
a l u m i n a c r u c i b l e s were a l m o s t 100% dense and c o n s e q u e n t l y
non-porous. The s p i n d l e s were i n t h e shape o f r o d s w i t h an
o u t e r d i a m e t e r o f 1.30 cms and were o b t a i n e d c o m m e r c i a l l y .
These A 1 0 2 3 s p i n d l e s were a t t a c h e d t o s t a i n l e s s s t e e l tubes
w i t h a b o u t 10 cms o f t h e s p i n d l e p r o j e c t i n g o u t o f t h e
tubes. The s t a i n l e s s t u b e s were then a t t a c h e d t o t h e v i s -
cometer. A p i e c e o f s t r a i g h t p l a t i n u m w i r e was f i x e d on t h e
a l u m i n a s p i n d l e 4 cms from t h e bottom ( t h i s was t h e p r e -
d e t e r m i n e d immersion depth o f t h e s p i n d l e ) u s i n g s t a i n l e s s
s t e e l clamps. A n o t h e r p l a t i n u m w i r e was immersed i n t h e
melt. When t h e a l u m i n a s p i n d l e was immersed t o t h e c o r r e c t
d e p t h , the e l e c t r i c a l c i r c u i t between the two platinum
w i r e s and the m o l t e n s l a g was completed. Circuit completion
was i n d i c a t e d by a z e r o r e s i s t a n c e measurement on an ohm-
meter. The c r u c i b l e s were 7.0 cms h i g h , 4.6 ems o u t e r d i a -
meter and 0.2 cm w a l l t h i c k n e s s .

(iii) A schematic drawing o f t h e f u r n a c e can be seen i n

F i g . 8. The f u r n a c e had a t y p e 2712-KSP K a n t h a l heating
element c a p a b l e o f g o i n g up to 1 2 0 0 ° C . I t had an i n t e r n a l
d i a m e t e r o f 6.03 cms (2 3/8 i n c h e s ) and a l e n g t h o f 30.48
cms (12 i n c h e s ) . A l u m i n a - w o o l i n s u l a t i o n was wrapped
around t h e f u r n a c e ; the i n s u l a t i o n had a t h i c k n e s s o f 3.80
cms (9.65 i n c h e s ) . In t h e c o r e o f t h e f u r n a c e , a dense
alumina tube o f l e n g t h 36 cms and an o u t e r d i a m e t e r o f 5.72
cms (5.01 cms i n n e r d i a m e t e r ) was placed. The isothermal
zone i n t h e f u r n a c e was about 5.00 cms and the l e n g t h o f
the c r u c i b l e was 6.00 ems but the s l a g h e i g h t ( m o l t e n ) in
the c r u c i b l e was about 5.00 ems. The c r u c i b l e (4.50 cms
O.D. and 4.20 ems I.D.) was supported i n t h e f u r n a c e by an
AI2O3 -rod w h i c h r e s t e d on the r a i s i n g d e v i c e - a l a b o r a t o r y
jack. The t e m p e r a t u r e o f the i s o t h e r m a l zone c o u l d be con-
t r o l l e d w i t h i n + 5°C.

(iv) The r a i s i n g d e v i c e was an o r d i n a r y l a b o r a t o r y j a c k

to w h i c h a v e r n i e r d e v i c e was f i x e d . T h i s was i n place of
the o r d i n a r y knob used f o r r a i s i n g o r l o w e r i n g the p i a t -
form. The h o r i z o n t a l movement o f t h e ' t h r e a d e d s c r e w ' was
 Al 0
e 9 Tube

8 Schematic View of the V e r t i c a 1 - F u r n a c e .

g r a d u a t e d i n terms o f t h e v e r t i c a l movement o f the p l a t f o r m
using a strain-gauge. The c r u c i b l e c o u l d be r a i s e d o r
l o w e r e d w i t h an a c c u r a c y o f G.05 cm , u s i n g t h i s d e v i c e .

(c) Calibration
The v i s c o m e t e r was c a l i b r a t e d u s i n g machine oils,
g l y c e r i n e and c a s t o r o i l a t d i f f e r e n t t e m p e r a t u r e s . The
v a l u e s o f v i s c o s i t i e s o f t h e l i q u i d s used f o r c a l i b r a t i o n
were t a k e n from a s t a n d a r d handbook on the p h y s i c a l pro-
27
p e r t i e s of l i q u i d s . V i s c o s i t i e s o f t h e s e l i q u i d s were
measured u s i n g the m o d i f i e d a l u m i n a s p i n d l e and the A l ^ O ^
c r u c i b l e on the ' 1 0 0 - s c a l e ' o f t h e v i s c o m e t e r . The cali-
b r a t i o n p l o t f o r t h i s m o d i f i e d v i s c o m e t e r i s shown i n F i g .
28
9. Tiede used a s i m i l a r method f o r c a l i b r a t i n g h i s
Brookfield v i s c o m e t e r which was used t o measure the viscos-
i t y of g l a s s .
(d) Experimental
The c r u c i b l e was f i l l e d w i t h about 450 gms. of
powdered s l a g and was i n t r o d u c e d i n t o t h e f u r n a c e from the
bottom. The w a t e r c i r c u l a t i n g i n the t o p p l a t t e n kept i t
c o o l which p r e v e n t e d t h e v i s c o m e t e r stem from g e t t i n g hot.
An u n s h e a t h e d , Pt-.P.t 13%. Rd t h e r m o c o u p l e was i n t r o d u c e d
from t h e t o p i n t o the m o l t e n s l a g ( i n the c r u c i b l e ) and
was used t o r e c o r d t h e t e m p e r a t u r e . Thin walled alumina
t u b e s were t r i e d f o r s h e a t h i n g m a t e r i a l s but t h e s l a g
 44

Fig. 9 Calibration Plot for the Modified Spindle.

p e n e t r a t e d through the tubes e a s i l y ; t h i c k w a l l e d tubes
c o u l d n o t be used as t h e t h e r m a l c o n d u c t i v i t y o f a l u m i n a i s
q u i t e low and t h e time t a k e n f o r one r e a d i n g would be a b o u t
one m i n u t e . On t h e o t h e r hand, u n s h e a t h e d thermocouple
beads were f o u n d to l a s t f o r a b o u t one run (1.5 h r s . ) .
The t h e r m o c o u p l e was not k e p t immersed i n the melt a l l the
time.

When the d e s i r e d t e m p e r a t u r e was r e a c h e d , t h e c r u c -

i b l e was r a i s e d by t h e r a i s i n g d e v i c e u n t i l t h e p r e d e t e r -
mined l e n g t h (4 cms) o f t h e s p i n d l e was immersed i n t o the
molten s l a g . The c o r r e c t l e v e l o f i m m e r s i o n was indicated
by a z e r o r e s i s t a n c e o f f e r e d by t h e s l a g i n the e l e c t r i c a l
c i r c u i t (2.2.4.2 (ii)). A f t e r t h e s p i n d l e was immersed,
viscometer r e a d i n g s were t a k e n .

A l l v i s c o s i t y measurements were done i n a i r d u r i n g

the h e a t i n g c y c l e . The h e a t i n g c y c l e was c h o s e n i n s t e a d o f
the c o o l i n g c y c l e as the t e m p e r a t u r e c o n t r o l i n t h e h e a t i n g
c y c l e was much e a s i e r . To e s t a b l i s h t h e v i s c o s i t y - t e m p e r a -
t u r e p l o t s f o r the s l a g s , a t l e a s t t h r e e r u n s were p e r f o r m e d
on e a c h s l a g . The v i s c o s i t y measurements were a l s o p e r -
formed a t o t h e r speeds (50 and 20 rpro) and t h e measurements
were f o u n d to a g r e e w i t h t h e ones o b t a i n e d a t 100 rpm.

(ei) Results
The r e s u l t s o f t h e v i s c o s i t y measurements a r e
t a b u l a t e d i n A p p e n d i x l a and t h e a v e r a g e v i s c o s i t y v a l u e s
are p l o t t e d a g a i n s t t e m p e r a t u r e i n F i g s . 10a and 10b. A l l
the measurements were o b t a i n e d between 750°C and 1050°C ex-
c e p t f o r s l a g C3 where t h e measurements were s t a r t e d a t
800°C. The measurements o b t a i n e d f o r s l a g C3 a t 750°C a r e
not l i k e l y t o be a c c u r a t e as t h e s l a g was " s e e d y " o r "
" g r a i ny."

A 'seedy' m o l t e n s l a g l i k e C3 was a l s o e n c o u n t e r e d
28
by T i e d e , f o r some g l a s s e s . Subsequent v i s c o s i t y measure
ments, o b t a i n e d o v e r s m a l l e r t e m p e r a t u r e i n t e r v a l s d e v i a t e d
from t h e r e s u l t s g i v e n i n F i g . 10. T h e r e was f r o t h i n g o f
s l a g s o v e r a narrow t e m p e r a t u r e range e s p e c i a l l y i n t h e
c a s e o f s l a g C4. During f n o t h i n g , the v i s c o s i t y suddenly
i n c r e a s e s t o a h i g h e r v a l u e and t h e n d r o p s q u i c k l y . This
phenomenon can be seen i n F i g . 11. A similar frothing
e f f e c t t o o k p l a c e i n t h e c a s e o f s l a g s CI and C2 b u t t h e
d e g r e e o f f r o t h i n g (measured by t h e sudden i n c r e a s e i n
v i s c o s i t y ) was much l e s s . In F i g . 10 t h i s sudden i n c r e a s e
i n v i s c o s i t y i s n o t shown f o r two r e a s o n s : ( i ) when e x p e r i
ments were f i r s t p e r f o r m e d - t h e r e a d i ngs i<n F i gs. 10a and
10b, t h i s e f f e c t was n o t n o t i c e d as no e x p e r i m e n t s were p e r
formed between 895°C and 9 1 0 ° C , ( i i ) i f t h i s e r r a t i c be-
h a v i o u r i s e x c l u d e d , t h e p l o t assumes t h e normal f o r m as
shown i n F i g . 10.
 Temperature (°C)

F i g . TOa V i s c o s i t y of Dore S l a g s .
 Temperature ( ° C )
1050 1000 950 900 850 800 750
n 1 1 1 1 1 r-

T"'x|0 4
(K"')

F i g . 1 0& N o r m a l i z e d V i s c o s i t y P l o t o f Dore Slags.

 49

i 1 1 1 1 1 1 r
CM

0 6 6 6 0 6 6 0 6
1 1 1 1 1 1 1 1 1
( j.w sN u
!) AjjsoDSjA 601
 50
2.2.4.3 S u r f a c e T e n s i o n and M e l t Density

The m e l t - d e n s i t y and t h e s u r f a c e t e n s i o n m e a s u r e -
ments, o f t h e s l a g s were combined as t h e same apparatus
and t e c h n i q u e c o u l d be used f o r both m e a s u r e m e n t s . For
t h i s reason t h e s e c t i o n s on ' A p p a r a t u s ' and 'Experimental
Procedure' a r e combined;' whiTe the?' i n t r o d u c t i o n ' and
1

' r e s u l t s ' s e c t i o n s a r e kept separate.

T h e r e a r e s e v e r a l methods a v a i l a b l e f o r m e a s u r i n g
the s u r f a c e t e n s i o n o f l i q u i d s ; c a p i l l a r y r i s e , drop w e i g h t ,
f i l m b a l a n c e , s e s s i l e drop and maximum b u b b l e pressure.
Most o f t h e s e methods c a n ' t be used f o r m o l t e n s l a g s , and
i n f a c t , most o f t h e s u r f a c e t e n s i o n measurements on s l a g s
have been done by u s i n g o n l y f o u r methods: ( i ) maximum
bubble p r e s s u r e , ( i i ) s e s s i l e drop, ( i i i ) pendant drop and
(iv) capillary rise. In t h e p a s t few y e a r s t h e maximum
b u b b l e p r e s s u r e method has been used more o f t e n than t h e
o t..h.e r s . 29-34

In t h e f o l l o w i n g s e c t i o n s t h e a d v a n t a g e s and d i s -
a d v a n t a g e s o f d i f f e r e n t methods a r e d i s c u s s e d .

(i) The s e s s i l e drop method i n v o l v e s t h e use o f a h i g h

35
temperature microscope. Kojima used t h i s method t o
determine the surface tension of Ca0-Si0 2 and C a O - S i O ^ - A l ° 3
2

slags containing sulphur. In t h i s method a s m a l l solid

 51

sample ( a b o u t 0.6 cm ) i s p l a c e d on an i n e r t s u b s t r a t e . The

sample i s then h e a t e d i n a f u r n a c e . P i c t u r e s o f the drop
formed a t d i f f e r e n t t e m p e r a t u r e s a r e t h e n t a k e n . The m a x i -
mum h e i g h t and t h e maximum r a d i u s a r e d e t e r m i n e d from t h e
p i c t u r e s and t h e s u r f a c e t e n s i o n i s c a l c u l a t e d u s i n g t h e
t a b l e s o f B a s h f o r t h and Adams. The d i m e n s i o n a l measure-
ments have t o be p e r f o r m e d a c c u r a t e l y i n o r d e r t o a v o i d
large errors i n c a l c u l a t i n g the surface tension.

In t h e p r e s e n t work t h i s method was n o t used t o

measure t h e s u r f a c e t e n s i o n o f Dore s l a g s b e c a u s e a h i g h
t e m p e r a t u r e m i c r o s c o p e was n o t a v a i l a b l e and t h e c o n s t r u c -
t i o n o f one would be v e r y time consuming.

(ii) The p e n d a n t - d r o p t e c h n i q u e has been used by Rasmussen

and N e l s o n 3 7 and K i n g e r y 38 t o d e t e r m i n e t h e s u r f a c e t e n s i o n
of molten AlgOg.

T h i s t e c h n i q u e c o u l d n o t be used i n t h e p r e s e n t
c a s e a l s o due t o t h e n o n - a v a i l a b i l i t y o f a h i g h t e m p e r a t u r e
microscope.

(iii) The c a p i l l a r y r i s e method i s one o f t h e e a s i e s t

and most p r a c t i c a l o f a l l methods when used t o measure
s u r f a c e t e n s i o n o f l i q u i d s a t room t e m p e r a t u r e . But t h i s
i s n o t so i n t h e c a s e o f Dore s l a g s ; h e r e t h e c a p i l l a r y
tube c o u l d n o t be made o f o p t i c a l l y t r a n s p a r e n t g l a s s .
 52

refractory oxides, platinum o r m o l y b d e n u m as t h e s l a g s

were v e r y r e a c t i v e .

The c a p i l l a r y r i s e method i s p e r h a p s t h e o l d e s t
method f o r m e a s u r i n g the s u r f a c e t e n s i o n o f l i q u i d s -
g o i n g b a c k t o t h e d a y s o f L e o n a r d o da V i n c i . When a
vertical capillary ( F i g . 12) i s p a r t l y i m m e r s e d i n a l i q u i d
which wets the c a p i l l a r y w a l l s p e r f e c t l y , the h e i g h t o f
r i s e o f the l i q u i d i n t h e t u b e i s g i v e n by t h e equation

h = 2.2

where r i s t h e r a d i u s o f t h e t u b e and p i s t h e d e n s i t y o f
the l i q u i d y and g have t h e i r u s u a l meanings.

The use o f t h e above e q u a t i o n (2.2) i s however

v e r y l i m i t e d i n p r a c t i c e due t o t h e f a c t t h a t no l i q u i d c a n
wet a n y c a p i l l a r y t u b e p e r f e c t l y . C o r r e c t i o n s h a v e t o be
made f o r c o n t a c t angles.

A simpler form f o r measuring l i q u i d surface tension

is the ' D i f f e r e n t i a l C a p i l l a r y R i s e ' method. In t h i s m e t h o d
two t u b e s o f d i f f e r e n t d i a m e t e r s a r e p a r t i a l l y i m m e r s e d i n
the l i q u i d F i g . 13. The h e i g h t d i f f e r e n c e between t h e
two l o w e r m e n i s c i i i s f o u n d a n d t h e n t h e s u r f a c e tension
39
c a l c u l a t e d by u s i n g t h e m e t h o d d e y e l o p e d by S u g d e n .
12 C a p i l l a r y R i s e i n a Tube,

13 D i f f e r e n t i a l C a p i l l a r y Rise in Tubes.
 54

In t h e p r e s e n t work the d i f f e r e n t i a l c a p i l l a r y rise

method was t r i e d w i t h o u t s u c c e s s due t o t h e s l a g g i n g r e a c -
t i o n between t h e c a p i l l a r y tube used (Al^0^) and t h e s l a g s .
40
Wanibe e t a l . also observed slagging reactions i n the
case o f FepQo,* CaO, S i ^ and A ^ O g s l a g s w i t h m u l l i t e c a p i l -
laries. Such a s l a g g i n g r e a c t i o n g i v e s r i s e t o a t r a n s i e n t
surface tension value. Due t o t h e s e p r o b l e m s both the
c a p i l l a r y r i s e and t h e d i f f e r e n t i a l c a p i l l a r y r i s e methods
were r e j e c t e d .

However, a few e x p e r i m e n t s were p e r f o r m e d u s i n g t h e

Differential R i s e method b e f o r e coming t o t h e above c o n -
clusion. I t was f o u n d t h a t t h e s l a g r i s e i n t h e c a p i l l a r y
t u b e s depended on t i m e . The d i f f e r e n t amounts o f s l a g rise
i n such c a p i l l a r i e s a t d i f f e r e n t t i m e l e n g t h s c a n be seen
i n F i g . 14. So c a p i l l a r y r i s e methods a r e s e r i o u s l y
affected .by t i m e : and , t h e s e methods c a n be used o n l y
when t h e l i q u i d r i s e i n t h e c a p i l l a r i e s has r e a c h e d a
s t a b l e and maximum h e i g h t v e r y q u i c k l y .

(iv) The o n l y method f o u n d t o be s u i t a b l e f o r measuring

the s u r f a c e t e n s i o n o f Dore s l a g s was t h e maximum b u b b l e
29
p r e s s u r e method. T h i s method has been used by Hara e t a l .
31
f o r t h e CaO-CaF^-S'iO^ s y s t e m . Cooper and K i t c h e n e r for
30
the CaO-SiO2-P2O5 s y s t e m and G u n j i and Dan f o r the
Ca0-Si0 -Al °3
2 2 system and a l s o by.-others . 4 1
~ 43
 55

Fig. 14 Increase of c a p i l l a r y rise of slags in alumina

tubes with time. T i m e f r o m 1 t o r ( i ) 30 sees,
( i i ) 60 s e e s a n d ( i i i ) 2 mins.
 56
In t h i s method a c a p i l l a r y tube i s d i p p e d i n t o t h e
l i q u i d ( m e l t ) and an i n e r t gas ( N o r A r ) i s p a s s e d t h r o u g h
2

it. When a s u f f i c i e n t l y h i g h p r e s s u r e i s a p p l i e d gas bub-

b l e s b r e a k f r e e from t h e c a p i l l a r y t i p . By m e a s u r i n g t h e
p r e s s u r e needed t o break t h e b u b b l e s f r e e t h e s u r f a c e t e n -
44
s i o n can be f o u n d by u s i n g S c h r o d i n g e r s e q u a t i o n ;
1

2r
,2
(rp )'
P i s

Y = 0.5 rg (Hp -hp ) 1

m s 2-.3
3(H -hp ) Pm 6(Hp -hp )'
s m s

where y = s u r f a c e t e n s i o n o f l i q u i d i n dyn.cm"
r = r a d i u s o f c a p i l l a r y tube i n cm„
g = g r a v i t a t i o n a l c o n s t a n t i n cm s e c
H = maximum m a n o m e t r i e h e i g h t i n cm
h = depth o f i m m e r s i o n i n cm
P m = d e n s i t y o f m a n o m e t r i e l i q u i d i n gm cm -3
p = d e n s i t y o f l i q u i d ( s l a g ) i n gm cm

The u n i q u e n e s s o f t h i s method l i e s i n t h e f a c t t h a t
i t s use i s i n d e p e n d e n t o f t h e c a p i l l a r y - s l a g c o n t a c t a n g l e
and t h e s l a g g i n g r e a c t i o n does n o t o c c u r as t h e s l a g c a n -
not e n t e r t h e t u b e . The amount o f c o o l i n g i s a l s o v e r y
s m a l l as t h e immersion depth can be kept s h o r t and l i t t l e
time i s r e q u i r e d t o p e r f o r m such an e x p e r i m e n t .

2.2.4.4 M e l t D e n s i t y
The m e l t d e n s i t y o f a slag i s needed t o c a l c u l a t e i t s
 57

surface tension. The d e n s i t i e s o f l i q u i d s a t room tempera-

t u r e ean be e a s i l y f o u n d by m e a s u r i n g i t s w e i g h t and v o l u m e ,
but i n t h e c a s e o f m o l t e n s l a g s . t h i s becomes d i f f i c u l t
because o f t h e h i g h t e m p e r a t u r e s involved. Melt density i s
u s u a l l y determined by ( i ) Archemedes p r i n c i p l e , ( i i ) t h e
l e v e l o f r i s e o f t h e m e l t i n a p l a t i n u m tube and ( i i i ) t h e
maximum b u b b l e p r e s s u r e method.

(i) The Archemedes Method

T h i s method r e q u i r e s a z e r o c o n t a c t a n g l e between
the body b e i n g immersed and t h e l i q u i d . I f t h e c o n t a c t VM
a n g l e i s n o t z e r o t h e n c o r r e c t i o n s have t o be made, as t h e
v e r t i c a l component o f t h e l i q u i d s u r f a c e t e n s i o n a f f e c t s
the b a l a n c e between t h e w e i g h t o f t h e body b e i n g immersed
and t h e upward t h r u s t b e i n g e x p e r i e n c e d by i t . T h i s method
i s used f r e q u e n t l y t o c a l c u l a t e d e n s i t i e s o f l i q u i d s without
taking the contact angle i n t o c o n s i d e r a t i o n . However,
the e f f e c t o f s u r f a c e t e n s i o n can be t a k e n c a r e o f by com-
p l e t e l y immersing two b o d i e s o f d i f f e r e n t w e i g h t s in a
l i q u i d and u s i n g t h e same s u s p e n s i o n w i r e . Here t h e s u r f a c e
t e n s i o n e f f e c t s c a n c e l o u t - a method based on t h i s principle
29

was used by Hara e t a.l.. t o s t u d y t h e d e n s i t y o f Cap^-CaO-

Si0 2 melts.

In t h e above method t h e r e a r e t h r e e main r e s t r i c t i o n s :

(i) t h e body b e i n g immersed s h o u l d be d e n s e r t h a n t h e m e l t ,
 58

(1.1) the s u s p e n s i o n w i r e s h o u l d n o t he a t t a c k e d by t h e melt,

and ( i i i ) t h e v i s c o s i t y o f t h e m e l t s h o u l d be r e a s o n a b l y
1 ow.

