Downloaded from jame.iut.ac.ir at 16:23 IRDT on Wednesday June 14th 2017
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Investigating Sulphate Binders Replacement for
Phosphate Binders in Tundish Plasters
S.M. Siadati, and A. Monshi
Downloaded from jame.iut.ac.ir at 16:23 IRDT on Wednesday June 14th 2017
Department of Materials Engineering, Isfahan University of Technology
(IUT), Isfahan, 84156, Iran
Abstract: One of the main reasons for the blocking and sticking of the expendable layer in tundish plaster to the permanent
layer and the subsequent increase in refractory consumption and associated costs is the use of low-melting phosphate binders. At
high temperatures in continuous casting of steel, phosphate binders provide low-melting point melts which cause reactions
between the two consuming and permanent layers, so that deskulling becomes difficult and the permanent layer is damaged. In
this work, the using sulphate binders such as sulphamic acid and sulphates of aluminum, magnesium, ammonium, sodium,
potassium, and calcium are studied as substitute binders. Some of the plaster properties manipulated by these different binders,
namely cold crushing strength(CCS), Bulk Density (B.D), and Apparent Porosity (AP%), were measured according to ASTM.
Studies by SEM and XRD showed that magnesium sulphate would be the best selection as a binder in tundish plaster. This binder
provides strength at low temperatures, but dissociates to MgO and SO3 at high temperatures. SO3 evaporates and MgO is an oxide
with a high melting point that does not react with the host oxide, usually MgO. No melting or reaction occurred and deskulling
was easy without any damage to the permanent layer.
Keywords: Working layer, Tundish, Binder, Sulphate bonds, Phosphate bonds.
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*
678
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CCS (M Pa)
Downloaded from jame.iut.ac.ir at 16:23 IRDT on Wednesday June 14th 2017
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SO3%
# F& - - P% Q
(M Pa)
(1400 C)
pH
(1100 C)
I 0 V KB
dmmºC
mmºC
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d
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N
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K-
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H` 7
Periclase
Magnesium sulphate
Enstatite
Forsterite
Mg(OH)2
(1400ºC)
I n te n s i ty
Intensity
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Periclase
Aluminium sulfate
Mg(OH)2
Forsterite
(1100ºC)
(1400ºC)
(110ºC)
(110ºC)
5
15
25
35
45
55
65
75
85
5
15
25
35
45
(2.)
& & AlS
# T- % )F% D%
+%
:
U7
UK
MgS
3 /@9-F
# T- % )F% D%
7 V /-/ ; A [
MgS
,/J `/& 8 7 H-. 2 ?
.
G[
% V KB
3^ I :?
0/7
& & ? eK < € J I a (
3. dmm C I
93
AlS
^2 7 xN 7 U N
mm C 2
I :,& 7 . ,-.% ,/ G UK
a&
2 T H: . A,
& `/& l 2 d I XK .,&
A, 7 dmm C I
7 & &9
I 3:
3: 3& & %K/ 3
: & & I , a& 7
3 %3 C,: 03 .
.,3&
3 9
- ? s2
bM :.
V KB
9
I
V KB
.
mm C I 3
AS
& &?
mm C 2,4 I8 7
. AmS2 MgS I : & &
& &
. % f&;
O/ [
,/
,- 7
37 M,/3 2 3 `fG I 3 ? G8 37 I :
. & & 9 V KB
,
f/ &
.
-?
. ,: % M 0& `/& (d) 2,^ A N b .
U3'X'G ,
G[
I :,& 7 `fG …
m C I3
7
I 3/@ C? ,3& M 3K ,- 3
.
,&
SO3
93
/= W 7
mm C I
9
%-/ J V KB
.
.% : & &
33 `fG
M 37 03/7 U3/
2 V /-/ ; A [
,- 7 2
lm C 2 •mm 2,334 I 33:
37 .,& 3 %3 S]3
V KB
3 `fG I 3 M 37 -/ 3J2 V 3/-/ ; A [
U 3
M 3G%3
3 & & 37
C,
^2 ? 7 U'X'G % f4 ,= 2 /(&
S3/G G 37 V `/- A [
33 2 C,33
I,/
](&
. 3 %3 3: & & /(& H: . 7 f-
: V KB
H`
=
`fG I
I 3: 3& &
9/7 ? :,& 7
93 I 7 U/ 9 /X= .,7 % H ` : & &
03/7 %3 . ,- 7 9
37 7 2 ? H/37
m
.,- (: Ams 2 Als S/G G 7 I : & &
N3
? . 3 %3 { 3W & & ? M; I `^ a 2 ,- 7 SO3V G2
3G
& & ? %^2 W I :? @ cf4 7 7
MgS
.,- `[/7 & & U'X'G
3 `fG I 3 ?