If the v i s c o s i t y of the melt i s q u i t e high ( i n

r e l a t i v e t e r m s ) t h e n t h e w e i g h t r e c o r d e d on immersing t h e
body w i l l be more o f a t r a n s i e n t n a t u r e , as t h e body w i l l
t a k e a f i n i t e time t o become c o m p l e t e l y immersed. In t h e
case o f s l a g s with the f r o t h i n g tendency (as i n t h e p r e s e n t
c a s e F i g . 11 and s e c t i o n 2.2.4.2) the v i s c o s i t y w i l l
change a b r u p t l y d u r i n g f r o t h i n g and t h i s w i l l a f f e c t t h e
weight r e c o r d i n g s .
A s i m i l a r f r o t h i n g b e h a v i o u r was n o t i c e d
31
by Cooper and K i t c h e n e r i n t h e c a s e o f CaO-Si 0 -P 0,. m e l t s
2 2

45
and by S p e i t h and H e i n r i c h s i n the case of F e 0 - S i 0 s l a g s . 2

The b i g g e s t p r o b l e m f a c e d i n u s i n g t h i s method i n
the p r e s e n t c a s e was t h a t a s u i t a b l e s u s p e n s i o n w i r e c o u l d
n o t be f o u n d . Even p l a t i n u m w i r e s a r e a t t a c k e d and d i s -
s o l v e d by t h e Dore s l a g . C l e a r l y , t h e above method c o u l d
not be a p p l i e d . Other, l e s s c r i t i c a l experimental problems
were a l s o e n c o u n t e r e d and t h e A r c h e m e d i a n method was f i n a l -
ly rejected.

(ii) C a p i l l a r y R i s e Method
The s e c o n d method o f m e a s u r i n g t h e m e l t - d e n s i t y o f
s l a g s and o x i d e s i s by d i r e c t l y o b s e r v i n g i t s r i s e i n a t u b e .
Rasmussen and Nelson used t h i s method t o measure t h e melt
density of A 1
2°3" I n t l r i s
method a molybdenum tube w i t h
one e n d s e a l e d i s u s e d ( a s m o l y b d e n u m h a s a h i g h m e l t i n g
p o i n t and does n o t r e a c t with. most o x i d e s ) . The oxide i s
put i n s i d e the tube n o r m a l l y i n t h e form o f c y l i n d r i c a l
rods. The molybdenum tube i s then heated i n a f u r n a c e
(which has a f a c i l i t y f o r x - r a y r a d i o g r a p h y ) and t h e l i q u i d
meniscus radiograph i s filmed. By t a k i n g i n t o a c c o u n t t h e
volume e x p a n s i o n o f t h e tube- t h e volume o f t h e l i q u i d and
hence i t ' s d e n s i t y c a n be f o u n d .

In p r i n c i p l e , t h i s m e t h o d i s v e r y s i m p l e b u t t h i s
method c o u l d n o t be u s e d b e c a u s e a h i g h v o l t a g e ( a b o u t
300 kV) x - r a y s o u r c e , n e e d e d f o r s u c h r a d i o g r a p h y , was n o t
available.

(iii) T h e maximum b u b b l e p r e s s u r e m e t h o d h a s b e e n used

by q u i t e a f e w w o r k e r s t o measure the m e l t - d e n s i t y o f
46
slags. Popel and E s i n used t h i s method t o determine t h e
density of Fe0-Si0 2 and C a 0 - F e 0 - S i 0 2 melts, and Gunji and
Dan used i t f o r t h e C a 0 - S i 0 2 and C a O - S i 0 - A l 0
2 2 3 systems.

In t h i s m e t h o d t h e p r e s s u r e r e q u i r e d t o form bub-!
b l e s ( a t a ' s t a b l e maximum m a n o m e t r i e h e i g h t ' ) , a t two d i f -
f e r e n t immersion h e i g h t s o f t h e c a p i l l a r y tube, i s measured
44
Then using Schrodi nger' s equation (.2.3); t h e d e n s i t y o f
 60
the m e l t can be f o u n d .

p - 2>4 .
(h =h )
1 2

where p s i s t h e d e n s i t y o f the melt-,

P m i s the d e n s i t y of the manometric l i q u i d (used
to measure p r e s s u r e c h a n g e s )
H-| and H2 a r e t h e maximum m a n o m e t r i c h e i g h t s a t
d e p t h s o f immersion o f h^ and h 2 respectively.

The u n i q u e n e s s o f t h i s method l i e s i n t h e f a c t t h a t
i t does n o t r e q u i r e c o n t a c t a n g l e s o r t h e s u r f a c e t e n s i o n
of the melt. I t can a l s o be used f o r h i g h l y v i s c o u s m e l t s
like Ca0-Si0 2 and CaO-Si 0,,-Al . For the convenience of
u s i n g a s i n g l e t e c h n i q u e t o measure b o t h t h e s u r f a c e t e n -
s i o n and m e l t d e n s i t y , a b u b b l e p r e s s u r e a p p a r a t u s was con-
structed for this investigation.

2.2.4.5 Experimental Procedure

Apparatus
The a p p a r a t u s t h a t was b u i l t f o r m e a s u r i n g t h e s u r -
f a c e t e n s i o n and t h e m e l t d e n s i t y o f the Dore s l a g s i s
shown s c h e m a t i c a l l y i n F i g . 15. The a p p a r a t u s c o n s i s t s o f
s i x p a r t s : ( i ) gas p u r i f i c a t i o n t r a i n , . ( i i ) manometer,
( i i i ) v e r t i c a l f u r n a c e , ( i v ) c a p i l l a r y tube, (v] r a i s i n g -
l o w e r i n g d e v i c e f o r t h e c r u c i b l e and ( v i ) t h e b u b b l e
 Tron»dueer

F i g . 15 A p p a r a t u s Used f o r the Maximum Bubble P r e s s u r e Method.

 62

frequency m o n i t o r i n g system.

(i) The N i t r o g e n gas used f o r b u b b l i n g was p u r i f i e d by

p a s s i n g i t t h r o u g h sodium h y d r o x i d e , c o p p e r f i l i n g s h e a t e d
at 800°C and t h e n t h r o u g h s i l i c a g e l . T h i s reduced the
w a t e r and oxygen c o n t e n t o f t h e N i t r o g e n gas t o a v e r y low
limit. B e f o r e t h e N i t r o g e n gas was p a s s e d t h r o u g h t h e
p u r i f i c a t i o n t r a i n , i t had a USP g r a d e p u r i t y w i t h <30 ppm
The b u b b l i n g r a t e was a c c u r a t e l y c o n t r o l l e d u s i n g a
micro-needle valve.

(ii) The manometer was made o f a U-shaped g l a s s tube of

i n t e r n a l d i a m e t e r 0.6 cm and t h e l e n g t h o f each l i m b was
about 60 cms. The manometer l i q u i d was w a t e r dyed r e d w i t h
an o r g a n i c c o l o r a n t and i t s d e n s i t y a t room t e m p e r a t u r e
(20°C) was 1.00 gm cm as measured by a p y c n o m e t r i c b o t t l e .
L i q u i d l e v e l s i n t h e manometer were measured using a t r a v e l -
l i n g t e l e s c o p e which was p l a c e d a t a d i s t a n c e o f 1.5 m
from t h e manometer.

(iii) The f u r n a c e used f o r t h e s u r f a c e t e n s i o n and den-

s i t y measurements was t h e same as t h e one used f o r t h e
v i s c o s i t y measurements ( F i g . 8 ) . A l l t h e measurements
were c a r r i e d o u t i n a i r .

(iv) The c a p i l l a r y tube was made o u t o f dense Al

which had an i n t e r n a l d i a m e t e r o f 0.242 cm- These were t h e
 63
o n l y t u b e s t h a t were i m m e d i a t e l y a v a i l a b l e . The t u b e s
were a b o u t 46 ems l o n g . The t u b e s were mounted v e r t i c a l l y
on a s t a n d , w i t h t h e a i d o f a p l u m b - l i n e , and then c o n n e c t e d
to t h e p u r i f i e d gas f l o w . The o u t e r d i a m e t e r o f t h e s e
t u b e s was 0.442 cm. A f t e r each measurement t h e c a p i l l a r y
t u b e s were t a k e n o u t and c h e c k e d f o r p o s s i b l e s l a g a t t a c k
but i n most c a s e s t h e t u b e s s u r v i v e d a b o u t 8 t o 10 measure-
ments w i t h o u t any s i g n i f i c a n t reaction.

(v) In most maximum b u b b l e p r e s s u r e e x p e r i m e n t s , t h e

c r u c i b l e i s n o r m a l l y f i x e d a t a c e r t a i n e l e v a t i o n and t h e
c a p i l l a r y tube i s l o w e r e d i n t o t h e m e l t . In t h e p r e s e n t
c a s e , due t o p r a c t i c a l p r o b l e m s , t h e c r u c i b l e was r a i s e d
using the r a i s i n g - l o w e r i n g device discussed p r e v i o u s l y .
T h i s d e v i c e had an a c c u r a c y o f 0.05 cms. The c r u c i b l e
was r a i s e d v e r y g e n t l y so as n o t t o d i s t u r b t h e l i q u i d -
slag surface.

(vi) The b u b b l i n g f r e q u e n c y i n f l u e n c e s t h e maximum

manometrie h e i g h t . V e r y h i g h b u b b l i n g r a t e s l e a d t o un-
s t a b l e and r a p i d growth and break-away o f b u b b l e s . In
a d d i t i o n , the i n e r t i a o f the manometrie l i q u i d prevents i t
from c h a n g i n g l e v e l s i n r e s p o n s e t o h i g h f r e q u e n c y p r e s s u r e
fluctuations. The e f f e c t o f b u b b l e f r e q u e n c y on t h e maximum
m a n o m e t r i e h e i g h t was s t u d i e d u s i n g w a t e r p u r i f i e d by p a s s i n g
i t t h r o u g h an i o n e x c h a n g e r e s i n . The r e s u l t s a r e shown i n
F i g . 16. When t e s t e d w i t h Dore s l a g m e l t s similar results
 64

Fig. 16 Dependence o f the Maximum M a n o m e t r i c H e i g h t on

Bubbling Interval.
were a l s o o b t a i n e d . G u n j i and Dan a l s o found similar
results. I t can be seen from t h e above f i g u r e t h a t a bub-
b l e f r e q u e n c y o f l e s s than 1 b u b b l e / m i n u t e i s necessary
in order to obtain r e l i a b l e r e s u l t s . To m o n i t o r t h e b u b b l e
frequency a P i e z o e l e c t r i c T r a n s d u c e r was a t t a c h e d t o t h e
c a p i l l a r y tube ( F i g . 1 5 ) . The p r e s s u r e s i g n a l s from t h e
t r a n s d u c e r were f e d t o a 3-ehannel a m p l i f i e r . The s i g n a l s
from t h e a m p l i f i e r were then f e d i n t o a Dual H i / L o e l e c -
t r o n i c f i l t e r and t h e e l e c t r i c a l s i g n a l s were r e c o r d e d on
a T e k t r o n i x O s c i l l o s c o p e w i t h a Time Base. Using this set-
up b u b b l e r a t e s o f l e s s than 1 b u b b l e / m i n u t e c o u l d be
measured. I t was f e l t however, t h a t a t r a n s d u c e r w i t h a
l o w e r p r e s s u r e r a t i n g would have been more s u i t a b l e f o r t h i s
work as t h e use o f an o s c i l l o s c o p e t o measure maximum mano-
m e t r i c h e i g h t would make t h e p r o c e d u r e o f d e t e r m i n i n g mano-
m e t r i c h e i g h t s much s i m p l e r . A t r a n s d u c e r with a lower
p r e s s u r e r a t i n g was n o t a v a i l a b l e and t h e e x i s t i n g t r a n s -
d u c e r c o u l d n o t be used t o measure t h e m a n o m e t r i c h e i g h t s .
T h i s i s because t h e t r a n s d u c e r had a r a t i n g o f 0 t o 60 p s i g
and t h e maximum m a n o m e t r i c h e i g h t r e c o r d e d i n t h e s e measure-
ments c o r r e s p o n d t o about 0.15 p s i g . On t h e o t h e r hand,
the f r e q u e n c y c o u l d be measured v e r y a c c u r a t e l y w i t h t h i s
system.

The e x p e r i m e n t a l p r o c e d u r e f o r m e a s u r i n g the s u r f a c e
 66

t e n s i o n and t h e d e n s i t y v a l u e s o f m o l t e n s l a g s was r e l a -
t i v e l y simple. F o r s u r f a c e t e n s i o n measurements t h e c a p i l -
l a r y was immersed t o a c e r t a i n d e p t h , t h e bubble r a t e kept
a t a f r e q u e n c y o f l e s s than 1 b u b b l e / m i n u t e and then t h e
maximum m a n o m e t r i e h e i g h t was d e t e r m i n e d . For density
measurements m a n o m e t r i e h e i g h t s were measured a t two d i f -
f e r e n t depths o f immersion, as d i s c u s s e d e a r l i e r .

2.2.4.6 Re s u i t s and A n a l y s i s

(a) Surface Tension

The maximum m a n o m e t r i e h e i g h t was measured from t h e
d i f f e r e n c e between t h e l i q u i d l e v e l s i n t h e two l i m b s o f
the manometer. These v a l u e s were f e d i n t o e q u a t i o n (2.3)-

and t h e v a l u e s o f y were computed. The v a l u e s o f t h e

e x p e r i m e n t a l measurements and t h o s e o f t h e o t h e r parameters
i n e q u a t i o n ( 2 . 3 ) f o r t h e f o u r Dore f u r n a c e s l a g s ( C I , C2,
C3 and C4) can be seen i n A p p e n d i x 2. The s u r f a c e t e n s i o n
v a l u e s o f t h e s l a g s as a f u n c t i o n o f t e m p e r a t u r e are plotted
i n F i g . 17. The low s u r f a c e t e n s i o n v a l u e s o f Dore s l a g s
r e f l e c t i n d i r e c t l y t h e i r s p r e a d i n g b e h a v i o u r on r e f r a c t o r i e s .
Y i s r e l a t e d t o t h e s p r e a d i n g c o e f f i c i e n t S by t h e e q u a t i o n

S " Y (1+COSQ)
l 2.5

where 8 i s t h e a n g l e o f c o n t a c t between t h e m o l t e n s l a g and

the s u b s t r a t e .
L9
 68

When a pure l i q u i d i n e q u i l i b r i u m w i t h i t s own

vapour i s heated, i t s temperature e v e n t u a l l y reaches the
c r i t i c a l p o i n t o f t h e s u b s t a n c e , where t h e r e i s no d i f f e r e n c e
between the l i q u i d and t h e v a p o u r and no s u r f a c e t e n s i o n
can e x i s t ; t h i s t e m p e r a t u r e i s c a l l e d t h e c r i t i c a l tempera-
ture (Tc). In g e n e r a l t h e g r e a t e r the t e m p e r a t u r e differ-
ence between t h e o p e r a t i n g t e m p e r a t u r e and t h e c r i t i c a l
t e m p e r a t u r e , t h e g r e a t e r t h e s u r f a c e t e n s i o n v a l u e becomes.
In some s l a g m e l t s t h e s u r f a c e t e n s i o n may n o t f o l l o w the
b e h a v i o u r o f a pure l i q u i d , as some complex s l a g systems
41
d i s s o c i a t e on m e l t i n g . In t h e p r e s e n t c a s e , t h e s u r f a c e
t e n s i o n o f the s l a g - m e l t s d e c r e a s e d l i n e a r l y w i t h i n c r e a s e ,
in temperature ( F i g . 17). F o r q u i t e a number o f o x i d e s
such a l i n e a r r e l a t i o n s h i p h o l d s t r u e w i t h i n t h e l i m i t s o f
experimental error. *

It s h o u l d be m e n t i o n e d h e r e t h a t s u r f a c e t e n s i o n
measurements were not p e r f o r m e d i n t h e narrow temperature
r e g i o n ( a b o u t 15°C) where f r o t h i n g t a k e s p l a c e . I t was
o b s e r v e d t h a t t h e manometrie l i q u i d behaved v e r y e r r a t i c a l l y
d u r i n g f r o t h i n g ; such an e f f e c t was n o t r e p o r t e d by Cooper
31
and K i t c h e n e r who worked on f o a m i n g m o l t e n silicates.
The e r r a t i c b e h a v i o u r o f t h e manometrie l i q u i d c o u l d pos-
s i b l y a r i s e from t h e f o r m a t i o n and b r e a k a g e o f b u b b l e s i n
the f r o t h w h i c h a f f e c t b u b b l e f o r m a t i o n and break-away at
the c a p i l l a r y t i p . During the p e r i o d of f r o t h i n g the
 69

maximum m a n o m e t r i c h e i g h t was somewhat l o w e r than expected

implying lower s u r f a c e t e n s i o n v a l u e s .
This e f f e c t i s in
31
agreement w i t h t h e work o f Cooper and K i t c h e n e r .
(b) Density
The d e n s i t y o f t h e s l a g s d e c r e a s e d w i t h i n c r e a s e i n
temperature. T h i s r e l a t i o n s h i p can be seen i n F i g . 18. The
experimental values recorded along with the other parameters
in equation (2.4) a r e given i n Appendix 2 f o r the f o u r dif-
f e r e n t s l a g s . The d e n s i t y o f a l i q u i d a f f e c t s i t s p h y s i c a l
p r o p e r t i e s i n d i r e c t l y as t h e d e n s i t y p a r a m e t e r i s i n v o l v e d
in t h e i r d e t e r m i n a t i o n .

2.2.4.7 C o n t a c t Angle

(a) Introduction
The w e t t i n g and s p r e a d i n g c h a r a c t e r i s t i c s o f a
l i q u i d on a s o l i d s u b s t r a t e can be d e t e r m i n e d by m e a s u r i n g
i t s s u r f a c e t e n s i o n and t h e c o n t a c t a n g l e t h a t i t makes
with the s o l i d .

When a l i q u i d drop s i t s on a s o l i d s u b s t r a t e ( F i g .
19) i t makes an a n g l e 'e' with i t , t h i s angle i s c a l l e d
the C o n t a c t A n g l e ; s m a l l c o n t a c t a n g l e s i m p l y e x t e n s i v e
s u b s t r a t e w e t t i n g by t h e l i q u i d . From Young's e q u a t i o n and
F i g . 19

Y S V
=
Y S L
+
Y L V Cos e 2.6
80 L

750 800 850 900 950 1000 1050

Temperature (°C)

Fig: 18 Density o{ Dore S l a g s ;

Fig. Surface Tensions Associated with a S e s s i l e Drop.
 72

and from e q u a t i o n (.2.6)

S = T l v (GosQ+vl ) 2.5

i t can be seen t h a t t h e s u r f a c e t e n s i o n Cv^y) o f a l i q u i d

and t h e c o n t a c t a n g l e i t makes w i t h a s o l i d s u b s t r a t e a r e
intimately linked. The s p r e a d i n g ( o r w e t t i n g ) o f a l i q u i d
on a s o l i d i s d e t e r m i n e d both by t h e s u r f a c e t e n s i o n ( y ^ y )
and t h e c o n t a c t a n g l e ( e ) .

T h e r e a r e many methods a v a i l a b l e f o r t h e m e a s u r e -
ment o f l i q u i d - s o l i d c o n t a c t a n g l e s . In t h e c a s e o f m e t a l s
and s l a g s t h e r e a r e two common methods ( i ) d i r e c t observa-
t i o n o f t h e c o n t a c t a n g l e by t a k i n g p i c t u r e s o f t h e m o l t e n
drop a t e l e v a t e d t e m p e r a t u r e s and ( i i ) c a l c u l a t i n g t h e
c o n t a c t a n g l e from t h e e q u i l i b r i u m d i m e n s i o n s ( h e i g h t and
r a d i u s ) of the drop. R e c e n t l y , P r a b r i p u t a l o o n g and P i g g o t '
4

determined t h e c o n t a c t a n g l e s o f A l , Ag, Au, Cu, In and Sn

on s a p p h i r e by t h e t h i n f i l m t e c h n i q u e . However i n t h e
c a s e o f s l a g s and metal o x i d e s t h e t h i n f i l m t e c h n i q u e may
not p r o v e v e r y h e l p f u l due t o t h e h i g h b o i l i n g p o i n t s o f
most o x i d e s .

From F i g . 19 i t seems t h a t t h e t h e o r y and t h e

experimental procedures f o r determining the contact angles
are q u i t e simple but i n p r a c t i c e i t i s not so. The f a c t o r s
 73

t h a t c o u l d a f f e c t t h e v a l u e s o f c o n t a c t a n g l e s between
l i q u i d s and s o l i d s u b s t r a t e s a r e numerous. In t h i s s e c t i o n
only the important f a c t o r s w i l l be c o n s i d e r e d .

Surface roughness o f the s o l i d s u b s t r a t e (assuming

i t i s 100% d e n s e ) seems t o a f f e c t c o n t a c t a n g l e v a l u e s t h e
most. The s u r f a c e r o u g h n e s s i s g e n e r a l l y e x p r e s s e d i n
terms o f t h e s u r f a c e r o u g h n e s s f a c t o r ' r ' . The term ' r '
i s t h e r a t i o o f t h e a c t u a l s u r f a c e a r e a o f t h e s o l i d sub-
s t r a t e to i ts geometric a r e a (A : A. );• where t h e a c t u a l
s u r f a c e a r e a i n c l u d e s t h e u n d u l a t i o n s p r e s e n t on t h e s u r -
face.

I f t h e r o u g h n e s s f a c t o r i s i n c l u d e d i n Young's
e q u a t i o n a f t e r r e a r r a n g e m e n t i t becomes:

Y L V Cos e = r('Y- -Y )
S V S L 2.7

So i t i s a p p a r e n t t h a t r can a f f e c t t h e v a l u e o f ev As an
example t h e r o u g h n e s s f a c t o r o f g r o u n d g l a s s can v a r y be-
tween 1.4 t o 2.2 and t h e c o n t a c t a n g l e o f h i g h - a r o m a t i c t a r
on p l a t e g l a s s can v a r y between 2 7 ° and 5 2 ° . Such l a r g e
v a r i a t i o n s o f c o n t a c t a n g l e a r e due t o t h e combined e f f e c t s
o f s u r f a c e r o u g h n e s s and c o n t a c t a n g l e h y s t e r e s i s . The
c o n t a c t a n g l e h y s t e r e s i s i s e x p l a i n e d by t h e a d v a n c i n g and
r e c e d i n g c o n t a c t a n g l e phenomenon.
 74
48
In 1935 Mack showed t h a t the use o f s m a l l drops
f o r m e a s u r i n g c o n t a c t a n g l e s possesses; s e v e r a l a d v a n t a g e s :
(i) s m a l l drops can be used on s m a l l p l a n e a r e a s o f an
irregular surface or on an a r e a w i t h an a p p r o x i m a t e l y con-
s t a n t c u r v a t u r e , ( i i ) s m a l l d r o p s have g r e a t e r v a r i a t i o n
i n h e i g h t f o r s m a l l e r v a r i a t i o n s i n c o n t a c t a n g l e s and ( i i i )
s m a l l drops assume the a d v a n c i n g contact angle while l a r g e r
drops e x h i b i t a f l u c t u a t i n g a n g l e w h i c h T i e s between the
advancing and r e c e d i n g c o n t a c t angles.

The a c u t e a n g l e o f c o n t a c t ( 0 ) i s g i v e n by:

e = 2 tan" 1
(h/x) 2,8

where h i s the g r e a t e s t h e i g h t o f the drop and x i s the

r a d i u s o f t h e base ( F i g . 19). The d i s t a n c e x can be e a s i l y
and a c c u r a t e l y measured as i t i s q u i t e l a r g e but the s m a l l
m a g n i t u d e o f 'h' i n t r o d u c e s e r r o r s i n i t s measurement. This
is e s p e c i a l l y true f o r small drops. In the c a s e o f s m a l l
drops the e v a p o r a t i o n i s q u i t e l a r g e , due to the l a c k o f
e q u i l i b r i u m between the l i q u i d and the s u r r o u n d i n g vapour -
t h i s a f f e c t s the v a l u e o f 'h'. The measurement o f 'h'
can o n l y be done a c c u r a t e l y i n a h i g h t e m p e r a t u r e microscope.

T h e s e p r o b l e m s can be s o l v e d by s u b s t i t u t i n g the
volume f o r t h e h e i g h t as a m e a s u r a b l e d i m e n s i o n o f the drop,
 75
This e l i m i n a t e s the problem of e v a p o r a t i o n o f the l i q u i d .
48
Mack o b s e r v e d t h a t an e v a p o r a t i n g drop m a i n t a i n e d i t s
o r i g i n a l r a d i u s l o n g a f t e r i t s h e i g h t , volume and c o n t a c t
a n g l e had been c o n s i d e r a b l y r e d u c e d .

When t h e c o n t a c t a n g l e , o f s m a l l d r o p s i s acute
the shape o f t h e drop ean .be a p p r o x i m a t e d by a s p h e r o i d a l
segment. The e q u a t i o n ( 2 . 8 ) m e n t i o n e d e a r l i e r assumes
such a shape b u t t h i s e q u a t i o n c a n n o t be used s u c c e s s f u l l y
f o r s m a l l d r o p s when t h e v a l u e o f 'h' i s v e r y s m a l 1 . So,
an e q u a t i o n was d e r i v e d i n terms o f t h e drop v o l u m e , u s i n g
drop r a d i u s a t t h e base and t h e c o n t a c t a n g l e as p a r a m e t e r s *
Consider a s e s s i l e drop which i s a s p h e r o i d a l segment
( f l a t t e n i n g o f s e s s i l e d r o p s i s d e a l t w i t h i n A p p e n d i x 3)
s i t t i n g on a s o l i d s u b s t r a t e and making an a n g l e e w i t h i t
a t i t s base ( F i g . 2 0 a ) . The same d r o p c a n be i n c o r p o r a t e d
i n a s p h e r e as i n F i g . ( 2 0 b ) .

The volume o f t h e s p h e r o i d a l segment ABC i s g i v e n by

V c = ~ TT h 2
(3r-h) 2.9

where h =<B D and r-j - CD

E q u a t i o n ( 2 . 9 ) can be f o u n d . i n any book .on M e n s u r a t i o n .
From F i g . 20. b , h = r-| t a n (.9/2)
l r

and t a n ( e ) = — ^
r^ + r t a n (o)
hence, h = tan(el 2.10
 76

Fig. 20 ( a ) S e s s i l e D r o p and ( b ) I n c o r p o r a t i o n o f t h e
Drop in (a) i n t o a R e p r e s e n t a t i v e C i r c l e .
 77

From t r i a n g l e ODC,

r-j2 +, (/ r -uh\ )2 = r2 2.11

and
r^ + h
2.12
2h
Substituting e q u a t i o n ( 2,. 1 2) i n t o C 2.9 ) y i e l d s 2.13

Vc = TT h' 2.14

After simplifying equation (2.14)

Tf.hr, .Tr.tr
2.15

and s u b s t i t u t i n g f o r h i n e q u a t i o n (2.15) from (2.10) the

f i n a l form o f t h e e q u a t i o n f o r V i s obtained.

V = 1,5708 r ^ tan (e/2) + 0.5236 r ^ tan Ce/2)

c
3
2.16

From t h e above e q u a t i o n , t h e v a l u e o f e can be c a l c u l a t e d by

knowing t h e v a l u e s o f V c and r ^ •

I t s h o u l d be m e n t i o n e d here t h a t t h e c o n t a c t a n g l e
o b t a i n e d from e q u a t i on (. 2.16) i s the experimental value
and i s c a l l e d t h e ' a p p a r e n t ' c o n t a c t a n g l e i n Appendix 3,
and i s r e p r e s e n t e d by 9 ' .

(b) Correction f o r Contact Angles

A s e s s i l e drop r e g a r d l e s s o f s i z e tends to get
 78

f l a t t e n e d by g r a v i t y . I t i s a l w a y s b e t t e r t o c o r r e c t the
experimentally measured v a l u e s o f t h e c o n t a c t angles.

48
Mack has shown t h a t t h i s can be done by u s i n g the
tables of Bashforth and Adams. In t h i s a n a l y s i s , drop
r a d i u s and the c a p i l l a r y c o n s t a n t o f the s l a g a r e used to
c o r r e c t f o r the f l a t t e n i n g o f the drop by g r a v i t y . The
o r i g i n a l a n a l y s i s by Mack has been m o d i f i e d t o s u i t the
needs o f the p r e s e n t work. -A c o m p l e t e d i s c u s s i o n o f the
m o d i f i c a t i o n s i s p r e s e n t e d i n A p p e n d i x 3.
(c) Experimental Procedure
Contact a n g l e s o f the f o u r s l a g s (CI , C2, C3 and
C4) on an a l u m i n a s u b s t r a t e were d e t e r m i n e d a t d i f f e r e n t
temperatures.

Small c y l i n d r i c a l s l a g p e l l e t s of diameter
0.3150 cm and h e i g h t 0.203 cm ( a p p r o x i m a t e l y ) were made by
d r i l l i n g s o l i d s l a g samples w i t h a h o l l o w diamond d r i l l .
A f t e r the d r i l l i n g o p e r a t i o n , the ends o f the cylindrical
s p e c i m e n s were c u t on a diamond saw to o b t a i n the desired
height. The d i a m e t e r and t h e h e i g h t o f the cylindrical
s p e c i m e n s were measured u s i n g a m i c r o m e t e r s c r e w - g a u g e and
hence the volumes were d e t e r m i n e d . The p e l l e t s were then
p l a c e d on 100% dense a l u m i n a p l a t e s (.1.5 cms x 1 .5 cms x
0.06 cm) and m e l t e d i n a h o r i z o n t a l tube e l e c t r i c furnace
 79

using nitrogen as the furnace atmosphere- These experi-

ments were conducted for varying lengths of time at differ-

ent temperatures. The radius of the molten slag drop was

then measured using a planimeter on enlarged pictures of

the slag drop. A typical enlarged picture (6x) of a slag

drop on an alumina substrate is shown in Fig. 21. The

perimeter of the slag spread is not a perfect circle and

so an average radius of the drop is computed from the area

measured by the planimeter. When the contact angle is

found from this 'average radius' the angle determined is

the average of all angles made by the drop on the substrate*

4s mentioned earlier, the contact angle varies from point

to point due to various reasons. Computation of contact

angles from radii measurements is more reliable than the

'optical observation' methods.

After calculating the contact angles:, corrections

are made using Appendix 3. The capillary constants of the

slags had to be known, in order to .;-.make ' these correc-

tions. Capillary constants were calculated from the surface

tension of the slags at different temperatures.

(d) Results

Contact angle decreased with increasing time at a

fixed temperature and reached a constant value after a

S e s s i l e d r o p p i c t u r e o f a s l a g p e l l e t on
an a l u m i n a s u b s t r a t e (Linear mag. = 6x).
 81

c e r t a i n length of time. In t h e p r e s e n t w o r k i t was found

that the angle remained c o n s t a n t a f t e r ab.out 150 seconds.
Such a t i m e dependent c o n t a c t a n g l e b e h a v i o u r has a l s o
b e e n r e p o r t e d by B a r t l e t t a n d H a l l " who w o r k e d on A1^03
and BeO. A l l the c o n t a c t angle measurementsJ i n t h i s study
w e r e o b t a i n e d a t t i m e s g r e a t e r t h a n 150 sees.

The c o n t a c t a n g l e v a l u e s f o r t h e f o u r s l a g s a r e
shown i n F i g . 22 and t h e d e t a i l e d c a l c u l a t i o n s l e a d i n g t o
t h i s f i g u r e are given i n Appendix 4. No c o n t a c t a n g l e
m e a s u r e m e n t s c o u l d be p e r f o r m e d at temperatures less than
800°C as t h e s l a g s t o o k a v e r y l o n g t i m e t o m e l t which
could p o s s i b l y reduce the a c c u r a c y of the measurements.
C o n t a c t a n g l e measurements were a l s o not p o s s i b l e a t tempera-
t u r e s above 1000°C as t h e s l i a g p e l l e t s m e l t e d e v e n before
t h e y c o u l d be p l a c e d i n t h e c o r r e c t t e m p e r a t u r e zone of
the f u r n a c e and t h e s l i g h t v i b r a t i o n s i n v o l v e d i n p e r f o r m i n g
t h i s o p e r a t i o n a f f e c t e d the measurements.

The interfacial tension ( y ^ ) between the s l a g s

and t h e a l u m i n a s u b s t r a t e were c a l c u l a t e d . These values
a r e shown i n A p p e n d i x 4 and t h e r e l a t i o n b e t w e e n y ^ and
temperature i s shown i n F i g . 23.

2.2,4.8 Conclusion

S l a g C4 i s t h e m o s t c o r r o s i v e o f a l l t h e o t h e r
 Contact Angles of
Slags on Alumina
30

O O

20 -O—C3

-A—C2

10

JL

750 800 850 900 950 1000 1050

Temperature (°C)

F i g . 22 C o n t a c t A n g l e s o f Dore S l a g s on Alumina
 84

' C - s l a g s ' a t 1.080°C. S l a g C4 i s more f l u i d than the

o t h e r s l a g s a t the o p e r a t i n g t e m p e r a t u r e due to t h e low
v i s c o s i t y and c o n t a c t a n g l e e x h i b i t e d by i t . The low con-
t a c t a n g l e v a l u e c a u s e s i t to spread* more e a s i l y . So i t
was d e c i d e d to s t u d y c o a t i n g c o m p o s i t i o n s on the b a s i s o f
s l a g C4 a t 1 0 8 0 ° C . I f a s u i t a b l e method o f r e d u c i n g slag
C4 p e n e t r a t i o n i n t o r e f r a c t o r i e s can be found then the
same method s h o u l d a l s o work f o r the o t h e r slags.

From the e x p e r i m e n t s c o n d u c t e d on the f o u r s l a g s

i t was observed t h a t the p h y s i c a l p r o p e r t i e s ( m e l t density,
v i s c o s i t y , s u r f a c e t e n s i o n and c o n t a c t - a n g l e ) depended on
the s l a g c o m p o s i t i o n . Lead was the m a j o r e l e m e n t p r e s e n t in
varying proportions i n the s l a g s and i t s e f f e c t on the s l a g
p r o p e r t i e s a r e shown i n F i g u r e s 24 and 25, where the p h y s i c a l
p r o p e r t i e s are c o r r e l a t e d .

The r e s u l t s are summarized i n T a b l e V I I . In t h i s

t a b l e , the s u b s c r i p t numbers i n d i c a t e the m a g n i t u d e o f the
terms (1>2>3>4). I t can be seen t h a t s l a g C3 has the highest
d e n s i t y because of i t s high lead content. The surface
t e n s i o n and c o n t a c t a n g l e f o l l o w the same p a t t e r n as they
are i n t i m a t e l y r e l a t e d . I t seems t h a t l e a d t e n d s to increase
both the s u r f a c e t e n s i o n and the c o n t a c t a n g l e whereas b i s -
muth r e d u c e s i t . The v i s c o s i t y t e n d s to be i n c r e a s e d by l e a d
and b i s m u t h t e n d s to r e d u c e i t .
 85

1 1 1 C3p
Density (P ) 8 Viscosity /
/

[Tj) at 900°C
C4

6h q
L5
E '—p.
C2 900
u
O
E
s
3 1^l
-v
900
CI ^
4}

C2
A

C4/
A'

30 40 50 60 70 80
wt. % Pb

F i g . 24 D e n s i t y and V i s c o s i t y o f Dore S l a g s vs Wt.%Pb

Content of the Slags. Dark c i r c l e represents
t h e p o i n t where Pb % and Bi % a r e c o m b i n e d .
 86

450
i>
1 1 1 3
25
Surfoce Tension (X) 8 Contoct /
/
Angle (#) ot 900°C
C3
/ •
/

400
900 /
20
E
o
C2
900
O
^ CD

350 CI.
15 -o

C4 C2 /
•
cr'

300
10r C 4

30 40 _L
50 60 70 80
wt. % Pb

F i g . 25 S u r f a c e T e n s i o n and C o n t e n t A n g l e o f S l a g s
vs Wt. % Pb C o n t e n t . F i l l e d hexagon and
s q u a r e a r e t h e p o i n t s f o r Pb % and B i %
combi ned.
T a b l e VII P h y s i c a l P r o p e r t i e s o f Dore S l a g s .

Slag Density Surface Tension Contact Angle Viscosity

C3 P'l
Y
l e
l n
l

C4 P 2
Y
4 n
4

C2 p
3 Y
2 9
2 n
3

CI p
4 Y
3 G
3 n 2
 88

Chapter 3

3. DEVELOPMENT OF COATINGS

The c o r r o s i o n o f r e f r a c t o r y b r i c k s by m o l t e n slags
i s g e n e r a l l y e n h a n c e d i f t h e b r i c k s a r e porous.. Molten
slag enters the bricks through pores, reacts with the r e -
fractory constituents, and c o r r o d e s t h e b r i c k . The penetra-
t i n g power o f a c o r r o s i v e m o l t e n s l a g i s t h e r a t e control-
l i n g s t e p i n t h e wear o f r e f r a c t o r i e s i n t h e s e e a s e s . If
slag penetration can be r e d u c e d , by s e a l i n g t h e p o r e s and with-
out r a d i c a l l y a l t e r i n g t h e t h e r m a l p r o p e r t i e s of refractor-
i e s , t h e n s l a g i n d u c e d c o r r o s i o n can be r e d u c e d . There are
two possibilities: ( i ) surface p o r e s o f a b r i c k can be
s e a l e d by a v e r y v i s c o u s liquid and ( i i ) most o f t h e p o r e s
can be f i l l e d by i m p r e g n a t i n g t h e b r i c k . The f o r m e r ap-
p r o a c h i s e a s i e r as b r i c k c o a t i n g s can be a p p l i e d w i t h i n -
e x p e n s i v e c o m m e r c i a l e q u i p m e n t such as s p r a y guns.

V e r y l i t t l e work has been done p r e v i o u s l y on

developing refractory coatings f o r bricks. Usachev e t a l .
developed a coating f o r f i r e c l a y r e f r a c t o r i e s used f o r
51

steel tapping launders, and Bar developed a coating f o r

usage i n t h e p r o d u c t i o n o f h i g h p u r i t y aluminum.
 89
3.1 Coating Composition

3.1.1 P r o p e r t i es 'Required-

The properties required f o r an i d e a l c o a t i n g are:

( i ) c h e m i c a l c o m p a t i b i l i t y w i t h both the b r i c k and the
s l a g , ( i i ) a f u s i o n temperature g r e a t e r than t h a t of the
s l a g s , ( i i i ) the p r e s e n c e o f f u s i b l e p h a s e s , and • ( i v ) ease
o f m a n u f a c t u r e and application.

(i) The coating should have c h e m i c a l c o m p a t i b i l i t y w i t h

the b r i c k * o r e l s e i t c o u l d a t t a c k and c o r r o d e the brick.
The c o a t i n g should a l s o be c o m p a t i b l e w i t h t h e s l a g so
t h a t s l a g c h e m i s t r y and f u r n a c e operation are not affected.
The c h e m i c a l c o m p a t i b i l i t y of a c o a t i n g w i t h a b r i c k should
depend, to a c e r t a i n d e g r e e , on the p e n e t r a t i n g power o f
the c o a t i n g . The p e n e t r a t i n g power depends on the v i s c o s i t y
and s u r f a c e t e n s i o n o f the c o a t i n g a t the operating
t e m p e r a t u r e , and on the pore s i z e and the pore volume o f
the b r i c k . The c o m p a t i b i l i t y o f a c o a t i n g w i t h a s l a g can
be a s s u r e d by i n c o r p o r a t i n g some o f the s l a g components
i n the c o a t i n g itself. M o r e o v e r , i f the c o a t i n g thickness
is small ( a b o u t 1 mm) compared w i t h the b r i c k thickness
(230 mm = 9 i n c h e s ) , t h e n the s l a g c h e m i s t r y s h o u l d not
be affected.

(ii) In Dore f u r n a c e s the l i q u i d u s t e m p e r a t u r e o f s l a g

 90

C4 i s 520°C and the o p e r a t i n g t e m p e r a t u r e o f the f u r n a c e i s

1080°C. The m e l t i n g p o i n t s o f the h u l k o f the p h a s e s i n a
c o a t i n g have to be h i g h e r than t h a t o f the s l a g and should
be even h i g h e r than the f u r n a c e o p e r a t i n g t e m p e r a t u r e . If
t h i s i s not the c a s e , t h e c o a t i n g w i l l melt a t the furnace
t e m p e r a t u r e and may wash away and s p e c i f i c a l l y i f the v i s c o s -
i t y i s low. A complex c o a t i n g c o n t a i n i n g s e v e r a l o x i d e s will
not have a s i n g l e m e l t i n g p o i n t a t a f i x e d t e m p e r a t u r e but
w i l l r a t h e r have s e v e r a l l i q u i d u s t e m p e r a t u r e s . Here the
term m e l t i n g p o i n t o f a c o a t i n g i n d i c a t e s the t e m p e r a t u r e
a t which the maximum amount o f the s o l i d phases p a s s i n t o
the l i q u i d s t a t e .

(iii) The p r e s e n c e o f f u s i b l e p h a s e s i n a p r o t e c t i v e c o a t -
i n g f o r r e f r a c t o r y b r i c k s i s e s s e n t i a l , as t h e s e a r e the
phases w h i c h s h o u l d p e n e t r a t e i n t o the pores and s e a l them.
These g l a s s y phases s h o u l d have a s u f f i c i e n t l y h i g h v i s c o s -
i t i e s a t the o p e r a t i n g t e m p e r a t u r e o r a t the pretreatment
t e m p e r a t u r e so t h a t t h e y c a n n o t be washed away e a s i l y . How-
e v e r i t s h o u l d be r e a l i z e d t h a t wash-out c a n n o t be completely
prevented i f the s l a g i s h i g h l y c o r r o s i v e . The amount o f
f u s i b l e p h a s e s t h a t need to be p r e s e n t in a c o a t i n g f o r suc-
c e s s f u l a p p l i c a t i o n , v a r i e s from s y s t e m to s y s t e m , depen-
d i n g on the c h e m i s t r y and p o r o s i t y o f r e f r a c t o r y b r i c k s .
I f the c o n c e n t r a t i o n o f the f u s i b l e p h a s e s i s s m a l l , and
the c o a t i n g has a h i g h v i t r i f i c a t i o n t e m p e r a t u r e , i t i s
 91

l i k e l y t h a t the c o a t i n g w i l l p e e l - o f f a t the operating

temperature. I f th.e amount o f t he f u s i b l e phase i s v e r y
l a r g e , the c o a t i n g w i l l p r o b a b l y be washed away by contin-
uous r e a c t i o n w i t h the s l a g . So, the p r e s e n c e o f an opti-
mum amount o f f u s i b l e phase in a coating, i s very important.

(iv) The ease o f m a n u f a c t u r e o f a c o a t i n g combined with

the a v a i l a b i l i t y o f raw m a t e r i a l s f o r c o a t i n g preparation,
and the method o f a p p l i c a t i o n s h o u l d be c o n s i d e r e d , as a l l
o f t h e s e f a c t o r s d e t e r m i n e the u s e f u l n e s s of a coating.

3.1.2 C h o i c e o f B r i c k and Slag

To s t u d y the s l a g p e n e t r a t i o n , into refractory

b r i c k s , a s u i t a b l e b r i c k had t o be f o u n d where the amount
of s l a g p e n e t r a t i o n c o u l d be f o l l o w e d e a s i l y - p r e f e r a b l y
by v i s u a l o b s e r v a t i o n . Magnecon b r i c k s c o u l d not be used
f o r Dore s l a g s , as b o t h a r e b l a c k i n c o l o u r . Alumina
b r i c k s ( o f p u r i t y 99%) were c h o s e n b e c a u s e t h e s e bricks
are w h i t e ; s l a g p e n e t r a t i o n is r e a d i l y observed. When
t e s t e d a t 1 0 8 0 ° C , b o t h the magnecon and the a l u m i n a b r i c k s
were w e l l below t h e i r r e f r a c t o r i n e s s l i m i t , so the lower
r e f r a c t o r i n e s s o f a l u m i n a b r i c k s s h o u l d not i n f l u e n c e s l a g
penetration. I t was a l s o r e a l i z e d t h a t i f a c o a t i n g worked
w e l l f o r a l u m i n a b r i c k s , i t s h o u l d work e q u a l l y w e l l for
magnecon b r i c k s , as the l a t t e r have more r e s i s t a n c e to the
 92
Dore s l a g s .

S l a g C4 i s t h e most c o r r o s i v e o f t h e f o u r Dore
s l a g s ( T a b l e I I ) , and has a low v i s c o s i t y . So, s l a g C4
was c h o s e n f o r r e f r a c t o r y - s 1 a g a t t a c k t e s t s .

3.1.3 Basis of Coating Development

By making use o f t h e s l a g and r e f r a c t o r y c h e m i s t r y ,

i t s h o u l d be p o s s i b l e t o d e v e l o p a p r o t e c t i v e c o a t i n g f o r
b r i c k s used i n Dore f u r n a c e s . The b a s i s o f s u c h d e v e l o p -
ment s h o u l d , o f c o u r s e , be t h e r e l e v a n t phase d i a g r a m s .
However, v e r y few u s e f u l phase d i a g r a m s a r e a v a i l a b l e f o r
s l a g - r e f r a c t o r y systems. T h i s a p p r o a c h would be f e a s i b l e
i n t h e c a s e o f f e r r o u s m e t a l l u r g i c a l p r o c e s s e s , where
most o f t h e phase d i a g r a m s (even f o r f o u r and f i v e component
systems) have been d e v e l o p e d . Phase d i a g r a m s p e r t a i n i n g
to t h e Dore s l a g s (CI t o C4) and t h e magnecon b r i c k s a r e
l i s t e d on T a b l e V I I I . T h e s e d i a g r a m s were o b t a i n e d from
21
the handbook "Phase Diagrams f o r C e r a m i s t s . " Little
can be l e a r n e d f r o m t h e s e d i a g r a m s , as most a r e b i n a r y o r
ternary in nature. S e v e r a l a d d i t i o n a l phase d i a g r a m s
would be needed t o a p p r o a c h t h i s work s y s t e m a t i c a l l y .