Al2 O3(S) + 3SO3(g)
H: 3. 3f/ & 2 03/7 U3'X'G M,3 ;
I3 2
3 /; 9-F
, % G8 7 mm ºC `/& AmS & & I 7 %T [G 9/-u
I 7 %0-. 2 9/-u
3& & ? %3^2 W I :? @ cf4 .
93 .
85
+%
M 0& ? A = 7
MgO(s) + SO3(g)
900°C
Al 2 (SO 4 )3(S)
75
5@== C &55==&55=
:[ r]
1100°C
65
(2.)
55== C & 55=
MgSO 4(s)
55
](33&
V `/- A [
W
I 033/7 V KB 3
3
,33- 7
`fG .c ,:
V `/- A [
j
Intensity
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Pe riclase
Am m unium Sulfate
Am m unium Magne s ium Sulfate
Mg(OH)2
Ens tatite
Fors trite
(1400ºC)
(110ºC)
5
15
25
35
45
55
65
75
85
(2.)
5@==ºC& 55=
K2O 2 Na2O
U/
2; ? ,@,/(3. 2
7 c `/- A [
H `33
b 3W 7
9/-\ :2 ,&
3a A 3]N 37 .
~ 37
03/7 dmm C I
/… G 9 0/7
<wT •- - ? H `
•3- - ? 3G
8 37 I 3:
MgS
3 %K/
& & V KB
•- - ?2
mm C I
%
CaS
2 m I 333 2
`fG
7
63G
H`
V KB
7
2 C,0&
% C,: 0 v p2 7
3
2 ,3 %G [( I : ,- 7 Z W (
A 0 ?; H ?;
%G [
I 3G (HMP)c ,3 A [(
`3/& (MSP) A [(3 c ,3
%: a03 ?; t 3
`a: ,- 7
: ,3- 7 9
jj
: ,- 7 9
I 7
^ S/. G
I2
7% 70
3& 2 (TPP)c ,3 A [( %XJ
.
I8 37 I :
C, V KB H `
I : ,- 7 7
V f&
(
G
@A =
72 G 4 M (K
,/J ( ) UK ? K& -u
ˆ'0 `/&
37 V 3/-/ ; A [ 3
C H`
H `3
2 I /6 W &2 MgO
`/- ? C,
V KB
(Mg2SiO4)
3…
@ 7
3 `fG ? C,& /T 7 Al2O3 AlS & &
C 3. H-3.2 SiO2 ,3-&
.
: & &
% C,: 0
. C 2; ^2 7 Q R I :? 2
3
: & & XRD I a
2 (MgSiO3)
37 I 2,34 3G 3.
/G (& I ,
3 % U/K0G /6 W &
^2
.,-.% O . V KB
3 % Q2o %a& ,/[ Q < A =
.
U/
3 `/- I 3: & 9/7 %7 R
3. ,: % M 0& dmm C I
7 f- . ? (& A o 9 @ 7 2 ,- 7 9 M, Q2o (r) UK
C [3
3 . 3 %3 & C,: 03
bM :.
.
H`
,- 7 9 .,& % %T 7 & &
3K& -u
% C,: 0 .
& & c. ](& V KB
H`
Q R I :?
9
MgS
3 &;2 C, M 2 : & 9/7 . Q R ? I ,
,- 7 . ,: % M 0& `/& dmm C
9 G c/(X. A [
3
3 /U9-F
6G
? 3 & @•/:
333& & ? XRD I 333a (333
7 dlm C 2,4 I
SEM
](&
+%
(r) UK3 SEM
& & V KB
xN 7 C, U/K0G Q R ? : & &
.
# T- % )F% D%
/… 3 G 9 3 . 2; ? ,33@ I /633 W & 9 3 ,&
,3
3…
AmS
&
V KB 3 9 G8 7 7) SoS & & ? SEM
I3
9/37 ? U3 .
%3K 2
3.
. ,: % M 0& ( dmm C
3b 37 : & ?
? o [& 9 U/ ,& . o [& a ,K
3
: & M,
,- 7 S/. G
- ? xN 7
6G
c , ,/(.
W I? ,@ 2?
: & 2
‹4 : & M,
/= W 7 8 7 I :
I 3 . A,3 37 3 PoS 3& & I 37 % 4 9/-u .
I 2;? ,3@ H & c/ J ,/(. f( ) 2,3^ : & &
c, A[
(1400°C)
(1100°C)
2 c/ J A [
%
@A =
,
(
7 .,-. % [
I : ,- 7 .