In t h e a b s e n c e o f r e l e v a n t phase d i a g r a m s and thermo-

dynamic d a t a , t h e f o r m a t i o n o f s t a b l e compounds between Dore
TABLE V I I I Phase Diagrams f o r Magnecon-Dore S l a g S y s t e m s

Lowest
System Type NO.
Eutectic (*C)

CaO-CuO-Cu 0 2 3 oxides 1013 2105

Pb0-Cr 0 2 3 2 787 2134

Cu0-Al 0 2 3 2 " 1165 2085

Al 0 -Cu0-Cu 0
2 3 2 3 1130 2087

Cu0-S10 2 2 1050 2142

PbO-Al 0 2 3 2 650 5166

AI O :B1 O
Z 3 2 3 2 820 4365

Cu 0(CuO 5 S ) - S 1 0
2 2 2 1060 164

Mg0-Cr 0 2 3 2 2320 262

Cu 0-Mg0
2 2 " 1190 274

B1 0 -HgO
2 3 2 785 326

Al 0 -Zn0
2 3 2 1720 299

Bi 0 -CaO
2 3 2 - 326

Bi 0 -Zn0
2 3 2 750 326

Ca0-Al 0 2 3 2 1360 2295

»
Ca0-A1 0 -Cu0 2 3 3 1550 626

Ca0-Al 0 -S10 -Zn0 2 3 2 4 1150 2669

CaO-Cr 0 2 3 2 1022 39

CaO-Cr 0 -MgO 2 3 3 - 597

CaO-Cr 0 -MgO-S10 2 3 2 4 1490 2665

Ca0-Cr 0 -Si0 2 3 2 3 - 651

CaO-MgO 2 2370 229

»
Ca0-Mg0-Si0 2 3 1700 2471

Ca0-Si0 2 2 - 2302

CaO-Si0 -ZnO 2 3 »
- 624

C r
2 3-0 A 1
2°3
2 - 309

Cr 0 -Al 0 -HgO
2 3 2 3 3 1950 710

Cr 0 -Al 0 -Si0
2 3 2 3 2 3 1580 2583

Cr 0 -CaO-MgO
2 3 3 »
- 597

Cr 0 -Mg0-Si0
2 3 2 3 - 715

Cr 0 -Pb0
2 3 2 787 2134

Cr 0 -Si0 2 » 1723
2 3 2 332

Cu0-Cu 0-Cr 0 2 2 3 3 1130 2125

Cu0-Cu 0-S10 2 2 3 2143

Ca0-Al 0 -Cr 0 - 2 3 2 3

5 1515 2699
Hg0-S10 2

CaO-A1 0 -MgO 2 3
3 1321 2469
»
Ca0-A1 0 -Hg0-Si0 2 3 2
4 1400 2647

Ca0-Al 0 -S10 2 3 2
3 1400 2493

Mg0-Al 0 2 3 2 1995 259

Pb0-Al 0 -S10 2 3 2 3 - 737

S10 -Al 0 -Ca02 2 3 3 1540 2267

f
 94

s l a g c o n s t i t u e n t s and o t h e r r e f r a c t o r y o x i d e s was investi-

gated. Thus, the development of a p r o t e c t i v e c o a t i n g f o r
r e f r a c t o r i e s was a p p r o a c h e d from a p u r e l y e x p e r i m e n t a l
viewpoint. Some commonly a v a i l a b l e metal o x i d e s were
chosen and t h e i r a b i l i t y t o form s u i t a b l e c o a t i n g s was
studied.

3.1.4 Coating Composition

The o x i d e s CaO, SiO,,, A ^ O ^ , MgO and Z r 0 2 were

c o n s i d e r e d as p o s s i b l e c o a t i n g m a t e r i a l s . F o r any o f t h e
above o x i d e s t o be s u i t a b l e , t h r e e c o n d i t i o n s must be s a t i s -
f i e d ; t h e o x i d e must ( i ) r e a c t and form h i g h m e l t i n g
temperature compounds w i t h the s l a g c o n s t i t u e n t s , ( i i ) form
t h e s e compounds e a s i l y , and ( i i i ) n o t be expensive.

3.1.4.1 Phase Diagrams R e l e v a n t t o C o a t i n g Composition

Development
The e f f e c t i v e n e s s o f the o x i d e s - CaO, S i 0,2 A1 0 ,
2 3

MgO and Z r 0 , i n f o r m i n g compounds o r s o l i d s o l u t i o n s wi th the

2

s i a g c o n s t i t u e n t s was s t u d i e d u s i n g the phase d i a g r a m s from Re-

f e r e n c e ( 2 1 ) . The b i n a r y o r t e r n a r y o x i d e systems along with
t h e i r numbers as t h e y a p p e a r i n R e f e r e n c e (21) have been
l i s t e d below w i t h t h e i r s a l i e n t f e a t u r e s . Please note t h a t
reactive oxides present in the s i a g s and -capable o f
f o r m i n g s t a b l e compounds a r e As^C ,., B i ^ O ^ . PbO, Cu,,0 and
1

sb o .
2 3

(a) ( i ) C a 0 - A s 0 2 5 (No. 5095) - T h e r e i s no b i n a r y phase

d i a g r a m a v a i l a b l e but a t e r n a r y w i t h Fe 0 i n d i -
X

c a t e s t h e e x i s t e n c e o f t h e compounds CaO.As 0,-,

2

ZCaO.As 0 , 3 CaO.As 0 , 4 C a O . A s ^ .
2 5 2 5 The compounds
3CaO.As 0 2 5 and 4 C a O . A s 0 g2 have m e l t i n g p o i n t s o f
1450°C and 1520°C r e s p e c t i v e l y .

( i i ) CaO-BigOg-(No. 326) - T h e r e a r e no compounds but

o n l y m o n o c l i n i c and r h o m b o h e d r a l s o l i d s o l u t i o n s .
The m o n o c l i n i c t o c u b i c t r a n s i t i o n o c c u r s a t 690°C
and t h e h i g h e s t CaO c o n t a i n i n g c u b i c phase has a
melting p o i n t of 900°C.
( i i i ) Ca0-Cu 0-Cu0 (No. 2105) - The o n l y compound
2 present
i n t h i s s y s t e m i s CuO. 2 CaO. This system has ,a, lowest
e u t e c t i c a t 1030°C ( i n a i r ) c o n t a i n i n g a b o u t 95 wt.
% CuO.
A

( i v ) CaO-PbO (No. J5140) - The o n l y compound p r e s e n t i n

t h i s s y s t e m i s PbO.2 CaO which has a m e l t i n g point
of 822°C. The l o w e s t e u t e c t i c i s a t 815°C w i t h
13.75 wt.% CaO.

(y) CaO-Sb 0 - No phase d i a g r a m i s a v a i l a b l e on t h i s

2 3
s y s t e m but some o f t h e compounds formed between
 96

t h e s e two o x i d e s have been d e t e r m i n e d . These

compounds i n c l u d e : Ca Sb, 0^, C a S b 0 , , Ca.Sb '0- ,
o o o o oo

C LI CO 4 O CO
C a c S b Z0 b , C a 3S b 20 ,6, and CaSb 0...
9 o t :
24 o o o

(b) ( i ) M g 0 - A s 0 2 5 (No. 4054) - No b i n a r y phase d i a g r a m i s

a v a i l a b l e f o r t h i s system; only a t e r n a r y with
water. The p o s s i b l e compounds a r e 3Mg0.As 0,-, 2

2 M g 0 . A s 0 , M g O . A s ^ and M g 0 . 2 A s 0 .
2 5 2 5

( i i ) Mg0-Bi 0.j (No. 326) - No compounds o r s o l i d

2 solu-
t i o n s e x i s t i n t h i s system. The e u t e c t i c i s a t
785°C w i t h a b o u t 18 wt. %MgO.

( i i i ) Mg0-Cu 0 (No. 274) - No compounds a r e p r e s e n t i n

2

t h i s system. The e u t e c t i c i s a t 1180°C.

( i v ) MgO-PbO - Not a v a i l a b l e .

(v) M g 0 - S b 0 2 3 - Not a v a i l a b l e .

( c ) (1) A l 0 - A s 0
2 3 2 5 (No. 4058) - O n l y t h e t e r n a r y phase
diagram with water i s a v a i l a b l e . It appears that
the compoundsAl 2 3" 2 ° 5 ' 0 A s 2 A 1
2°3' 3 A s
2°5 a n d

Al 0 .3As 0
2 3 2 5 are p r e s e n t . The m e l t i n g p o i n t s o f
t h e s e compounds a r e not known.

( i i ) A^Qg-Bi^jQ-j (.No. 327) - Tfiere a r e no compounds i n

t h i s s y s t e m , and o n l y two s o l i d s o l u t i o n s - one i s
 97

m o n o c l i n i c and t h e . o t h e r b c c . The m e l t i n g p o i n t s o f
t h e bcc and m o n o c l i n i c s o l i d s o l u t i o n s a r e a t 770°C
and 810°C r e s p e c t i v e l y .

( i i i ) A ^ O ^ - P b Q (N . 0 280) - T h e r e i s one compound i n t h i s

s y s t e m , PbO.Al 0 , w i t h a m a l t i n g p o i n t "of 1000°C
2 3

and t h e l o w e s t e u t e c t i c i s a t 865°C w i t h a b o u t 90%

PbO.

(iv) Al 0 -Cu 0-Cu0

2 3 2 (No. 2085) - The e u t e c t i c i s a t
1165°C w i t h a b o u t 8 wt. % A 1 0 . 2 3 The compounds a r e
CuAl 0 2 4 and CuA.lD - 2

(v) A l 0 - S b 0
2 3 2 3 - Not a v a i l a b l e .

(d) ( i ) S i 0 - A s 0 - Not a v a i l a b l e .
2 2 5

(ii) Si0 -Bi" 02 2 3 (No. 328) - T h e r e a r e no compounds.

Two s o l i d s o l u t i o n s , one c u b i c arid the o t h e r bcc
a r e p r e s e n t . The l o w e s t e u t e c t i c i s a t 8 0 0 ° C .

( i i i ) S i 0 ~ C u 0 (No. 164) - T h e r e a r e no compounds

2 2

present. The l o w e s t e u t e c t i c i s a t 1060°C w i t h

8 wt. % S 1 0 . 2

( i v ) S i 0 - P b 0 (No. 51-70) - The compounds a r e P b S i 0 ,

2 4 g

Pb SiQ , Pb Si 0
2 4 3 2 7 and PbSIOg. The l o w e s t e u t e c t i c
i s a t 718°C.
 98

(v) S i 0 - S b 0
2 2 3 - Not a v a i l a b l e .

(e) ( i ) Z r 0 - A s 0
2 2 5 - Not a v a i l a b l e .

( i i ) Z r 0 - B i " 0 (No. 328) - T h e r e a r e no compounds.

2 2 3

Two s o l i d s o l u t i o n s a r e p r e s e n t ; one i s mono-

c l i n i c and t h e o t h e r i s c u b i c .

( i i i ) Z r 0 - C u 0 - C u 0 (No. 2145) - T h e r e a r e no compounds

2 2

or s o l i d s o l u t i o n s p r e s e n t . The l o w e s t e u t e c t i c
i s a t 1160°C.

( i v ) Z r 0 ~ P b O (No. 2330) - T h e r e a r e no compounds o r

2

solid solutions present.

(v) Zr0 -Sb„0„

9 - Not a v a i l a b l e .

From t h e above i t can be seen t h a t most o f t h e

i n f o r m a t i o n a v a i l a b l e on an o x i d e and s l a g components is
on CaO and s l a g c o n s t i t u e n t s . Moreover, i t i s e v i d e n t
from t h e b i n a r y systems, t h a t compounds formed between CaO
and o x i d e s i n t h e s l a g s have r e l a t i v e l y h i g h m e l t i n g p o i n t s .
On t h e o t h e r hand, CaO a l s o has a h i g h m e l t i n g p o i n t -
2787°C and i s r e a d i l y a v a i l a b l e i n i t s h y d r o x i d e and
carbonate forms. For t h e s e r e a s o n s CaO was c h o s e n as
a base compound f o r c o a t i n g d e v e l o p m e n t .

3.1.4.2 C o a t i n g D e v e l o p m e n t E x p e r i m e n t s

(i) Viscosity
For t h i s i n v e s t i g a t i o n v i s c o s i t i e s o f t h e s l a g C4
 99

w i t h v a r y i n g p r o p o r t i o n s o f CaO ( 1 0 , 15, 20 and 25 wt.%) were

measured. The CaO was added i n t h e form o f C a C O H ^ and mixed
and ground t h o r o u g h l y i n a b a l l m i l l . The v i s c o s i t y m e a s u r e -
ments were c a r r i e d o u t w i t h t h e a p p a r a t u s used b e f o r e .

The v i s c o s i t i e s o f t h e CaO and s l a g m i x t u r e s a r e

g i v e n i n A p p e n d i x l a and p l o t t e d i n F i g . 26. M i x t u r e s con-
t a i n i n g more t h a n 20 wt. %CaO were e x t r e m e l y g r a i n y b e c a u s e
o f compound f o r m a t i o n and l i t t l e l i q u i d r e m a i n e d . So no
v i s c o s i t y measurement was p o s s i b l e f o r m i x t u r e s c o n t a i n i n g
more than 20 wt. .% CaO. I t can be seen from F i g . 10 and
F i g . 26 t h a t t h e a d d i t i o n o f 20 wt. % CaO c a u s e s a 60 f o l d
i n c r e a s e i n t h e v i s c o s i t y o f s l a g C4. The l o w e s t m e l t i n g
phase i n t h i s m i x t u r e i s 6 7 0 C , as d e t e r m i n e d by t h e DTA
G

technique ( F i g . 27). The m e l t i n g p o i n t o f t h e pure C4 s l a g

i s 520°C. A l a r g e i n c r e a s e b o t h i n m e l t i n g p o i n t and v i s -
c o s i t y can thus be a t t a i n e d by a d d i n g a b o u t 20 wt. % CaO t o
the s l a g .

I t was o b s e r v e d d u r i n g t h e v i s c o s i t y measurement
t h a t more e x t e n s i v e f r o t h i n g o c c u r r e d i n t h e m i x t u r e con-
t a i n i n g 20 wt. % CaO and s l a g C4 than i n t h e pure s l a g . It
was a l s o o b s e r v e d t h a t t h e f r o t h i n g t e m p e r a t u r e was extended
o v e r a t e m p e r a t u r e range o f a b o u t 80°C - compared w i t h 15°C
f o r t h e pure s l a g . The i n c r e a s e i n b o t h t h e e x t e n t o f

i
 --15 CaO + C4
I
E
in

0-5 —10 CaO + C4

o C>
o
01

CP

°00

-0-5 JL
7-5 8 0 8 5 9 0 9-5 100
T"x|0 (K"') 4

F i g . 26 N o r m a l i z e d . V i s c o s i t y P l o t f o r CaO - Slag C4 M i x t u r e s
 j

LOL
 1 02

f r o t h i n g and the f r o t h i n g t e m p e r a t u r e r a n g e on a d d i n g CaO

to the s l a g c o u l d be due to the i n c r e a s e in slag v i s c o s i t y ,
31

as p r o p o s e d by C o o p e r and Kitchener. However, the

f r o t h i n g d e c r e a s e d a l o n g w i t h the f r o t h i n g t e m p e r a t u r e range
on s u c c e s s i v e heating and c o o l i n g r u n s p e r f o r m e d w i t h the
same sample. A f t e r about four c y c l e s the f r o t h i n g almost
disappeared.
(ii) I d e n t i f i c a t i o n o f Compounds i n F i r e d C a O - S l a g
Mixtures

X - r a y d i f f r a c t i o n p l o t s were made on C a O - s l a g C4
mixtures a f t e r heating them to 1 0 8 0 ° C ; the r e s u l t s are tabu-
l a t e d i n T a b l e IX. T h e s e e x p e r i m e n t s showed t h a t CaO and
s l a g C4 c o n s t i t u e n t s reacted and formed s e v e r a l compounds
i n d i c a t i n g t h a t CaO was e f f e c t i v e in trapping the s l a g c o n -
stituents. The a b s e n c e o f low a n g l e s c a t t e r i n g i n the x-ray
diffractometer p l o t s i n d i c a t e d the p r e s e n c e o f v e r y little
glassy phases. On the o t h e r hand, p r e s e n c e of some g l a s s y
phase i s e s s e n t i a l i n c o a t i n g s for sealing pores. However,
i t was still d e c i d e d to t e s t the p r o t e c t i v e q u a l i t y of t h i s
m i x t u r e o f 20 wt. %CaO and s l a g C4 as a c o a t i n g m a t e r i a l on
an a l u m i n a b r i c k a g a i n s t slag penetration. This coating was
called A4.
 103

Table IX Phases I d e n t i f i e d i n CaO + S l a g C4 M i x t u r e s

wt. % CaO wt. % S l a g Phases Identified

5 95 Ca^ Big 0 l g , PbO and Bi' 0

2 3

15 85 Ca^ B i 0 c 7 C and some PbO.

1, D I D

25 75 C a PbO^, C a B i
2 7 1 Q 0 2 2 and some
f r e e CaO.

50 50 F r e e CaO
 104
3.1.5 C o a t i n g A4

3.1.5.1 C o a t i n g M a t e r i a l s

The c o a t i n g c o m p o s i t i o n i d e n t i f i e d as A4 was pre-

p a r e d u s i n g 98% pure C a ( 0 H ) 2 and the s l a g C4. The Ca(0H) 2

d i s s o c i a t e s to CaO and H 0 2 a t about 450°C.

3.1.5.2 C o a t i n g P r e p a r a t i o n

A smooth p a s t e o f 20 wt. %CaO and s l a g C4 was made

by s u s p e n d i n g p a r t i c l e s o f s l a g C4 and CaO i n w a t e r , w i t h
a s m a l l amount o f a d e f l o c u l a t i n g a g e n t and gum a r a b i c . The
s l u r r y was t h e n mixed and ground i n a c e r a m i c b a l l m i l l f o r
about 12 h o u r s .

3.1.5.3 C o a t i n g A p p l i c a t i o n s

T h i s p a s t e was a p p l i e d on one s u r f a c e o f s m a l l
a l u m i n a b r i c k s ( d i m e n s i o n s were a b o u t 2.5 cm x 2.5 cm x 2.5
cm) u s i n g a p a i n t b r u s h . A p p r o x i m a t e l y 54 gms o f t h e 20 wt.
3
% CaO and s l a g C4 m i x t u r e i n 100 cm o f water gave the b e s t
fluid consistency for application.

The c o a t i n g was f i r s t d r i e d a t ambient temperature

and then i n an oven a t 100°C. The c o a t e d b r i c k was slowly
heated to 1100°C, maintained at t h a t temperature f o r one
h o u r , and c o o l e d t o room temperature.
 105
A f t e r performing s e v e r a l experiments as d e s c r i b e d
a b o v e , i t was o b s e r v e d t h a t a v e r y t h i c k c o a t i n g a p p l i c a t i o n
p r o d u c e d s u r f a c e c r a c k s on the c o a t i n g . A c o a t i n g t h i c k n e s s
o f a b o u t 1 mm was f o u n d to be o p t i m a l .

3.1.5.4 T e s t i n g o f C o a t i n g A4

S l a g C4 b u t t o n s (1.0 gm) were p l a c e d on an u n c o a t e d

t e s t b r i c k and on an A4 c o a t e d t e s t b r i c k . These b r i c k s
were then h e a t e d i n an e l e c t r i c b o x - f u r n a c e ( t h e same f u r n a c e
was used p r e v i o u s l y f o r f i r i n g t h e ' g r e e n ' c o a t i n g s ) t o a b o u t
1080°C and h e l d a t t h i s t e m p e r a t u r e f o r a b o u t an h o u r . The
b r i c k s were t h e n c o o l e d to room t e m p e r a t u r e and s e c t i o n e d
t h r o u g h t h e s l a g b u t t o n u s i n g a f i n e diamond saw.

3.1.5.5 D e t e r m i n a t i o n o f S l a g - P e n e t r a t i o n Depth

A t y p i c a l sectioned brick a f t e r a slag button test

i s shown i n F i g . 28; s i m i l a r o b s e r v a t i o n s were made f o r a l m o s t
a l l slag button t e s t s . A s c h e m a t i c d r a w i n g o f a s l a g pene-
t r a t i o n d e p t h p r o f i l e i s shown i n F i g . 28-b., The maximum
p e n e t r a t i o n d e p t h , d, r e p r e s e n t s t h e w o r s t c a s e o f s l a g
a t t a c k ; t h i s d e p t h was t a k e n as t h e s l a g p e n e t r a t i o n d e p t h .
T h i s v a l u e was used f o r a l l measurments on s l a g a t t a c k .
T h i s d e p t h was measured u s i n g a v e r n i e r c a l i p e r .
 106

(a)

rr
d

_ . J .

Al 2 0 3 BRICK

(b)

F i g . 28 (a) P i c t u r e o f a S l a g - P e n e t r a t e d A l u m i n a Brick and

(b) S c h e m a t i c View o f the B r i c k i n ( a ) .
 107

3.1.5.6 R e s u l t s and D i s c u s s i o n

The s l a g p e n e t r a t i o n i n t o t h e A4 c o a t e d b r i c k was
only s l i g h t l y l e s s than the p e n e t r a t i o n i n t o the uncoated
t e s t b r i c k , F i g . 29. T h i s poor r e s u l t i n d i c a t e d t h a t t h e
c o a t i n g d i d not prevent , or reduce slag penetration. This
r e s u l t was n o t u n e x p e c t e d as t h e c o a t i n g had v e r y l i t t l e
f u s i b l e phases to seal-up t h e p o r e s i n t h e b r i c k (section
3.1.T)./- The a b s e n c e o f any f u s i b l e phases a t t h e o p e r a t i n g
t e m p e r a t u r e r e s u l t e d i n a p o r o u s c o a t i n g and t h e p o r e s i n
the b r i c k remained exposed. A l t h o u g h t h i s e x p e r i m e n t was n o t
successful i t formed a b a s i s f o r f u r t h e r development.

3.2 CaO - S i 0 2 - Slag Coatings

3.2.1 Coating Composition

A C a O - s l a g c o a t i n g does n o t s t o p s l a g p e n e t r a t i o n
because t h i s mixture c o n t a i n s very few'. f u s i b l e p h a s e s .
However,CaO does i n c r e a s e t h e l o w e s t l i q u i d u s temperature
o f s l a g C4.

I t was r e a l i z e d a t t h i s s t a g e t h a t a s u i t a b l e c o a t -
i n g must have some f u s i b l e phases a t t h e o p e r a t i n g o r p r e -
heat treatment temperature! A suitable glass forming oxide
had t o be u s e d . S i l i c a r e a c t s w i t h most o f t h e s l a g c o n -
s t i t u e n t s f o r m i n g low t e m p e r a t u r e e u t e c t i c p h a s e s , (see
2 3 4 5 6 7 8 9 60 1
!...!...!...... I i I I I i I I I I i : 1
' 1

Slag penetration in A^O^ bricks:

(i) b r i c k 'a' i s a t e s t b r i c k and
( i i ) b r i c k '!' i s a b r i c k w i t h c o a t i n g A4.
 109

s e c t i o n 3.1.4) and s i l i c a i s a l s o a good g l a s s - f o r m e r .

S i l i c a was added t o t h e A4 c o a t i n g m i x t u r e . A coating
m i x t u r e o f o n l y CaO and S i 0 2 c o u l d n o t be v e r y e f f e c t i v e
as t h e l o w e s t e u t e c t i c i n t h i s s y s t e m i s a t 1436°C ( F i g .
30).

A l l subsequent experimental c o a t i n g s contained

CaO, S i 0 2 and s l a g C4 i n v a r y i n g p r o p o r t i o n s , e x c e p t c o a t i n g
C8 which a l s o c o n t a i n e d A l 0 . o o

3.2.2 Low CaO - S i 0 2 Coatings

I n i t i a l l y s m a l l amounts o f S i 0 2 were added along

w i t h s m a l l q u a n t i t i e s o f CaO t o r e l a t i v e l y l a r g e q u a n t i t i e s
of s l a g C4 t o s t u d y t h e e f f e c t o f S i 0 2 on t h e f o r m a t i o n o f
f u s i b l e phases i n t h e c o a t i n g s .

C o a t i n g s o f d i f f e r e n t c o m p o s i t i o n s A6, A8, C7, C8

and C9 were made. The c o m p o s i t i o n s o f t h e s e c o a t i n g s a r e
t a b u l a t e d i n T a b l e X. These c o a t i n g m i x t u r e s were p r e -
p a r e d as b e f o r e .

D i f f e r e n t i a l thermal a n a l y s i s experiments were

performed on the above coating mixtures. A typi-
cal DTA plot for c o a t i n g >C8 ( a s can be seen i n
Fig. 31) showed t h a t i n s i g n i f i c a n t amounts of fusible
2400

2000

1723 <

•600 _
Cristobalite + L i q .

'. Tridymite+ Liq.

1200 Tridymite + Pseudowollastonite (a-CaSi0 ) 3

1125°
a ' - C a S i 0 + CaO
z 4

Tridymite + Wollastonite ( B-CoSi0 ) 3 S-CaSiOj

870° +
800 - Ca Si 0
3 2 7 ,Ca Si 0 4-y-Ca Si0
3 2 7 2 4

a-Quartz + Wollastonite
725°
J- 1 y - Ca SiQ, + CaO
2

_L
10 30 - ^ - ^ ^ - ^ 90
Si0 2 CaOSiOj 3CaO-2Si02 2Ca0 Si0 2 3CoO S i 0 2 C a 0

Bert Phillips and Arnulf Muan, J. Am. Ceram. Soc, 42 [9] 414 (1959).
Based mainly on data of G. A. Rankin andlF.IE. Wright, Am. J. Sci. [4], 39, 5 (1915) and J. W.
Greig, Am. J. Sci., [5], 13, 1-14; [74] 133-54 (1927). Changes with respect to stability relations
of tricalcium and dicalcium silicates based on data of D. M . Roy, / . Am. Ceram. Soc, 41 [8] 293-
99 (1958) and J. H . Welch and W. Gutt, J. Am. Ceram. Soc, 42 [1] 11-15 (1959).

F i g . 30 CaO - S i 0 ? Phase Diagram.

 Ill

Table X Composition of Coatings

Composition (wt. % )
Coating No.
Si Oo CaO A1
2°3 S l a g C4

A4 - 20 - 80

A6 10 10 - 80

A8 20 10 - 70

C8 15 15 - 70

C7 15 15 10 60

C9 20 20 —
60

C6 80 10 —
10

DI 70 20 —
10

D2 60 30 ' —
10
Sample. COATING C8 Date. 19-Jul-83 Time. 9.47.06
Sizes 0. 00 DT A Operators DIPANKAR
Rate* 15. 0

F i g . 31 DTA P l o t f o r C o a t i n g C8.
 113
phases were p r e s e n t i n t h i s s y s t e m . T h i s i s i n d i c a t e d by t h e
a b s e n c e o f s m a l l and b r o a d e n d o t h e r m i c peaks such as t h o s e
found i n F i g . 27. In o r d e r t o i n c r e a s e t h e f u s i b l e p h a s e s i n
the c o a t i n g m i x t u r e s the concentration of S i 0 2 had t o be
increased. T h i s was done by i n c r e a s i n g t h e c o n c e n t r a t i o n
of S i 0 2 i n the coating mixtures w h i l e d e c r e a s i n g t h e amount
o f s l a g C4 and k e e p i n g t h e CaO t o a low l e v e l o f a b o u t 20
wt. % i n t h e c o a t i n g s .

3.2.3 High S i 0 2 Coatings

The amount o f S i 0 2 was i n c r e a s e d t o as h i g h as 80

wt. %: i n t h e c o a t i n g m i x t u r e s to create s i g n i f i c a n t con-
c e n t r a t i o n s o f glassy phases. C o a t i n g s C6, DI and D2,
c o n t a i n i n g v a r y i n g p r o p o r t i o n s o f CaO, S i 0 2 and s l a g C4,
were made. The c o m p o s i t i o n s o f t h e s e c o a t i n g s c a n be seen
i n T a b l e X.

3.2.3.1 X-ray D i f f T a c t o m e t e r S t u d i e s o f t h e C o a t i n g s

The c o a t i n g m i x t u r e s were f i r e d a t 1080°C and

r a p i d l y c o o l e d t o ambient t e m p e r a t u r e . The p h a s e s present
i n t h e c o a t i n g s were then d e t e r m i n e d by x - r a y diffraction.
In t h e low C a 0 - S i 0 2 c o a t i n g s some f r e e s l a g c o n s t i t u e n t s
were f o u n d t o be p r e s e n t e . g . , PbO and B i ^0 ^ and t h e c o a t i n g s
d i d n o t a p p e a r t o be v e r y amorphous. In t h e case o f t h e
 114
h i g h CaO-SiG^ c o a t i n g s . t h e r e was no f r e e s l a g b u t C a S i O ^
and S i O 2 ( c r i s t o b a l i t e ) were p r e s e n t . The p r e s e n c e o f g l a s s y
phases was a l s o i n d i c a t e d by a broad peak a t s m a l l a n g l e s i n
the x - r a y d i f f r a c t o m e t e r p l o t s .

3.2.3.2 C o a t i n g Preparation

Large batches of coating mixtures were prepared

f o l 1 owing the procedure o u t l i n e d before. From t h e s e mixtures
smooth p a s t e s were made and then a p p l i e d t o a l u m i n a b r i c k s as
mentioned e a r l i e r . These c o a t e d b r i c k s were f i r e d a t a slow
h e a t i n g r a t e o f 1 5 0 ° C / h o u r up t o 500°C t o p r e v e n t cracking of
the c o a t i n g s . From 500°C t o 1100°C t h e h e a t i n g r a t e was i n -
creased t o about 250°C/hour.. A t t h e maximum t e m p e r a t u r e
o f 1 1 0 0 ° C , t h e s p e c i m e n s were h e l d f o r one h o u r . The b r i c k s
were then c o o l e d t o room t e m p e r a t u r e and were r e a d y f o r s l a g
penetration tests.

To form a c o a t i n g m i x t u r e of the right consistency

f o r good c o a t i n g f i n i s h and t o m i n i m i z e c r a c k i n g , i t was
found t h a t t h e c o a t i n g s s h o u l d have t h e f o l l o w i n g powder t o
water r a t i o s :
Coatings Weight o f Powder/100 gms. o f Water
A6 83.0 gms
C6 41.5 gms
C8 32.1 gms
DI 33.0 gms
D2 30.7 gms
 1 1 5

I t s h o u l d be m e n t i o n e d here t h a t c o a t i n g C8 was
made to s t u d y the e f f e c t o f A ^ O ^ on s l a g p e n e t r a t i o n .

3.2.3.3 S l a g P e n e t r a t i o n Tests

The c o a t e d and p r e f i r e d a l u m i n a b r i c k s were s u b j e c t e d

to s l a g b u t t o n t e s t s and the p e n e t r a t i o n d e p t h s were measured
as d e s c r i b e d earlier.

3.3 R e s u l t s and Discussion

C o a t i n g s A6, A8, C7, C8 and C9 ( a l l w i t h low SiOy)

y i e l d e d a modest r e d u c t i o n i n s l a g p e n e t r a t i o n - F i g . 3 2 ( a ) .
However, the r e d u c t i o n i n p e n e t r a t i o n was not s i g n i f i c a n t
( p r o b a b l y due t o the a b s e n c e o f any f u s i b l e p h a s e s i n t h e s e
coatings).

From the p e r f o r m a n c e o f c o a t i n g C8, i t was r e a l i z e d

that A 1 0 2 3 was not a good c o a t i n g m a t e r i a l .

The h i g h S i 0 2 c o n t a i n i n g c o a t i n g s performed reason-

ably w e l l . The e x t e n t o f s l a g p e n e t r a t i o n i n t o alumina
b r i c k s c o a t e d w i t h c o a t i n g s C6, DI and D2 ( a l l wi th h i g h
S i 0 ) i s compared w i t h s l a g p e n e t r a t i o n i n t o the
2 uncoated
t e s t b r i c k in F i g . 32(b).
F i g . 32 a Slag penetration in A l b r i c k s :
(i) brick 'a' is a test-brick,
(ii) brick '2' is w i t h c o a t i n g A8,
(iii) brick '4' is w i t h c o a t i n g C7 and
(iv) brick '3' is w i t h c o a t i n g C8.
 50 1 2 3 4 5 6 _2

Slag penetration in A l ^ O ^ b r i c k s :
(i) b r i c k 'a' is a test brick,
(ii) b r i c k 40 i s w i t h c o a t i n g C6,
(iii) b r i c k 56 i s w i t h c o a t i n g DI and
(iv) b r i c k 44 i s w i t h c o a t i n g D2.
 118

Chapter 4

4. IMPREGNATION OF REFRACTORY BRICKS

BY OXIDES AND SALTS

4.1 I n t r o d u c t i on

I t became a p p a r e n t from the c o a t i n g e x p e r i m e n t s that

a p p l i c a t i o n of a c o a t i n g cannot prevent s l a g p e n e t r a t i o n into
r e f r a c t o r y pores. For t h i s r e a s o n , an a l t e r n a t i v e method t o
b l o c k the p o r e s had to be f o u n d . I t was d e c i d e d t o a t t e m p t
to f i l l the p o r e s o f the b r i c k s by i m p r e g n a t i n g t h e b r i c k s
w i t h o x i d e s and s a l t s . The o n l y known p r a c t i c e f o r impregna-
t i n g b r i c k s i s i n the c a s e o f t h e BOF and QBOP p r o c e s s e s where
carbon i s impregnated into magnesite and chrome-magnesite
bricks.

The c a r b o n i s i n t r o d u c e d i n t o t h e s e b r i c k s by two
methods: ( i ) the b r i c k c o n s t i t u e n t s a r e mixed w i t h a p i t c h
b e f o r e the b r i c k i s p r e s s e d and baked, and ( i i ) f i r e d r e -
f r a c t o r i e s are impregnated with molten p i t c h by vacuum
impregnation techniques. Carbon i n f i l t r a t e d b r i c k s cannot
be used i n Dore f u r n a c e s b e c a u s e o f the h i g h l y o x i d i s i n g
envi ronment. 1
 119
4.2 Impregnation

4.2.1 C a l c u l a t i o n of Bri c k P o r o s i t y

A l u m i n a b r i c k s were used f o r i m p r e g n a t i o n s t u d i e s
b e c a u s e o f the ease w i t h which s l a g p e n e t r a t i o n profiles
c o u l d be s t u d i e d , as m e n t i o n e d i n s e c t i o n ( 3 . 1 . 2 ) . To
study the impregnation c h a r a c t e r i s t i c s of these b r i c k s
i t was n e c e s s a r y to know t h e i r a p p a r e n t volume porosity
( i . e . open pore v o l u m e ) .

The a p p a r e n t p o r o s i t y o f a r e f r a c t o r y b r i c k ( e x p r e s -
sed as a p e r c e n t a g e ) i s t h e r a t i o o f t h e volume o f t h e open
p o r e s p r e s e n t i n a b r i c k t o the t o t a l volume o f t h e b r i c k .
T h i s i s measured i n t h e f o l l o w i n g way: i.) a c o n v e n i e n t l y
s i z e d d r y b r i c k i s w e i g h e d i n a i r (W-j), ( i i ) the b r i c k i s
then b o i l e d i n w a t e r f o r a b o u t 40 m i n u t e s ( f o r a sample
m e a s u r i n g a p p r o x i m a t e l y 2.5 cm x 2.5 cm x 2.5 cm) and w e i g h -
ed w h i l e s u s p e n d e d i n w a t e r (W ) 2 and ( i i i ) t h e w a t e r -
saturated w e i g h t o f t h e b r i c k i n a i r i s measured (W* ).
3

The w e i g h t measurements a r e summarized:

Dry w e i g h t = toy gms

Suspended w e i g h t = W 2 gms
Saturated weight = w" 3 gms
The % volume porosity x 100. 4.1
 F i v e b r i c k samples were t a k e n and t h e a v e r a g e
p o r o s i t y was d e t e r m i n e d . The r e s u l t s a r e g i v e n i n T a b l e X I .

T a b l e XI P o r o s i t y of Alumina Bricks

W (gms) W (gms) W (gms) (Apparent)

1 2 3

% Vol. Porosity

47.29 30.98 51.35 19.95

51.15 33.51 55.53 19.90
48.50 31.78 52.71 20.10
47.79 31.31 51.91 20.00
54.50 35.71 59.21 20.05

The a v e r a g e volume ( a p p a r e n t ) p o r o s i t y (%) o f t h e

a l u m i n a b r i c k s was f o u n d t o be 20.00%.

4.2.2 Oxide Impregnation

I t i s o b v i o u s from t h e s t u d i e s o f t h e c o a t i n g
d e v e l o p m e n t t h a t CaO r e a c t s w i t h most o f t h e s l a g con-
s t i t u e n t s t o form compounds and s o l i d s o l u t i o n s . So i t
was d e c i d e d t o i m p r e g n a t e t h e a l u m i n a b r i c k s w i t h CaO
to r e d u c e s l a g p e n e t r a t i o n . S e v e r a l methods can be used
to i m p r e g n a t e t h e b r i c k s w i t h CaO and f i l l the pores.
These i n c l u d e : ( i ) CaO i n aqueous s o l u t i o n , ( i i ) C a ( 0 H ) ?
 121
i n aqueous s o l u t i o n and ( i i i ) CaO suspended i n water.
CaO has a v e r y low s o l u b i l i t y i n water a t 20°C (0.100 gm
Ca0/100 cm water). T h i s low s o l u b i l i t y - l i m i t does n o t
p e r m i t a s i g n i f i c a n t i n t r o d u c t i o n o f CaO.

A sample c a l c u l a t i o n was p e r f o r m e d to v e r i f y this

contention. A 20% porous b r i c k , w i t h a volume o f 16.42
cm and a mass o f 47.80 gms was c o n s i d e r e d . I f a l l the
open p o r e s were f i l l e d w i t h CaO s o l u t i o n t h e amount o f
3
s o l u t i o n i n t h e p o r e s would be 3.284 cm (approximately
3.284 gms). T h i s amount o f s o l u t i o n c o n t a i n s 0.00328 gms
o f CaO which y i e l d s a wt. % CaO impregnation of only
about 0.0069. T h i s s m a l l amount o f CaO i m p r e g n a t i o n could
not r e d u c e s l a g p e n e t r a t i o n .

A s i m i l a r c a l c u l a t i o n suggests that the i n t r o d u c t i o n

o f CaO as a s a t u r a t e d s o l u t i o n o f C a ( 0 H ) 2 yields a retained
CaO c o n t e n t o f o n l y 0.0096 wt. %CaO a f t e r h e a t i n g a t 450°C.
T h i s i s because
the s o l u b i l i t y of Ca(0H) 2 i n water i s o n l y
3
about 0.185 gm/100 cm o f w a t e r .

The i m p r e g n a t i o n o f a l u m i n a b r i c k s w i t h CaO by
suspending CaO o r C a ( 0 H ) 2 i n w a t e r was c o n s i d e r e d n e x t .

A w a t e r s u s p e n s i o n o f c o a r s e CaO p a r t i c l e s was
made by s u s p e n d i n g c o m m e r c i a l l y a v a i l a b l e CaO powder w i t h
 122

the h e l p o f a d e f l o c u l at.ing a g e n t . The s t r e n g t h o f t h e

3

s u s p e n s i o n was 50 gms o f CaO powder i n 100 cm of water.

A sample c a l c u l a t i o n r e v e a l e d t h a t a s u s p e n s i o n o f t h i s
s t r e n g t h would y i e l d a n e t .weight; g a i n o f a p p r o x i m a t e l y 2.78
wt. % CaO i n t h e a l u m i n a b r i c k s i f a l l t h e p o r e s were f i l -
l e d by t h e i n f i l t r a t i n g l i q u i d . Two methods were used t o
i n f i l t r a t e t h e CaO-water s u s p e n s i o n i n t o t h e a l u m i n a b r i c k s .
The methods employed were d i f f e r e n t i n o p e r a t i o n a l techni-
que b u t t h e o b j e c t i v e o f s o a k i n g t h e a l u m i n a b r i c k s w i t h
the s u s p e n s i o n was the same.

4.2.2.1 Vacuum S u c t i o n
A vacuum s t u c t i o n d e v i c e was a v a i l a b l e as shown i n
Fig. 33. The bottom p l a t e of the c y l i n d r i c a l part of the
d e v i c e had h o l e s punched i n t o i t and t h i s p l a t e was c o n -
n e c t e d t o an a s p i r a t o r by f l e x i b l e r u b b e r t u b i n g . The
a l u m i n a b r i c k samples were p l a c e d on t h e s e h o l e s making s u r e
t h a t t h e b r i c k f a c e i n c o n t a c t w i t h the. c i r c u l a r p l a t e was
reasonably f l a t . The a r e a c o v e r e d by t h e h o l e s i n t h e p l a t e
was s m a l l e r than t h e a r e a o f t h e b r i c k f a c e . i n c o n t a c t w i t h
the p l a t e .

The aluminum'; h o l d e r was f i l l e d w i t h t h e CaO-

water m i x t u r e . T h i s m i x t u r e was s u c k e d t h r o u g h t h e b r i c k
u s i n g an a s p i r a t o r . In o r d e r t o d e t e r m i n e t h e amount o f
 123

Acrylic Tube

Collector Flask

Fig. 33 A p p a r a t u s Used f o r Vacuum S u c t i o n .

 124
CaO i m p r e g n a t e d i n t o t h e b r i c k t h e b r i c k was h e a t e d t o
a b o u t 500°C after infiltration t o remove t h e w a t e r and
c o n v e r t t h e Ca(OH),, t o CaO, and from t h e n e t w e i g h t g a i n e d
the e x t e n t o f i n f i l t r a t i o n was d e t e r m i n e d . The r e s u l t s o f
t h i s t e s t a r e shown i n T a b l e X I I .

Table XII CaO I m p r e g n a t i o n i n A l u m i n a Bricks

Dry Wei g h t o f Weight A f t e r CaO Wt. % CaO

Bricks I m p r e g n a t i on I m p r e g n a t i on
W (gms)
1 W (gms)
2

45.15 45.28 0.29

47.69 47.83 0.29
43. 33 43.46 0.30
49.25 49.41 0.32
50.46 50.61 0.29

The maximum i m p r e g n a t i o n t h a t c o u l d be a c h i e v e d by
t h i s method was a b o u t 0.3%, w e l l below t h e 2.75% o r i g i n a l l y
expected from the c a l c u l a t i o n . I t a p p e a r s t h a t CaO p a r t i -
c l e s do n o t e n t e r t h e p o r e s o f t h e b r i c k s . In o r d e r t o
d e t e r m i n e t h e amount o f l i q u i d p e n e t r a t i o n u s i n g t h e vacuum
s u c t i o n d e v i c e , a l u m i n a b r i c k s were i m p r e g n a t e d w i t h w a t e r
at 20°C. ..\ , ' • ' ••• r
 125
About 75% o f t h e p o r e s i n t h e b r i c k s can be f i l l e d
by an i n f i l t r a t i n g l i q u i d u s i n g t h e vacuum s u c t i o n d e v i c e .
The s m a l l w e i g h t g a i n a r i s i n g from CaO i m p r e g n a t i o n en-
c o u n t e r e d d u r i n g i n f i l t r a t i o n was most p r o b a b l y b e c a u s e
the i n f i l t r a t i n g p a r t i c l e s were n o t e n t e r i n g t h e p o r e s o f
the bricks. T h i s can be a t t r i b u t e d t o t h e b l o c k a g e o f
s u r f a c e p o r e s by CaO p a r t i c l e s which p r e v e n t s f u r t h e r p a r t i -
cle penetration.

4.2.2.2 B o i l i n g

The open volume p o r o s i t y o f b r i c k s i s f o u n d from t h e

amount o f w a t e r i n c o r p o r a t e d i n t o a b r i c k sample.by boiling
the b r i c k s i n w a t e r f o r about 40 m i n u t e s .

S i n c e t h e vacuum s u c t i o n procedure was u n a b l e t o

fill a l l the p o r e s p r e s e n t i n t h e b r i c k s , i t was d e c i d e d
to i m p r e g n a t e t h e b r i c k s by b o i l i n g them i n a s u s p e n s i o n o f
CaO i n w a t e r . A s u s p e n s i o n was made as b e f o r e and t h e b r i c k s
were t h e n b o i l e d i n them o v e r a b u r n e r f o r a b o u t 40 m i n u t e s .
The l e v e l o f w a t e r i n t h e b o i l i n g v e s s e l was k e p t c o n s t a n t by
a d d i n g s m a l l amounts o f w a t e r a t r e g u l a r i n t e r v a l s . This
t e s t was p e r f o r m e d on a few b r i c k samples and then t h e b r i c k s
were f i r e d t o 50O°C and t h e wt. % i n c r e a s e due t o CaO r e t e n -
t i o n was c a l c u l a t e d . The r e s u l t s a r e t a b u l a t e d i n T a b l e
xiri.
 126
Table XIII Wt. %CaO I m p r e g n a t i o n i n Alumina B r i c k s

W (gms) W (gms) wt. % CaO

1 2
• I m p r e g n a t i on

51. 36 51.61 0.48

47.84 48.09 0.52

49.18 49.43 0.51

B o i l i n g t h e b r i c k s i n c r e a s e s t h e wt. % CaO i m p r e g n a -
t i o n but t h i s i n c r e a s e i n impregnation i s s t i l l q u i t e s m a l l .
The amount o f c a r b o n i m p r e g n a t e d i n t o mag-chrome b r i c k s i s
i n the o r d e r o f 2 wt. %.

So b o t h the above methods a r e n o t s u i t a b l e f o r o x i d e

impregnation into b r i c k s . However, i t s h o u l d be p o s s i b l e
to i n f i l t r a t e o x i d e s i n t o r e f r a c t o r y b r i c k s i f t h e o x i d e
p a r t i c l e s a r e made s m a l l e r t h a n t h e p o r e s i n t h e b r i c k s
b u t t h i s work was n o t p u r s u e d .