% ˆ'0
.7I
;H
5@==ºC
*
H% $
# SEM &
/ X9-F
j"
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Intensity
Pe riclas e
Calcium s ulphate
M g(OH) 2
(1400ºC)
(110ºC)
5
15
25
35
45
55
65
75
85
(2")
5@==º C & & 55=
CaS
&
# D%
+%
3 /Z9-F
25ºC
20
110ºC
18
1100ºC
16
1400ºC
CCS (M Pa)
14
12
10
8
6
4
2
0
TPP
HMP
MSP
Binder Type
J1 K
,3
3: 3& & 3 : S/. G
,3 M; S3/. G
.
3. I ,- 7
3f I 37 I G8 7 U/(& J , 7
H-3. 2 …
9/-\ : .
#
V KB
,-.%
f
. %87
I 3:? 93
H `3
3f/ &
I ? V KB
mmmºC
% 3N
/= W : ,- 7 9 ? C [ ? % & , , •- - ?
^2 I 0/7 Na2O
Q Xw
7 . 9 I 7 f/ & 2
M 7 8 72 Q R I :?
3 %3 U/K0G
rlºC Q2o
2 3<wT •3- - ? H `3 x3N 7`/& Q R
.[n],& % V KB
j
37 3^ G 37 3. ,3--.%3 3•
M 03& (•) UK3
I
H: . `/&
JV ^
3& & 3 93 ? SEM 2 63G .,- (/&
: ,- 7 9 ? U= 4 Q R I :?
ln C Q2o w & 7 Mg3(PO4)2 /Y&
3. ( m)UK3
3 / A 9-F
^2 P2O5 % .
4.
%3372o 2? A 3 ]/. G (MgO) ? (33& 3 -/ ? 3 7 %G [(33 ,33- 7
3w & 37 Mg(PO3)22
" G -: %
& au . ,: %
.,& C, c: 7 A o I T 6G xN 7 8 7
3. ,3: % M 0& : & & 9 ? SEM 2 6G2 (l) 2,^
I G … 3 H3 & ,3- 7 S3/. G
I 2;? ,3@
3XN 37 [(3 ,/(3. 7
c ,3 ,/(3. ,3
](& V KB
H`
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7I
;H
5@==ºC
'
H % $ 6% )
6E
# SEM &
/>9-F
# F H I [% / ? 4&
Na2O%
P2O5%
•/d
rm/r
(NaPO3)6
c , A [(
d /
ln/r
Na5P3O10
c , A [( %XJ I G
l/
nd/
NaH2PO4
7I
;H
5@== ºC
'
% / /
H % $ 6% )
,- 7
A [( c ,
# XRD
`a:
&
+ % /2\ 9-F
j#
% 8 7 ](& V KB
I 3:
9/3-\ :
3
3 . 3 `fG U3/
3 K- U33/
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,- 7 9 ., %7 ? S - x/4 9
M,3
2; %3 M |
3 7 G8 3 7 I 3 :
2
%7 R ?
2 C . I /@ X^ V ^ ,4
S/ ; M2,7 2
4 C,& /T 7
H ,3& G V a03/J V 3a-:
3//|G 3& @•/3:
2 %& 3/ I :
3f
& @•/:
V ^ S/. G
3/@%3 A 3= (I` Q R ? U]T)
.,: % & y
8 % / / S/. G
/= W 7 %G [
G[
I
KB (33 I :,33& 72 C,33
Uƒ )8 7 I :
I :,& 7 0/7 `fG U/
H ,3& G I 3
^ S/. G
C [
I : ,- 7 9/7
/= W 9 I
2 ,& 2;
A B/3p G 37 .,& 03& 8 2 M,
< w
03/7 U3'X'G f 2
I 7 : ,- 7 9 ] -
. ,- 7
•3- - ? x3N 7 8 37 I 3:
.,-. %
7 I ,- 7 9/-u ( KX N
I 3 . V KB 3
V KB 3 9/ 3J I :
?
I : ,- 7
/3= W , 7 0/7 ,- 7 S/. G
-/ 3 J I 3 :
.,3-. %3 3•
8
u : I,/
? U3]T H ,3& G V a0/J I
H/7
J /X'G ,-
G [ 3 {2 3W M 3u 9/-\ : . /@ A = %
,3
03/7 ,3- 7 I,/3
I 3 . V KB 3
- ? ? ,3-.% & f S/. G
7 M,&
SO3
37 (H ,3& G V a0/J I ) %& /
3 %3 x3N 7 3f/ &
?
7 9/ J I :
R /@
^2 7
, 7
%] -
. X7 2 I . 8 , ,
V `/- A [
,- 7 8 7
*0%&
1. blocking
2. tundish
3. binder
4. sintering
5. aggregate
] %
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jq
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I K/ 33 ) ? ,33@
33 ( 33 ^ G) .~ M 33
B .h*
. n M G M & ^ A 0 & (? ,@
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"*