4.2.3 Salt Impregnation

I t was d e c i d e d a t t h i s s t a g e t o i n f i l t r a t e t h e
a l u m i n a b r i c k s w i t h a h i g h l y s o l u b l e c a l c i u m s a l t and t h e n
c o n v e r t t h e s a l t t o C a ( 0 H ) , i f p o s s i b l e , by p a s s i n g NH.OH
?
 127
through the b r i c k . The s o l u b l e s a l t chosen was CaCl,,. The
r e a c t i o n used t o c o n v e r t C a C l 2 to Ca(0H) i s :
2

CaCl 2 +2 NH 0H4 Ca(OH) 2

+
2 NH^Cl 4.2
Both t h e v o l a t i l i z a t i o n o f NH C1 and t h e c o n v e r s i o n o f Ca(0H)
4 2

to CaO can be done by h e a t i n g t h e i m p r e g n a t e d b r i c k s t o 500°C.

S e v e r a l a l u m i n a b r i c k samples were i m p r e g n a t e d w i t h
a CaCl 2 s o l u t i o n by b o i l i n g them i n t h e s o l u t i o n . The b r i c k s
were t h e n s l o w l y h e a t e d t o 500°C t o e n s u r e t h a t a l l o f t h e
s a l t i n t h e b r i c k was i n t h e f o r m o f C a C l 2 (anhydrous). The
w e i g h t o f t h e s e b r i c k s was measured and t h e n NH^OH s o l u t i o n
p a s s e d t h r o u g h t h e b r i c k s by vacuum s u c t i o n . The b r i c k s
were r e h e a t e d t o 500°C t o c o n v e r t t h e Ca(0H) 2 t o CaO and
v o l a t i l i z e t h e NH^Cl and t h e n r e w e i g h e d . The wt. % o f
CaCl 2 and CaO i m p r e g n a t i o n a r e shown i n T a b l e XIV.

When NH4OH s o l u t i o n was p a s s e d t h r o u g h t h e b r i c k s

i t washed C a C l 2 out o f the pores i n the b r i c k l e a v i n g very
little CaCl 2 behind. A b r i c k i m p r e g n a t e d w i t h a b o u t 2.5
wt. % C a C l 2 p r o d u c e d o n l y about 0 . 5 wt. % i n c r e a s e due t o CaO
r e t e n t i o n * whereas t h e w e i g h t i n c r e a s e e x p e c t e d from 2.5
wt. % C a C l 0 i s a b o u t 1.5%. T h i s method was a b a n d o n e d .
T a b l e XJV CaO Impregnation i n Alumina Bricks

Dry Wt. Wt. After CaCl 2 Wt. % C a C l

2 Wt. After CaO Wt. % CaO
Impregnation Impregnation Conversion Impregnation
(gms) (gms) (gms)

50.45 51.74 2.50 50.70 0.50

46.23 47.46 2.60 46.48 0.54

48.78 50.07 2.58 49.04 0.53

ro
co
4.2.4 S l a g P e n e t r a t i o n T e s t s on G a C 1 ? Impregnated B r i c k s

I t was o b s e r v e d i n the p r e v i o u s s e c t i o n , t h a t the

alumina b r i c k samples c o u l d e a s i l y be i m p r e g n a t e d with CaCl
s o l u t i o n and 2.5 wt. % C a C l 2 c o u l d be r e t a i n e d i n the b r i c k s
In o r d e r t o e v a l u a t e the e f f e c t i v e n e s s o f CaCl,, impregnated
alumina bricks s l a g p e n e t r a t i o n t e s t s were c o n d u c t e d on
them. The r e s u l t s are shown i n F i g . 34. The r e s u l t s i n d i -
c a t e t h a t the s l a g p e n e t r a t i o n i n a C a C l 2 impregnated brick
was l e s s than t h a t o f c o a t i n g s C6, DI and D2. On the b a s i s
of t h i s o b s e r v a t i o n i t was concluded that CaCl 2 c o u l d be
used as an i n f i l t r a t i n g m a t e r i a l to f i l l - u p the pores of
refractories.

After this preliminary test the e f f e c t o f the con-

centration of C a C l 2 i n r e f r a c t o r i e s on the s l a g p e n e t r a t i o n
b e h a v i o u r was studied. B r i c k s were i m p r e g n a t e d with differ
ent wt. % o f C a C l 2 by two methods as d e s c r i b e d below.

(a) The maximum pore volume o f t h e b r i c k samples t h a t

c o u l d be f i l l e d by the vacuum s u c t i o n t e c h n i q u e was about
75% o f the t o t a l pore volume. By a d o p t i n g the c a l c u S r
lation g i v e n below, a p r e - d e t e r m i n e d weight % increase
c o u l d be obtained.
3
L e t the volume o f the b r i c k = V cm , then volume
3
o f l i q u i d i n f i l t r a t e d i n t o the b r i c k = 0.15 V cm
(75% o f 20% v o l . p o r o s i t y ) .
 130

I i I i I i 1 i I i I i I i I i I * !

F i g . 34 Alumina b r i c k s a f t e r slag-button tests.

(i) b r i c k 'a' i s a t e s t b r i c k ,
( i i ) b r i c k 'b' i s w i t h c o a t i n g D2 and
( i i i ) b r i c k 'c' i s w i t h a b o u t 2 wt. % C a C l 2

impregnation.
 131
L e t the w e i g h t of the b r i c k = M gms, and the
r e q u i r e d wt. % o f s o l i d s i n the b r i c k = m.

L e t the w e i g h t o f G a C l 2 t h a t w i l l be infil-
t r a t e d i n t o the b r i c k = x gms (unknown)

Then, m = j^fy 4.3

From the above e q u a t i o n x can be f o u n d as m and M are known.

A f t e r d e t e r m i n i n g the v a l u e of x a s o l u t i o n of x
gms of C a C l 2 was made i n w a t e r and i t s d e n s i t y measured w i t h
a pycnometer. Once the d e n s i t y was known the strength
o f the s o l u t i o n c o u l d be f o u n d u s i n g a t a b l e a v a i l a b l e i n
any handbook on I n o r g a n i c Chemistry. Then several solutions
were made f o r d e s i r e d amounts o f i m p r e g n a t i o n . The bricks
were i m p r e g n a t e d by the vacuum s u c t i o n method described
before. The wt. % i m p r e g n a t i o n was c a l c u l a t e d on the basis
o f the amount o f a n h y d r o u s C a C l 2 i n the brick.

(b) When b r i c k s were b o i l e d i n a l i q u i d or s o l u t i o n a b o u t

100% o f the open p o r e s c o u l d be f i l l e d i n a b o u t 40 m i n u t e s .
However, the b o i l i n g o p e r a t i o n r e d u c e d the volume o f w a t e r
present i n the s o l u t i o n due to e v a p o r a t i o n and so the liquid
i n the b o i l i n g v e s s e l was k e p t a l m o s t a t the same l e v e l at
a l l t i m e s by a d d i n g s m a l l amounts o f w a t e r . This technique
c o u l d be i m p r o v e d by r e - c i r c u l a t i n g the steam p r o d u c e d i n
 1 32
the form o f w a t e r t o t h e b o i l i n g v e s s e l .

The above methods (a and b) showed v a r i a t i o n s o f

+ 5% i n t h e v a l u e s o f m, t h e w e i g h t % o f s o l i d s i n t h e b r i c k .
It should be m e n t i o n e d h e r e t h a t t h e above methods worked
quite s u c c e s s f u l l y f o r small b r i c k samples ( 2 . 5 em x 2.5 cm
x 2.5 cm) g i v i n g a l m o s t a u n i f o r m d i s t r i b u t i o n o f C a C l 2 within
the b r i c k body b u t i n t h e c a s e o f l a r g e r b r i c k s t h i s may n o t
work as w e l l . C a d 2 penetration of surface l a y e r s t o a depth
o f a few c e n t i m e t r e s should provide an a d e q u a t e b a r r i e r
against slag penetration. A number o f b r i c k s were i m p r e g n a -
ted with d i f f e r e n t concentrations o f C a G l ^ s o l u t i o n s and
dried. Using these bricks the e f f e c t of the CaCl 2 con-
centration (present i n a b r i c k ) on s l a g p e n e t r a t i o n was
studied. Slag-button t e s t s were u s e d .

4.2.5 E f f e c t o f D i f f e r e n t wt.% C a C l 2 I m p r e g n a t i o n on

Slag Penetration

When t h e maximum s l a g p e n e t r a t i o n distance i s plotted

a g a i n s t t h e wt.•:'•% C a C l 2 impregnation i n the AlgO^ b r i c k s ,
the s l a g p e n e t r a t i o n f i r s t d e c r e a s e s and t h e n i n c r e a s e s as
shown i n F i g . 35. The minimum s l a g p e n e t r a t i o n was 0.5 cm
f o r a 2.5% i m p r e g n a t i o n (measured e x p e r i m e n t a l l y ) and 0.49
cm f o r a b r i c k c o n t a i n i n g 3% C a C l , whereas t h e s l a g pene-
2

t r a t i o n i n a b r i c k w i t h no c o a t i n g o r i m p r e g n a t i o n i s 1.20
 133

Ail ^tA ferf

i
mmM
9 20 1 2 3 4 5 6 7 8 9

F i g . 35 B r i c k s w i t h v a r y i n g amounts o f CaCl,,
impregnation No. 37 = 0.7 wt.%, No. 51 =
1.2 wt.%, No. 38 = 2.0 wt.%, No. 2 = 2.5
wt.%, No. 47 = 3.0 wt.% and No. 36 = 4.0 wt,
 134
cms. B r i c k s c o n t a i n i n g more than 3.0 wt. % C a C ^ showed i n -
creased slag penetration. T h i s can be a t t r i b u t e d to the
f o r m a t i o n o f m i c r o and macro c r a c k s i n the b r i c k . With an
i n c r e a s e d amount o f s o l i d s i n the b r i c k ( g r e a t e r than 3%)
the w a t e r ( f r o m the s o l u t i o n and w a t e r o f c r y s t a l 1 i s a t i o n )
would f i n d i t more d i f f i c u l t t o e s c a p e ( i n the form o f steam)
through the pores d u r i n g f i r i n g . The s t r e s s e s generated
i n the b r i c k due to e n t r a p p e d water vapour could cause
cracks to appear. The c r a c k s can be seen i n F i g s . 3& and 37.
Larger c o n c e n t r a t i o n s of C a C ^ p a r t i c l e s i n the cracked
r e g i o n s a r e i n d i c a t i v e o f t h e f a c t t h a t a l a r g e r amount o f
steam was generated in these areas. Such c r a c k s are
c l e a r l y v i s i b l e w i t h o u t any m a g n i f i c a t i o n i n b r i c k s w i t h
a b o u t 5 or 6% impregnation.

So : the b e s t i m p r e g n a t i o n of A^O^ b r i c k s was by

a b o u t 3 wt. % G a C ^ - T h i s c o n c e n t r a t i o n can r e d u c e slag
penetration significantly.

The b e s t c o a t i n g (D2) reduces the s l a g p e n e t r a t i o n

by a f a c t o r o f 1.41. A 3 wt.% impregnation with CaClg
reduces s l a g p e n e t r a t i o n by a f a c t o r o f 2.40. Both f a c t o r s
have been computed on t h e b a s i s o f s l a g p e n e t r a t i o n i n t o
pure A l ^ O g b r i c k s w i t h o u t c o a t i n g s o r impregnation.

By s t u d y i n g the e f f e c t s o f c o a t i n g s and impregnation

 135

30 1 2 3 4 5 6 7 8 9

F i g . 36 C r a c k s i n b r i c k s due to e x c e s s i v e CaCl 2

impregnation No. 46 = 3.5 wt. %, No. 28 =

5.5 wt. %, No. 36 = 4.0 wt. %, No. 47 = 3.0
wt. %.
F i g . 37 SEM p i c t u r e o f a c r a c k i n a 5.0 wt. % CaCl
impregnated b r i c k . White p a r t i c l e s a r e
CaCl 9 (x 40).
 137
on s l a g - b r i c k i n t e r a c t i o n s , i t was d e c i d e d t o use a combina-
t i o n o f both t o reduce s l a g p e n e t r a t i o n i n t o the b r i c k s .
I f the s l a g can p a s s - b y t h e c o a t i n g and e n t e r i n t o t h e b r i c k
impregnated C a C ^ p a r t i c l e s s h o u l d s t i l l s t o p f u r t h e r pene-
t r a t i o n . By using t h e b e s t c o a t i n g s and t h e optimum amount o f
i m p r e g n a t i on,, t h e s l a g p e n e t r a t i o n c o u l d be r e d u c e d signifi-
cantly.

4.2.6 Impregnation and C o a t i n g

W i t h o u t a c o a t i n g , t h e optimum amount o f impregnation

was a b o u t 3.0 w t . % C a C l | . However, t o o b t a i n a t o t a l p i c t u r e
of the e f f e c t of combining coating.and impregnation, d i f f e r -
e n t t y p e s o f c o a t i n g s w i t h v a r y i n g amounts o f impregnation
were t e s t e d .

The a l u m i n a b r i c k samples were i m p r e g n a t e d with dif-

f e r e n t amounts o f C a C ^ ( f r o m a b o u t 0.5 wt. % t o a b o u t 6.0
wt.%) by the b o i l i n g method. The c o a t i n g c o m p o s i t i o n s chosen
to c o a t t h e s e i m p r e g n a t e d b r i c k s were A4, A6, C6, C8, DI
and D2.

The c o a t i n g s were a p p l i e d t o t h e s e b r i c k s as b e f o r e
t o a t h i c k n e s s o f a b o u t 1 mm and then t h e s l a g p e n e t r a t i o n
t e s t s were p e r f o r m e d and t h e maximum s l a g - p e n e t r a t i o n
d i s t a n c e was m e a s u r e d . The depth o f s l a g p e n e t r a t i o n ( i n
 1 38

cms) vs t h e wt.% i m p r e g n a t i o n was p l o t t e d f o r a l l c o a t i n g s

to d e t e r m i n e t h e optimum amount o f C a C ^ i m p r e g n a t i o n f o r
each c o a t i n g . These can be seen i n F i g s . 38 and 39. I t
was d e c i d e d t o c o n v e r t t h e wt.% i m p r e g n a t i o n on t h e x - a x i s
to a r a t i o o f wt.% i m p r e g n a t i o n t o % p o r o s i t y m u l t i p l i e d by
a f a c t o r o f 1000. A s i m i l a r method was used p r e v i o u s l y by
most o f t h e w o r k e r s on c a r b o n - i m p r e g n a t e d refractories.

C o a t i n g s DI and D2 p r o v i d e d t h e b e s t r e s i s t a n c e t o
slag penetration a f t e r C a C ^ impregnation. I t appears t h a t
t h e r e i s an optimum amount o f i m p r e g n a t i o n which provides
a maximum r e s i s t a n c e t o s l a g p e n e t r a t i o n . T h i s knowledge
i s i m p o r t a n t t o a s c e r t a i n t h e most s u i t a b l e c o n d i t i o n s f o r
both i m p r e g n a t i o n and c o a t i n g d e v e l o p m e n t . Particularly
i t i s e a s i e r and c h e a p e r t o i m p r e g n a t e a t a low c o n c e n t r a -
t i o n , which i n a d d i t i o n , r e d u c e s t h e chance o f c r a c k s a p p e a r -
ing i n b r i c k s .

The b e s t c o m b i n a t i o n o f c o a t i n g s a n d / C a C l g impregna-
t i o n i s DI w i t h about 2.5 wt.% i m p r e g n a t i o n . Some o f t h e
s l a g p e n e t r a t e d b r i c k samples a r e shown i n F i g s . 40 and 41,
These f i g u r e s show t h e amount o f s l a g p e n e t r a t i o n a t 1080°C
i n t o A l ^ O ^ b r i c k s w i t h d i f f e r e n t amounts o f i m p r e g n a t i o n and
the s i x d i f f e r e n t c o a t i n g s . F i g u r e 42 compares t h e s l a g
p e n e t r a t i o n i n t o A 1 0 ~ b r i c k s which a r e : ( i ) o n l y c o a t e d
?
 100 150 200
wt.% Impregnotion ^ \QQQ
% Porosity
i g . 38 S l a g P e n e t r a t i o n D i s t a n c e vs Wt. % CaCl 2 Impregnation for Coatings
A6, C8 and DI.
 50 100 150 200 250 300
wt. % Impregnation
% Porosity x 1000

F i g . 39 S l a g P e n e t r a t i o n D i s t a n c e vs Wt. % CaCl„ I m p r e g n a t i o n f o r C o a t i
ngs
A4, D2 and C6.
 141

F i g . 40 C o a t i n g A4 w i t h v a r y i n g amounts o f C a C l ^
Imprgnation a f t e r slag button t e s t s . Impre-
gnation increases in a clockwise direction
s t a r t i n g from b r i c k No. 52.
 142

F i g . 41 C o a t i n g DI w i t h v a r y i n g amounts o f CaCl,,.
 143

F i g . 42 Compares s l a g p e n e t r a t i o n i n A ^ O ^ bricks.
a) = p u r e Al 0 2 3 b r i c k , (b) and ( c ) = o n l y
c o a t i n g s , (d) o n l y C a C l ^ impregnation,
(e) and ( f ) = c o a t i n g s and impregnation.
 144

(DI and D2), ( i i i ) c o a t e d and i m p r e g n a t e d (DI and D2 w i t h

the optimum amount o f i m p r e g n a t i o n ) and ( i v ) n e i t h e r c o a t e d
nor i m p r e g n a t e d (a t e s t b r i c k ) . A11 of these ..
f i g u r e s show s e c t i o n e d b r i c k s i n an e l e v a t i o n v i e w . F i g . 43
shows t h e s l a g s p r e a d on b r i c k s w i t h o n l y c o a t i n g s (DI and
D2) and c o a t i n g s w i t h i m p r e g n a t i o n . Since the weight of the
s l a g b u t t o n s were t h e same i n a l l e x p e r i m e n t s the spreading
of s l a g s h o u l d be more i n t h e c a s e where p e n e t r a t i o n i s
l e s s and v i c e v e r s a . In t h e c a s e o f t h e combined use o f
c o a t i n g s and i m p r e g n a t i o n any i m p r e g n a t i o n w i t h amounts o f
CaCl 2 more than t h e optimum r e s u l t e d i n enhanced s l a g
penetration. Besides forming cracks i n the b r i c k s too
much C a C l ^ a l s o c a u s e d c r a c k i n g and f l a k i n g o f t h e c o a t i n g .

4.3 R e a c t i o n s Between C o a t i n g s , CaCl 2 and S l a g

It i s important to assess the nature of r e a c t i o n s

t h a t may be o c c u r r i n g between t h e c o a t i n g s , C a C l 2 and t h e
slag. At h i g h t e m p e r a t u r e s , t h e components used f o r making
c o a t i n g s a r e l i k e l y t o r e a c t and form o t h e r compounds.
Experiments were p e r f o r m e d to determine the nature of r e a c - i
t i o n products formed at 1080°C.

(i) S l a g s and C o a t i n g s
The c o a t i n g s were mixed w i t h t h e s l a g i n r a t i o s o f
1:1. The m i x t u r e s were then f i r e d a t 1080°C f o r 4 h o u r s ,
 145

F i g . 43 Slag spreading on A l b r i c k s . Clockwise

f r o m top l e f t : c o a t i n g DI, c o a t i n g D2, coating
D2 and C a C l 2 i m p r e g n a t i o n , a n d c o a t i n g DI and
CaCl 9 impregnation.
quenched and p u l v e r i z e d . The powder was then s u b j e c t e d t o
x-ray d i f f r a c t i o n . From t h e d i f f r a c t o m e t r i c p l o t s , attempts
were made t o i d e n t i f y t h e compounds. T h e r e were o n l y v e r y
few b r o a d and s m a l 1 p e a k s i n t h e p i o t s , i n d i c a t i n g t h e p r e -
m

sence o f p o o r l y c r y s t a l l i n e m a t e r i a l s and i n s m a l l con-

centrations. No f r e e o x i d e s c o u l d be d e t e c t e d w h i c h means
that a l l the slag c o n s t i t u e n t s reacted with the coatings
to form f u s i b l e p h a s e s . I t i s very l i k e l y that these
g l a s s y p h a s e s a r e v i s c o u s and s e a l t h e p o r e s preventing
further entry of slag into the b r i c k . The p r e s e n c e o f
free CaSi0 3 i n these mixtures also i n d i c a t e s that a l l the
coating m a t e r i a l s d i d not r e a c t with the s l a g .

(ii) Coatings CaCl 2 and S l a g

M i x t u r e s o f c o a t i n g s , .CaC.^ and s l a g i n t h e r a t i o
of 1:1:1 ( b y w e i g h t ) were made as b e f o r e and x - r a y d i f -
fractometry conducted on them. No f r e e s l a g o r C a C l ^ c o u l d
be d e t e c t e d b u t t h e r e was some C a S i O ^ . The p r e s e n c e o f
g l a s s y p h a s e s was a g a i n evident.

The r e a c t i o n p r o d u c t s f o r m e d w i t h t h e c o a t i n g s ,
C a C ^ and s l a g C4, a r e v e r y g l a s s y and a l l t h e ' h a r m f u l '
o x i d e s i n t h e s l a g a r e e f f e c t i v e l y t r a p p e d by r e a c t i o n w i t h
the c o a t i n g m a t e r i a l s a n d C a C l . ?
 147

4.4 SEM S t u d i e s on S l a g P e n e t r a t i o n

S c a n n i n g e l e c t r o n m i c r o s c o p y (SEM) s t u d i e s were
p e r f o r m e d on s e c t i o n e d b r i c k s (as shown b e f o r e ; e.g. F i g .
42), i n o r d e r to determine the depth of p e n e t r a t i o n of
s l a g c o n s t i t u e n t s . The b r i c k s were s c a n n e d from t h e top
s u r f a c e o f t h e b r i c k (where t h e s l a g i s p l a c e d ) to a
c e r t a i n depth w i t h i n t h e b r i c k body. The X - r a y Energy
A n a l y z e r on t h e SEM was used t o d e t e r m i n e t h e p r e s e n c e o f
s l a g e l e m e n t s (Cu, Pb, Sb, B i , As and Zn) qualitatively,
by c o m p a r i n g t h e A l peak a m p l i t u d e ( f o r an A 1 0 2 3 brick)
to o t h e r peak a m p l i t u d e s . The A l peak a m p l i t u d e remained
c o n s t a n t a t d i f f e r e n t d e p t h s as was e x p e c t e d . By comparing
the d e c r e a s e i n peak a m p l i t u d e s o f t h e s l a g e l e m e n t s w i t h
i n c r e a s i n g d e p t h , t h e s l a g p e n e t r a t i o n w i t h depth i n t h e
b r i c k can be d e t e r m i n e d .

F i g . 44 r e p r e s e n t s a s l a g a t t a c k e d pure a l u m i n a
refractory. The x - r a y peaks o f t h e SEM scan c o r r e s p o n d t o
Al and t h e s l a g e l e m e n t s a t a depth o f a b o u t 10 mm from
the t o p s u r f a c e o f the b r i c k .

F i g . 45 (a and b) shows t h e a m p l i t u d e o f t h e peaks

a t t h e s u r f a c e o f t h e b r i c k and a t a d e p t h o f a b o u t 5 mm
for a CaCl 2 i m p r e g n a t e d a l u m i n a b r i c k which was s u b j e c t e d
to a s l a g (C.4) p e n e t r a t i o n t e s t . T h i s shows t h a t t h e s l a g
( r e p r e s e n t e d by i t s e l e m e n t s ) p e n e t r a t i o n was r e d u c e d due to
 •Al

ENERGY (KeV)

F i g . 44 SEM-EDX P l o t f o r a Slag A t t a c k e d Alumina B r i c k (1 cm

4^
from the top s u r f a c e ) . CO
 149

•"AL

,*5L
(a) Top Surface

ENERGY (KeV)

Pi

00
(b) 5 mm from Top S u r f a c e

5C • Co.

ENERGY (KeV)

Fig.45 SEM-EDX P l o t f o r a S 1 a g - A t t a c k e d C a C l 2 Impregnated

Alumina Brick.
 1 50

AL

(a) Top S u r f a c e

ENERGY (KeV)

•AL
(b) 5 mm from Top S u r f a c e

;- JPfc/Bi

ENERGY (KeV)

F i g . 46 SEM-EDX P l o t f o r a S l a g A t t a c k e d Alumina
B r i c k w i t h C o a t i n g D2.
 151

i m p r e g n a t i on.

F i g s . 4 6 (a and b) show s i m i 1 a r EDX p l o t s f o r an

a l u m i n a b r i c k w i t h c o a t i n g D2.

Figs., 47 (a and b) show EDX p l o t s f o r an A1,,0 3

b r i c k w i t h b o t h C a C ^ i m p r e g n a t i o n and c o a t i n g D2.

A l l t h e s e f i g u r e s (45 - 47) show t h a t s l a g p e n e t r a -

t i o n i s r e d u c e d by t h e c o a t i n g s , C a C l ^ i m p r e g n a t i o n and
a l s o by t h e c o m b i n a t i o n o f c o a t i n g s and i m p r e g n a t i o n .

I t s h o u l d be m e n t i o n e d here t h a t i t i s not p o s s i b l e
to do ' p o i n t s c a n n i n g ' on t h e SEM so t h e d i s t a n c e s were
measured a p p r o x i m a t e l y a t a m a g n i f i c a t i o n o f 100k on a
'Reduced A r e a ' s c a n . The a r e a o c c u p i e d by t h e 'Reduced
Area 1
scan a t an i n c l i n a t i o n o f 45° c o r r e s p o n d s t o a sample
-4 2
a r e a o f 24.5 x 10 cm which i s a s q u a r e w i t h 0.495 mm
sides. U s i n g t h i s i n f o r m a t i o n and t h e v e r n i e r arrangement
to move t h e s p e c i m e n , t h e a p p r o x i m a t e d e p t h s from t h e s u r -
f a c e c o u l d be d e t e r m i n e d .

The i r o n peaks o b s e r v e d i n t h e SEM p l o t s a r e due t o

the p r e s e n c e o f i r o n i n t h e b r i c k o r i n t h e s l a g .
 1 52

AL

00
(a) Top S u r f a c e
LU
St

ENERGY ( K e V )

•AL

OO
( b ) 10 mm f r o m Top S u r f a c e

ENERGY ( K e V )
F i g . 47 SEM-EDX P l o t f o r a S l a g A t t a c k e d A l u m i n a Brick
with C a C ^ Impregnation a n d C o a t i n g D2,
 1 53
4.5 C o a t i n g s and I m p r e g n a t i o n on Magnecon B r i c k s

The magnecon b r i c k s a r e n o r m a l l y used i n t h e Dore

f u r n a c e s as t h e y were f o u n d t o l a s t l o n g e r than any o t h e r
commercial bricks. T h i s has been f o u n d i n t h e i n d u s t r y
by t r i a l and e r r o r . I t i s e x p e c t e d t h a t t h e c o a t i n g s and
C a C l ^ i m p r e g n a t i o n used i n t h e c a s e o f a l u m i n a b r i c k s
s h o u l d a l s o work f o r magnecon b r i c k s i n r e d u c i n g s l a g pene-
tration. The p r e s e n c e o f MgO i n l a r g e q u a n t i t i e s ( a b o u t
53% by w e i g h t ) i n t h e s e b r i c k s s h o u l d h e l p i n r e d u c i n g s l a g
p e n e t r a t i o n due t o i t s h i g h r e f r a c t o r i n e s s ( m e l t i n g p o i n t
of 2 8 0 0 ° C ) .

The a p p a r e n t ( o r open) p o r o s i t y o f t h e s e magnecon

b r i c k s i s ^ 20% as d e t e r m i n e d i n t h i s s t u d y . So the
i m p r e g n a t i o n p r o c e d u r e used f o r A ^ O ^ b r i c k s c o u l d be used
f o r Magnecon b r i c k s - w i t h o u t a l t e r a t i o n .

The f o u r c o a t i n g s w h i c h worked b e s t w i t h A l ^ O ^
b r i c k s were chosen f o r t e s t s w i t h magnecon r e f r a c t o r i e s ;
t h e s e were C6, C8, DI and D2. The optimum amount o f
C a C ^ i m p r e g n a t i o n n e c e s s a r y f o r each c o a t i n g was determined
from F i g s . 38 and 39. The b r i c k s were t h e n impregnated,
c o a t e d , p r e f i r e d a t 1080°C and then s u b j e c t e d t o s l a g
penetration tests. The b r i c k s were then s e c t i o n e d and
s u b j e c t e d t o SEM EDX t e s t s a s m e n t i o n e d e a r l i e r . The
r e s u l t s o f the SEM t e s t s on magnecon b r i c k s w i t h c o a t i n g D2
and C a C ^ i m p r e g n a t i o n can be seen i n F i g s . 48 a and b .
S l a g p e n e t r a t i o n can be d r a s t i c a l l y r e d u c e d by t h e combined
use o f C a C l 2 i m p r e g n a t i o n and c o a t i n g s , as can be seen from
these f i g u r e s .
 155
1{

to
LU

ENERGY (KeV)
F i g . 48 A SEM-EDX p l o t f o r Magnecon b r i c k w i t h c o a t i n g
D2 a t 0.5 cm from Top S u r f a c e .

lr: • "• Co.

ENERGY (KeV)
F i g . 48 b SEM-EDX p l o t f o r a Magnecon b r i c k w i t h c o a t i n g
D2 and Ca'Cl i m p r e g n a t i o n a t 0.5 cm from Top
2

Surface.
 1 56

Chapter 5

SUMMARY AND CONCLUSIONS

The p h y s i c a l p r o p e r t i e s o f Dore s l a g have been

determined. The r e s u l t s can be summarized as f o l l o w s :

(a) The l o w e s t l i q u i d u s t e m p e r a t u r e s o b s e r v e d i n Dore

s l a g a r e between 550 and 600°C.

(b) The s l a g - m e l t s have t h e d e n s i t i e s 5.0 t o 7.0 g/cm

i n t h e t e m p e r a t u r e range 750 - 1050°C. The m e l t
d e n s i t y b e i n g c o n t r o l l e d p r i m a r i l y by t h e c o n c e n t r a -
t i o n o f PbO and B i " 0 . 2 3

(c) The m e l t s a r e h i g h l y f l u i d i n t h e t e m p e r a t u r e range

750 - 1050°C, h a v i n g t h e v i s c o s i t y o f 0.4 t o 0.8
_2
N . S. m

(d) The s u r f a c e t e n s i o n v a l u e s o f t h e m e l t s a t 750°C

a r e i n t h e range 325 - 450 dyne . c m -1
i . e . very
low as compared to s i l i c a t e s l a g s (which a r e i n the
range o f 700 dyne . cm"'' o r more).

(e) The s l a g s made v e r y s m a l l c o n t a c t a n g l e s (15 t o 3 0 ° )

on a l u m i n a s u b s t r a t e s i n t h e t e m p e r a t u r e r a n g e 800
 to 1000°C ( t h e Dor© f u r n a c e o p e r a t i n g range).
T h i s i n d i c a t e s t h a t s l a g s w i l l s p r e a d e a s i l y on
the r e f r a c t o r y s u r f a c e and p e n e t r a t e very e a s i l y
i n t o the pores o f r e f r a c t o r y b r i c k s .

A t t e m p t s were a l s o made to d e v e l o p c o a t i n g composi-

t i o n s t o p r e v e n t s l a g from p e n e t r a t i n g i n t o r e f r a c t o r i e s .
Subsequently,iimpregnations o f b r i c k s w i t h o x i d e s and s a l t s
were a t t e m p t e d . F i n a l l y a combination o f both impregnation
and c o a t i n g was developed, w h i c h a p p e a r s to be e f f e c t i v e
i n p r e v e n t i n g s l a g p e n e t r a t i o n and d i s s o l u t i o n o f r e f r a c t o r y
bricks. T h e s e r e s u l t s can be summarized as f o l l o w s :

(i) Coating compositions were d e v e l o p e d using CaO,

S i d 2 and a s m a l l c o n c e n t r a t i o n o f s l a g s . Calcium
o x i d e was f o u n d to be e f f e c t i v e i n f i x i n g - u p the
harmful oxide c o n s t i t u e n t s in s l a g s . A l a r g e con-
c e n t r a t i o n of S i 0 2 was needed to d e v e l o p a glassy
phase f o r s e a l i n g - u p the p o r e s . The f i n a l and
best composition c o m t a i n s 30 wt. %. o f CaO, 60 wt. %
of S i 0 2 and 10 wt. % slag.

(ii) S l a g - p i l l t e s t s on c o a t i n g b r i c k s r e v e a l e d that
o n l y a p p l i c a t i o n o f a c o a t i n g c o u l d not s t o p s l a g
penetration, although i t was reduced t o some e x t e n t .

F u r t h e r s t u d i e s on i m p r e g n a t i n g the b r i c k s w i t h CaO
 1 58

and CaCl£ show t h a t an optimum i m p r e g n a t i o n o f b r i c k s w i t h

^ 2 wt. % C a C l 2 » and a c o a t i n g o f a m i x t u r e o f 30% CaO, 60%
Si02 and 10% s l a g on t h e i m p r e g n a t e d b r i c k s have been able
to s t o p s l a g p e n e t r a t i o n into the r e f r a c t o r y bricks.
 159
SUGGESTIONS FOR FUTURE WORK

T h i s s t u d y s h o u l d be c o n s i d e r e d as t h e f i r s t attempt
to d e v e l o p s l a g - r e s i s t a n t r e f r a c t o r i e s by i m p r e g n a t i o n and
c o a t i n g , and t h u s , i t i s p r e l i m i n a r y i n n a t u r e . Extensive
s t u d i e s must be made t o d e v e l o p g e n e r a l c r i t e r i a , b e f o r e
t h i s t e c h n i q u e can be a p p l i e d t o a l a r g e number o f d i v e r s e
s l a g - r e f r a c t o r y systems. Even f o r r e f r a c t o r i e s f o r t h e
Dore f u r n a c e s , f u r t h e r e x p e r i m e n t s s h o u l d be p e r f o r m e d f o r
improvement and o p t i m i z a t i o n o f s l a g r e s i s t i v i t y . The
f o l l o w i n g s t u d i e s s h o u l d be made t o improve impregnation:

1) C o n v e r s i o n o f C a C ^ i n s i d e t h e b r i c k t o CaCO^
u s i n g (NH-^JgCO I t i s hoped t h a t b e c a u s e o f
l o w e r water s o l u b i l i t y o f CaCO^ as compared
to Ca(0H)2> r e t e n t i o n o f C a C 0 would be e a s i e r .
3

This i s important as CaCl,, i m p r e g n a t e d b r i c k s

may n o t be s u i t a b l e f o r use a t v e r y h i g h tempera-
tures e . g . , as i n s t e e l p l a n t s .

2) Other impregnating m a t e r i a l s such as Magnesium

c h r o m i t e - MgCr0 xH,,0
3 which i s h i g h l y w a t e r
soluble. T h i s compound' a t h i g h temperatures
t r a n s f o r m s t o MgCr^O^ which i s h i g h l y s l a g -
resistant.
C o a t i n g f o r m u l a e must be d e v e l o p e d from different
types of slags, s p e c i a l l y f o r steel plant use.
 161

BIBLIOGRAPHY

1. C h a k l a d e r . A . C D . , R e f r a c t o r y P r a c t i c e s and Problems
in M e t a l l u r g i c a l I n d u s t r i e s A Report prepared f r o the
O n t a r i o R e s e a r c h F o u n d a t i o n , M i s s i s s a u g a , Ont. A u g u s t ,
1981, pp. 208.
2. B a r d e n h e u e r ,V.G. , A r c h E i s e n h u t t e n w e s e n , 4J_ ( 1 1 ) ,
p. 1093, ( 1 9 7 0 ) .
3. N o r t o n F.H., R e f r a c t o r i e s , M c G r a w - H i l l Book Co.,
(1968).
4. G a r v i e B-C. and N i c h o l s o n , P.S., J . Am Ceram. S o c ,
55, p. 152, ( 1 9 7 2 ) .
5. Smith R.D., A n d e r s o n H.U. and Moore R.E., Am. Ceram.
Soc. B u l l . , 5_5 ( 1 1 ) , p.979 , ( 1976).
6. Hasselman D.P.H., High Temp-High P r e s s u r e , 8 ( 2 ) , p.
237, ( 1 9 7 6 ) .
7. R o s s i R . C , Am. Ceram. S o c . B u l l . , 4_8, p. 736, ( 1969).
8. K i n g e r y W.D., J . Am. Ceram. S o c , 3_8, p. 3, ( 1 9 5 5 ) .
9. Hasselman D.P.H., Am. Ceram. S o c . B u l l . , 49, p.1033,
(1970).
10. C a r n i g l i a S.C., J . Am. Ceram. S o c , 5_5 ( 1 2 ) , p.610,
(1972).
11. Kuszyk J.A. and B r a d t R . C , I n d . H e a t . , 42 ( 3 ) , p . 6 1 ,
(1975).
12. L a r s o n D.R. and Hasselman D.P . H., T r a n s . B r i t . Ceram.
S o c . , 74 ( 2 ) , p. 59 , ( 1975).
13. Oh T a e - I l e t a l . , Am. Ceram. S o c B u l l . , 56_ ( 7 ) ,
p.649 , ( 1 9 7 7 ) .
14. Dowsing R . J . , Met. M a t e r . , p.23, May 1979.
15. Park H.K. and B a r r e t t L.R., T r a n s . J . B r i t . Ceram.
S o c , 7 8 (5) , p.90, ( 1 9 7 9 ) .
16. Kappmeyer K.K. and Hubble D.H., High Temp. O x i d e s
P a r t 1, V o l . 5, p.1 , ( 1 9 7 0 ) .
 162
17. Howe R.A. and McGee T.D., Am. Ceram. Soc. Bull.,
55 ( 2 ) , p.205, ( 1 9 7 6 ) .
18. B r e z n y B. and Landy R.A., T r a n s . J . B r i t . Ceram.
S o c , 7J_ ( 6 ) , p. 163, ( 1 9 7 2 ) .
19. Robinson P . C , R e f r a c t o r i e s J . , 42 ( 6 ) , p.218,
(1966).
20. C h e s t e r s J.H., I r o n and S t e e l I n s t . Spec. Rep.,
74, p. 26, ( 1 9 6 2 ) .
21. Phase Diagrams f o r C e r a m i s t s , The Am. Ceram. Soc,
Columbus, O h i o .
22. C u l l i t y B.D., E l e m e n t s o f X-ray D i f f r a c t i o n ,
Addison-Wesley Pub. Co., ( 1 9 7 8 ) .
23. M i c h e l , Jean-Raymond, M.A.Sc. T h e s i s , The U n i v e r s i t y
o f B r i t i s h C o l u m b i a , 1973. " R h e o l o g i c a l B e h a v i o u r
o f C a 0 - S i 0 - A l 0 and C a O - S i 0 ~ A 1 0 - C a F S l a g s " .
2 2 3 2 2 3 2

24. D a v i e s M.W. and W r i g h t R.D., Chem. and I n d . , p.359,

Mar. 1970.
25. Kato M. and Minowa S., T r a n s . I r o n and S t e e l Inst.
J a p a n , 9 ( 1 ) , p.31, ( 1 9 6 9 ) .
26. B o c k r i s J.O'M and Lowe D . C , P r o c . Roy. S o c (London)
A226, p.423, ( 1 9 5 4 ) .
27. Handbook o f C h e m i s t r y and P h y s i c s , CRC P r e s s I n c . ,
Boca R a t o n , F l o r i d a .
28. T i e d e R.L., J . Am. Ceram. S o c , 42 ( 1 1 ) , p.539,
(1959).
29. Hara S. e t a l . , P r o c 1 s t I n t l . Sym. on M o l t e n S a l t
Chem. and T e c h . , Apr. 20-22, ( 1 9 8 3 ) , J a p a n .
30. G u n j i K. and Dan T., T r a n s . I r o n and S t e e l Inst.
J a p a n , 1_4(3), ( 1 9 7 4 ) .
31. Cooper C.F. and K i t c h e n e r J.A., J . The I r o n and
S t e e l I n s t . , p.48, Sep. 1959.
32. Popel S . I . and E s i n O.A., Zhur. Neorgan. Khim.,
2, p. 632, ( 1 9 5 7 ) .
 163

33. Ono K. e t a l . , J . Japan I n s t . M e t a l s , 3J3, p.299 ,

(1969).
34. Sharma S.K. and P h i l b r o o k W.O., S c r i p t . Met., 4,
p.107, ( 1 9 7 0 ) .
35. K o j i m a Y., T r a n s . I r o n and S t e e l I n s t . J a p a n ,
11 ( 5 ) , p.349, ( 1 9 7 1 ) .
36. B a s h f o r t h and Adams, An A t t e m p t t o T e s t t h e T h e o r y
o f C a p i l l a r y A c t i o n , Cambridge ( 1 8 8 3 ) .
37. Rasmussen J . J . and N e l s o n R.P., J . Am. Ceram. S o c ,
54 ( 8 ) , ( 1 9 7 1 ) .
38. K i n g e r y W.D., J . Am. Ceram. Soc. , 4_2, p.6, ( 1 9 5 9 ) .
39. Sugden S., J . Chem. Soc. ( L o n d o n ) , V o l . 2, p.1483,
(1921).
40. Wanibe Y. e t a l . , T r a n s . I r o n and S t e e l I n s t . J a p a n ,
23, p.322, ( 1 9 8 3 ) .
41. Boni R.E. and Derge G. , J . M e t a l s , p.53, J a n . 1956.
42. F i s c h e r W.A. e t a l . , A r c h . E i s e n h u t t e n w e s e n , 47 ( 1 0 ) ,
p.607, ( 1 9 7 6 ) .
43. Ono K. e t a l . , J . Japan I n s t . M e t a l s , 3_3, p.299,
(1969).
44. Schrb'dinger Von E r w i n , A n n a l e n Der P h y s i k , 46^,
p.413, ( 1 9 1 5 ) .
45. S p e i t h and H e i n r i c h s , J . The I r o n and S t e e l Inst.,
p.48, Sep. 1959.
46. Popel S . I . e t a l . , A k a d e m i i Nauk SSSR D o k l a d y Phys.
Chem. , 1_1_2, p.26, ( 1 9 5 7 ) .
47. P r a b r i p u t a l o o n g K. and P i g g o t t M.R., Surface Science,
44_, p.585, ( 1 9 7 4 ) .
48. Mack G.L. and Lee D.A., J . Phys. Chem., 40, p.159,
(1936).
49. B a r t l e t t R.W. and H a l l J.K., Am. Ceram. Soc. B u l l . ,
44 ( 5 ) , p.444, ( 1 9 6 5 ) .
 164

50. Usachev I.M. e t a l . , S t a l ( Engl i s h ) , 1J_, p.874,

(19 7 0 ) .
51. La Bar R.G., Aluminum Co. o f A m e r i c a , O f f . Gaz.,
19 June 1979, P a t . No. U.S4158568 ( U . S . A . ) .
52. Andrade E.N. d a C , P h i l . Mag. , T 7 , p.497,
(1934).
53. Macedo and L i t o v i t z , S u r f a c e and C o l l o i d S c i e n c e ,
V o l . 3, Ed. Egon M a t i j e v i c , I n s . C o l l o i d and S u r .
S c i . , Potsdam, New Y o r k .
54. C h a k l a d e r A . C D . , G i l l W.W. and M e h r o t r a S.P.,
S u r f a c e s and I n t e r f a c e s i n C e r a m i c and C e r a m i c -
M e t a l S y s t e m s , Ed. Pask J . and Evans A., Plenum
Pub. C o r p . , ( 1 9 8 1 ) .
 165

Appendix 1

VISCOSITY OF SLAGS

(a) Introduction

The r h e o l o g i c a l b e h a v i o u r o f s l a g s a f f e c t s the heat

49 50 51
transfer rates, ' the mass t r a n s f e r r a t e s , the momentum
t r a n s f e r r a t e s , m i x i n g and the v e l o c i t y o f d r o p l e t s falling
through i t . However, i n the p r e s e n t work none o f the above
are as i m p o r t a n t as the i n c r e a s e of 'refractory-penetrating'
power o f the s l a g due to i t s low v i s c o s i t y . I t was esta-
b l i s h e d i n the p r e s e n t work t h a t one o f the main r e a s o n s
f o r the h i g h c o r r o s i o n r a t e s o f the r e f r a c t o r i e s , was the
e x t r e m e l y low v i s c o s i t y o f the Dore f u r n a c e slags.

The v i s c o s i t y of a l i q u i d can be d e f i n e d as the

measure o f i t s r e s i s t a n c e t o f l o w c a u s e d by i n t e r n a l
friction forces. T h i s i n t e r n a l f r i c t i o n f o r c e i s due to
the r e s i s t a n c e o f f e r e d to f l o w when l i q u i d l a y e r s move
a g a i n s t each other.

On a m i c r o s c o p i c l e v e l , viscous f l o w can be d e s c r i -
bed i n two s t e p s ; the f o r m a t i o n o f h o l e s and the j u m p i n g of
'flow u n i t ' i n t o these h o l e s . The a c t i v a t i o n e n e r g y f o r
viscous f l o w i s e s s e n t i a l l y the e n e r g y r e q u i r e d f o r a f l o w
u n i t t o jump i n t o a h o l e . T h i s e n e r g y i s made up o f two
p a r t s : ( i ) t h e e n e r g y n e c e s s a r y t o form a h o l e compatible
w i t h t h e shape and s i z e o f t h e f l o w u n i t , and ( i i ) t h e
e n e r g y r e q u i r e d t o d e t a c h t h e f l o w u n i t from i t s s u r r o u n d -
i n g s , and move i t i n t o t h e h o l e .

52
Andrade has shown t h a t t h e t e m p e r a t u r e dependence
o f v i s c o s i t y can be r e p r e s e n t e d by an A r r h e n i u s t y p e equa-
tion
n = A exp(EnVRT) Al.l
where 1

n = v i s c o s i t y of the l i q u i d
A.J = a constant
= a c t i v a t i o n energy f o r v i s c o u s flow
R = gas c o n s t a n t
T = temperature i n degree K e l v i n

Equation A l . l h o l d s t r u e f o r most l i q u i d s and

53
slags. R e c e n t l y , Maeedo and L i t o v i t z developed a general
r e l a t i o n f o r t h e v i s c o s i t y o f l i q u i d s and s o l i d s . This
t h e o r y i s i n f a c t based on t h e o l d t h e o r y o f ' h o l e s ' and
'flow u n i t s ' . In t h i s t h e o r y a q u a s i - c r y s t a l l i n e model i s
assumed f o r t h e l i q u i d . The i m p o r t a n t e q u a t i o n s w i l l be
mentioned here:
L_ = A A1.2
" ~ P
j P
E * V P
 167

where
P. = p r o b a b i l i t y o f a m o l e c u l a r jump,
P^ = p r o b a b i l i t y o f the f l o w u n i t attaining
s u f f i c i e n t e n e r g y t o break r e s t r a i n i n g b o n d s ,
Py = p r o b a b i l i t y t h a t s u f f i c i e n t l o c a l f r e e volume
i s a v a i l a b l e t o accommodate t h e f l o w u n i t .

The f a c t o r s i n E q u a t i o n Al.2 o f the M-L analysis are:

where
Ey = p o t e n t i a l e n e r g y b a r r i e r a t c o n s t a n t volume,,
R = gas c o n s t a n t
T = absolute temperature;
m = m o l e c u l a r mass
k = Boltzmann's constant
V.j = m o l e c u l a r volume o f f l o w u n i t
Y = a f a c t o r between 0.5 and 1.0
Vg = molar f r e e volume a s s o c i a t e d w i t h a z e r o
free-volume c o n d i t i o n f o r the f l o w u n i t
V. =f molar f r e e volume o f t h e f l o w u n i t
 Equations AT.1 and AT.2 both show t h a t t h e
r e l a t i o n between v i s c o s i t y and t e m p e r a t u r e i s an A r r h e n i
type r e l a t i o n . So the f a l l of v i s c o s i t y with a r i s e i n
temperature s h o u l d be o f an e x p o n e n t i a l n a t u r e f o r most
l i q u i d s and m o l t e n s l a g s .
 169
Appendix l a

VISCOSITY MEASUREMENTS

The v i s c o s i t y d a t a f o r Dore s l a g s a r e t a b u l a t e d i n
T a b l e A l a . l and t h e p l o t s o f v i s c o s i t y ( n ) vs t e m p e r a t u r e
(°C) and i n v e r s e t e m p e r a t u r e (K~^) are given i n s e c t i o n
(2.2.4.2). The v a l u e s r e p o r t e d were measured a t a s p i n d l e
speed o f 100 rpm b e c a u s e o f t h e low v i s c o s i t i e s o f t h e
slags. The c o u n t s r e c o r d e d by t h e a l u m i n a s p i n d l e were
c o n v e r t e d t o a b s o l u t e v i s c o s i t y (N.S. m ) u s i n g F i g . 9.
The v i s c o s i t y measurements on CaO and s l a g C4 m i x t u r e s
are given i n Table A l a . 2 .
 1 70

Table A a .1 V i s c o s i t y o f Dore S l a g s .

1/1 « io" Counts on Alumina Spindle Avenge Vtaxoslty M log M

Temperature
•C K (1) <») (111) Counts Polte

i.S! 8.80 8.85 6.95 8.80 7.93 0.90

(0 S l i g C3 600
6.20 5.15 5.20 6.07 0.78
eso 6.91 5.25

4.15 4.30 4.15 4.20 4.90 0.69

too 6.53

950 e.ie 3.(0 3.55 3.65 3.60 4.20 0.62

7.86 2.70 2.75 2.95 2.80 3.27 0.51

1000

1050 7.56 2.45 2.35 2.40 2.40 2.BO 0.45

5.60 5.75 5.75 5.70 6.65 0.62

( H ) Slag CI 750 9.76

4.70 4.50 5.05 4.75 5.54 0.74

800 9.32
4.20 4.16 4.10 4.15 4.B4 0.69
650 8.91
3.45 3.50 3.45 4.03 0.61
goo 8.53 3.40

2.60 3.10 2.65 2.B5 3.33 0.52

950 8.16
2.55 2.45 2.80 2.60 3.03 0.46
1000 7.86

2.35 2.20 2.20 2.25 2.63 0.42

1050 7.56

4.26 4.20 4.15 4.20 4.90 0.69

750 9.76
(1H) Slag a 4.43 0.65
9.32 3.80 3.65 3.95 3.80
800
3.20 3.05 3.05 3.10 3.60 0.56
850 8.91
2.90 2.60 2.70 2.80 3.27 0.52
900 8.53

2.40 2.45 2.50 2.45 2.85 0.46

950 8.18

2.30 2.15 2.15 2.20 2.57 0.41

1000 7.86
1.80 1.85 2.05 1.90 2.22 0.35
1050 7.56

3.30 3.4D 3.35 3.35 3.91 0.59

(Iv) Slag C4 750 9.78

3.05 2.95 3.44 0.54

BOO 9.32 2.95 2.85

2.35 2.55 2.40 2.60 0.45

850 8.91 2.30

2.10 2.05 2.10 . 2.45 0.39

900 8.53 2.15

1.75 1.85 1.75 2.04 0.31

950 8.16 1.65

1.50 1.3D 1.40 1.66 0.22

1000 7.86 1.40

1.20 1.35 1.25 1.46 0.16

1050 7.56 1.20
 Tab 1e A 1 a.2 V i s c o s i t i e s o f CaO and S l a g M i x t u r e s .

Temperature 1/T x 10 Counts on Alumina Spindle Average V i s c o s i t y (n) log (n)

(D (11) (111) Counts Poise

(1) 10 wt.% CaO

+ Slag C4 750 9.775 46.50 50.00 48.10 48.20 56.23 1.75

770 9.588 39.55 36.00 39.35 38.30 44.67 1.65

780 9.497 37.65 35.15 34.30 35.70 41.65 1.62

840 8.965 26.00 26.50 30.60 27.70 32.36 1.51

850 8.905 31.50 32.00 34.30 32.60 38.02 1.58

880 8.673 35.15 34.50 37.45 35.70 41.69 1.62

9Z5 8.347 29.25 29.00 26.95 28.40 33.11 1.52

960 8.110 19.45 20.90 19.95 20.10 23.44 1.37

1000 7.855 20.10 19.15 18.35 19.20 22.39 1.35

1050 7.559 13.00 14.10 13.70 13.60 15.85 1.20

(11) 15 wt.% CaO

750 9.775 67.15 68.60 68.55 68.10 79.43 1.90
+ Slag C4
770 9.588 56.70 58.00 55.10 66.60 66.07 1.82

780 9.497 52.00 49.75 49.75 50.50 58.88 1.77

830 9.066 70.50 71.45 71.95 71.30 83.18 1.92

850 8.905 95.35 92.85 93.80 94.00 109.65 2.04

900 8.525 68.00 69.35 66.95 68.10 79.43 1.90

950 8.177 58.00 55.70 56.10 56.60 66.07 1.82

1000 7.855 44.15 42.80 42.05 43.00 50.12 1.70

1050 7.559 36.15 35.25 35.70 35.70 41.69 1.62

(111) 20 wt.% CaO

925 8.347 92.50 95.15 94.35 94.00 109.65 2.04
+ Slag C4
960 8.110 87.10 92.40 89.90 89.80 104.71 2.02

1000 7.855 88.25 86.35 88.50 87.70 102.33 2.01

1050 7.559 78.15 76.00 80.45 78.20 91.20 1.96

 Appendix 2

SURFACE TENSION AND DENSITY OF SLAGS

(i) The s u r f a c e t e n s i o n v a l u e s o f t h e s l a g s ( y ) i n
dyne cm"^ a r e g i v e n i n T a b l e A 2 . 1 . The terms l i s t e d i n
this table are:

r = i n n e r r a d i u s o f c a p i l l a r y tube
g = a c c e l e r a t i o n due t o g r a v i t y
H = maximum manometrie height
P M = d e n s i t y o f manometrie fluid
h = depth o f c a p i l l a r y tube immersion
P s = density of melt (slag).

_ q

(ii) The d e n s i t i e s o f t h e s l a g s ( p ) s i n gm cm are

g i v e n i n T a b l e A2.2. The terms l i s t e d i n t h i s t a b l e a r e
explained below:
h-j and h^ - t h e two d e p t h s o f i m m e r s i o n o f t h e
c a p i l l a r y tube
H-| and = t h e two maximum manometrie heights at
h, and h . 0
 1 73

T a b l e A2.1 Surface Tension

2rp, (rp ) 2 t
leap.
s
r H h
9 "m °s ("»m - N» 6(H»„-h, ) dViucnf'
3<Kp„-"e,>
2
s

•c CD cm sec -2
cms gm cm ^ cm

(t) Slag C3 800 0.121 981 15.10 1.00 1.00 7.00 8.10 0.0695 0.0018 447.50
850 0.121 981 14.65 1.00 1.00 6.60 8.05 0.0666 0.0016 445.00
900 0.121 981 14.40 1.00 1.00 6.40 8.00 0.0645 0.0016 442.50
950 0.121 981 14.55 1.00 1.00 6.60 7.95 0.0669 0.0017 441.00
1000 0.121 981 14.10 1.00 1.00 6.20 7.90 0.0633 0.0015 440.00

1050 0.121 981 14.00 1.00 1.00 6.20 7.80 0.0641 0.0015 437.50

(II) Slag U 750 0.121 981 13.40 1.00 1.00 6.50 6.90 0.0759 0.O022 381.30

BOO 0.121 981 13.25 1.00 1.00 6.35 6.90 0.0742 0.0021 378.80

850 0.121 981 12.65 1.00 1.00 6.05 6.60 0.0716 0.0019 375.00

900 0.121 961 12.60 1.00 1.00 5.75 6.75 0.0667 0.0018 372.50

950 0.121 981 12.20 1.00 1.00 5.55 6.65 0.0673 0.0017 368.80

1000 0.121 981 12.05 1.00 1.00 5.45 6.60 0.0666 0.0017 365.00

1050 0.121 981 11.60 1.00 1.00 5.10 6.50 0.O633 0.0015 362.50

(111) Slag CI 750 0.121 981 12.85 1.00 1.00 6.40 6.45 0.0800 0.0024 351.30

BOO 0.121 981 12.50 1.00 1.00 6.10 6.40 0.0769 0.0022 350.00

850 0.121 981 12.15 1.00 1.00 5.85 6.30 0.0749 0.002! 347.50

900 0.121 981 11.75 1.00 1.00 5.50 6.25 0.0710 0.0019 345.00

950 0.121 981 11.40 1.00 1.00 5.20 6.20 0.0676 0.0017 343.00

1000 0.121 981 11.25 1.00 1.00 5.10 6.15 0.0669 0.0016 341.30

1050 0.121 981 10.85 1.00 1.00 4.75 6.10 0.0626 0.0015 339.50

(Iv) Slag C4 750 0.121 981 13.10 1.00 . 1.00 6.90 6.20 0.0B98 0.0030 335.00

BOO 0.121 981 12.75 1.00 1.00 6.65 6.10 0.0880 0.0029 327.50

850 0.121 981 12.40 1.00 1.00 6.45 5.95 0.OB74 0.0028 321.30

900 0.121 981 12.00 1.00 1.00 6.10 6.90 0.0834 0.0026 318.60

950 0.121 981 11.75 1.00 1.00 6.00 5.75 0.0842 0.0026 312.50

1000 0.121 961 11.65 1.00 1.00 5.95 5.70 0.0842 0.0026 306.30

1050 0.12) 98) 11.15 l.nn 1.00 5.65 5.50 0.01129 0.0025 :"I7.50
 1 74

Table A2.2 Density o f Slags

Temperature h (Hg-H^
h
1 2 H
l h
2 p
s
°C cm cms cms cms cms gm cm ^

(1) Slag C3 800 1.00 1.50 15.10 18.60 3.50 7.00

850 1.00 1.50 14.65 17.95 3.30 6.60

900 1.00 1.50 14.40 17.60 3.20 6.40

950 1.00 1.50 14.55 17.85 3.30 6.60

1000 1.00 1.50 14.10 17.20 3.10 6.20

1050 1.00 1.50 14.00 17.10 3.10 6.20

( i i ) Slag C2 750 1.00 1.50 13.40 16.65 3.25 6.50

800 1.00 1.50 13.25 16.45 3.20 6.35

850 1.00 1.50 12.85 15.85 3.00 6.05

900 1.00 1.50 12.50 15.40 2.90 5.75

950 1.00 1.50 12.20 15.00 2.80 5.55

1000 1.00 1.50 12.05 14.75 2.70 5.45

1050 1.00 1.50 11.60 14.15 2.55 5.10

(i.1i) Slag CI 750 1.00 1.50 12.85 16.10 3.20 6.40

800 1.00 1.50 12.50 15.55 3.05 6.10

850 1.00 1.50 12.15 15.10 2:>90 5.85

900 1.00 1.50 11.75 14.50 2.75 5.50

950 1.00 1.50 11.40 14.00 2.60 5.20

1000 1.00 1.50 11.25 13.80 2.55 5.10

1050 1.00 1.50 10.85 13.25 2.40 4.75

(iv) Slag C4 750 1.00 1.50 13.10 16.55 3.45 6.90

800 1.00 1.50 12.75 16.10 3.30 6.65

850 1.00 1.50 12.40 15.60 3.20 6.45

900 1.00 1.50 12.00 15.05 3.05 6.10

950 1.00 1.50 11.75 14.75 3.00 6.00

1000 1.00 1.50 11.65 14.60 2.95 5.95

1050 1.00 1.50 11.15 13.95 2.80 5.65

 1 75

Appendix 3

CORRECTION FOR . THE EFFECT OF

GRAVITATIONAL FORCE ON THE
SHAPE OF A S E S S I L E DROP

I t was m e n t i o n e d p r e v i o u s l y ( S e c t i o n 2.2.4.7)
t h a t g r a v i t y a f f e c t s t h e shape o f s e s s i l e drops and thus:;
the c o n t a c t a n g l e formed between t h e l i q u i d and t h e s u b s t r a t e .
48
Mack has worked on t h e e f f e c t o f g r a v i t y on t h e shape o f
36
a s e s s i l e drop u s i n g t h e t a b l e s o f B a s h f o r t h and Adams.
However, t h e e q u a t i o n d e v e l o p e d by Mack c o u l d n o t be used
in t h i s study. Thus an a l t e r n a t e e q u a t i o n has been developed
which does n o t r e q u i r e t h e t a b l e s by B a s h f o r t h and Adams.
I t s h o u l d be r e a l i z e d t h a t t h e a p p r o a c h used here i s a p p l i c -
a b l e o n l y f o r a c u t e c o n t a c t a n g l e s and f o r t h e shape o f t h e
drop shown i n F i g . A 3 . 1 .
C o n s i d e r a drop o f l i q u i d r e s t i n g upon a s o l i d
s u r f a c e OP under t h e i n f l u e n c e o f g r a v i t y and s u r f a c e t e n s i o n
( F i g . A3.2). The s o l i d l i n e s PR and PR' a r e t h a a c t u a l
forms o f two drops making c o n t a c t a n g l e s o f 9 and 9'
r e s p e c t i v e l y w i t h OP. The d o t t e d l i n e s PQ and PQ' a r e t h e
forms o f t h e drops i n t h e a b s e n c e o f g r a v i t y and a r e s p h e r i -
cal s u r f a c e s . The s u r f a c e s PQ and PR have a common tangent
PM, and PQ' and PR' have a common t a n g e n t PM .1
The q u a n t i t i e s
Fig. A3.2 S e s s i l e Drop under the
Influence of Gravity.
 1 77
x and V a r e m e a s u r e d . V i s t h e volume o f t h e drop and can
be o b t a i n e d by r o t a t i n g t h e a r e a OPR. 360° about t h e v e r t i c a l
a x i s OR. From t h e geometry i n F i g . A3.2,

tan(9/2) = (h+e)/x A3.1

L e t t h e d i f f e r e n c e between t h e two volumes g e n e r a t e d by

t h e a r e a s P0Q' and POR' be d e n o t e d by A V . 1

i.e. AV 1
= V P 0 Q I - V P Q R , A3.2

and i f (9-9 ) 1
i s s m a l l , AV' w i l l be n e a r l y e q u a l t o
a V = V
P 0 Q " P0R*
V s i n c e b
y construction V P ( ) R = V Q'
p 0 5

AV = v p o p - v p 0 Q 1

(Tr/6)[(h+e) + 3-x (h+e) - ( h + 3 x h ) ]

3 2 3 2
A3.3

S i n c e e i s v e r y s m a l l , t h e term e may be i g n o r e d and t h e

equation A3.. 3 r e d u c e s t o

3 h
2
+ e(x 2
+ h ) - (2 AV/TT = 0
2
A3.4

The g e n e r a l s o l u t i o n o f t h e q u a d r a t i c e q u a t i o n f o r
'e' i s e x p r e s s e d a s

YT
2 + h2 • 2 2 8hAV
+
A3.5
2h 2h 2 2 2

TT(X + h)
A f t e r expanding t h e terms o f t h e above e q u a t i o n ,
a c c o r d i n g t o t h e b i n o m i a l t h e o r e m , and s u b s t i t u t i n g t h e
 1 78

value of e/x in equation A 3 . 1 one obtains

tan ( e / 2 ) . = tan ( e ' / 2 ) + (2AV/TTX ) C o s 3 2

(6'/2)

1 2
fi
- (2AV/WJT) tan ( e ' / 2 ) C o s 0
(e'/2) + . . . A3.6

In the above equation e' is the measured contact

angle also represented by 6 avg (Table A 4 . 1 ) and 6 is the

true contact angle (after corrections) also represented

by e c Q r r (Talbe A4.1).

Mack tabulated values for the term AV/X for dif-

ferent values of e' and x/a. However, in his work the x/a

ratio varies from 0.1 to 0.5 and in the present work the x/a

ratio was as large as 1.3. The values from Mack's table

were plotted and then extrapolated into the necessary 'x/a'

3

region, Fig. A3.3. From this figure the value of AV/x

can be found for any value of e' and x/a. Here x is the

radius of the sessile drop and a is the capillary constant

of the liquid (a = 2y/pg;] where 'y' is the surface tension

of the liquid, 'p' is its density and 'g*. i s the accelera-

3

tion due to gravity). Once the value of AV/X is found the

value of e (or 9 ) c a n be c o m p u t e d f r o m e q u a t i o n A 3 . 6 .
c o r r

T h i s c o r r e c t i o n has been a p p l i e d to t h e e x p e r i m e n t a l

values of a' ( e „ „ )w in Table A4.1 in order to obtain the

avg,

true contact angle (0 )« corr The contact angle values plotted

i n F i g . 22 a r e e c 0 r r -
A3.3 P l o t Used f o r C o n t a c t A n g l e Corrections.
 1 80
Appendix 4

CONTACT- ANGLES OF DORE SLAGS

The v a l u e s o f t h e c o r r e c t e d c o n t a c t a n g l e s (9 )
. corr x

a l o n g w i t h t h e r a d i i o f t h e s e s s i l e drops ( r ) , t h e volume
of t h e drops and t h e u n - c o r r e c t e d v a l ue o f •©' (8 a v g)' a r e g i v e n
r 3

i n T a b l e A4.1 f o r t h e f o u r s l a g s . The c o r r e c t i o n used here

i s from A p p e n d i x 3.

The i n t e r f a c i a l s u r f a c e t e n s i o n v a l u e s were c a l c u -
lated using the following equation

Y
SL = Y
SV " LV
Y C o s 9

f o r t h e f o u r s l a g s and a l u m i n a . . The v a l u e o f f<-y f o r a l u m i n a

was o b t a i n e d from t h e e q u a t i o n

Y
s v = 892 - 0.12 T 5 4

where T i s t h e t e m p e r a t u r e i n °C. The v a l u e s o f Y ^ L *

and Cos 6 c o r r a r e l i s t e d i n T a b l e A4.2.
 181

T a b l e A 4.1 Contact Angles of D i f f e r e n t Slags

Temp. Volume radius (cm) f3 6

e
avg
cm^ 8 corr
°C r
l r
2 6
1
2

0.3484 0.3475 24.91 25.09 25.00 28.27

i ) Slag C3 800 0.0149

0.3813 0.3792 19.25 19.55 19.40 22.4.0

850 0.0149

0.3965 0.3929 18.75 19.25 19.00 22.08

900 0.0163

0.4025 0.3963 17.30 18.10 17.70 20.66

950 0.0157

0.0164 0.4125 0.4094 16.82 17.18 17.00 19.91

1000

0.4027 0.4001 15.45 15.75 15.60 18.53

i i ) Slag C2 800 0.0140

0.4702 0.4571 11.50 12.50 12.00 14.91

850 0.0165

0.4623 0.4854 11.15 ')9.65 10.40 13.05

900 0.0152

0.4727 0.4826 10.10 9.50 9.80 12.38

i950 0.0147

0.5037 0.4881 9.15 10.05 9.60 12.11

1000 0.0161

0.4442 0.4339 12.55 13.45 13.00 15.90

i i i ) Slag CI 800 0.0152

0.4849 0.4980 10.50 9.70 10.10 12.89

850 0.0165

0.4862 0.4975 9.10 8.50 8.50 11.26

900 0.0144

950 0.0158 0.5251 0.5141 7V95 8i 45

:
8.45 10.80

0.5486 0.5315 7.05 7.75 7.75 9.77

1000 0.0160

0.4904 0.4766 10.15 . 11.05 10.60 13.52

( i v ) Slag C4 800 0.0165

0.4906 0.4833 8.80 9.20 9.00 11.80

850 0.0143

0.5427 0.5590 7.10 6.50 6.80 9.47

900 0.0156

0.5635 0.5726 6.55 6.25 6.40 9.00

950 0.0161

0.5655 0.5779 6.40 6.00 6.20 8.73

1000 0.0159
 1 82

T a b l e A4.2 I n t e r f a c i a l Tension of Different Slags

Temp. SV e Cose„„„„
corr Y (dyne-cm" ) 1
Y
LV
Y S L

corr
°C dynectn" 1
dynecm" 1

800 704.00 447.50 28.27 0.8807 309.90

850 748.00 445.00 22.40 0.9245 336.60
900 792.00 442.50 22.08 0.9267 381.94
950 836.00 441.00 20.66 0.9357 423.36
1000 880.00 440.00 19.91 0.9402 466.31

800 704.00 378.80 18.53 0.9482 344.82

850 748.00 375.00 14.91 0.9663 385.64
900 792.00 372.50 13.05 0.9742 429.11 .
950 836.00 368.80 12.38 0.9767 475.80
1000 880.00 365.00 12.11 0.9777 523.14

800 704.00 350.00 15.90 0.9617 367.41

850 748.00 347.50 12.89 0.9748 409.26
900 792.00 345.00 11.26 0.9808 453.62
950 836.00 343.00 10.80 0.9823 499.07
1000 880.00 341.30 9.77 0.9855 543.65

800 704.00 327.50 13.52 0.9723 385.57

850 748.00 321.30 11.80 0.9789 433.48
900 792.00 318.80 9.47 0.9864 477.54
950 836.00 312.50 9.00 0.9877 527.34
1000 880.00 306.30 8.73 0.9884 577.25