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Silica sol addition [%]
C-M.O.R.
CCS
Green strength as a function of silica sol
addition. Castables with a total of 4.1% water and 8%
silica according to recipes given in Table 6.
After drying however, the picture is changed. In
Figure 17, it is seen that both MOR and CCS
ddition of silica sol. Somehow,
during the drying at 110C, the silica sol improves
bonding. The mechanism behind is difficult to explain,
that the silanol groups
may condense to bonding
This condensation is illustrated in
Dried strength as a function of silica sol
addition. Castables with a total of 4.1% water and 8%
silica according to recipes given in Table 6.
Figure18: Suggested
12
silanol condensation during
drying of microsilica containing ULCC and NCC.
Although probable, we do not have firm evidence of
this mechanism. Nevertheless we do
strengthening following the drying. This
strengthening seems to be dependent on the amount
of silica sol so even if the silica sol gives weaker
green-bodies, it contributes to higher dried strength.
The overall conclusion may therefore be
in the following way: If it is possible to have a liquid
silica sol additional to the dry-mix, and t
in green-strength is not a problem, then it may be a
good idea to make castables where
microsilica is supplemented with silica sol.
resistance has not been tested, but is expected to yield
similar results as the non-silica sol compositions.
Hot strength
This paper is not intended to present much about the
hot-properties of this type of castable, just a few
figures taken from another source
bond systems.
It is an old experience that if microsilica
together with cement, often 5 mass% of each,
refractoriness may suffer severely. Figure
comparison between the refractoriness under load
(R.U.L.) of three castables based on the compositons
given in Table 2 and 3 with 8 mass% microsilic
two LCC differ in the type of cement used, one is a
common 70% CAC the other a
clearly seen that the reduction in CaO
leads to improved refractoriness. The big
improvement comes for our microsilica
NCC with properties that can make it
temperatures up to 1800C. All this is due to mullite
formation, a topic that has been treated extensively in
earlier
15
publications. Briefly described, the
microsilica, in absence of cement, reac
and forms mullite. The situation is quite different if
cement is present. A liquid is formed that has a
composition close to 50 mass% 70% CA
combination with 50 mass% microsilica. So if e.g. a
castable with 5 mass% microsilica and
cement is tested, then 10 mass% liquid forms at
1500C. The result is a catastrophic failure of the
1.8
10.1
9.3
4 6
C-M.O.R.
CCS
5.7 6.1
49.3
52.0
4 6
condensation during
drying of microsilica containing ULCC and NCC.
, we do not have firm evidence of
Nevertheless we do observe
the drying. This
strengthening seems to be dependent on the amount
silica sol so even if the silica sol gives weaker
bodies, it contributes to higher dried strength.
conclusion may therefore be formulated
f it is possible to have a liquid
mix, and the lowering
strength is not a problem, then it may be a
good idea to make castables where some of the
microsilica is supplemented with silica sol. Explosion
resistance has not been tested, but is expected to yield
sol compositions.
present much about the
properties of this type of castable, just a few
other source
10
with the same
that if microsilica is used
together with cement, often 5 mass% of each,
suffer severely. Figure 19 shows a
comparison between the refractoriness under load
(R.U.L.) of three castables based on the compositons
with 8 mass% microsilica. The
two LCC differ in the type of cement used, one is a
common 70% CAC the other an 84% CAC. It is
reduction in CaO (84% cement)
leads to improved refractoriness. The big
improvement comes for our microsilica-gel bond
NCC with properties that can make it applicable at
temperatures up to 1800C. All this is due to mullite
formation, a topic that has been treated extensively in
publications. Briefly described, the
microsilica, in absence of cement, reacts with alumina
and forms mullite. The situation is quite different if
cement is present. A liquid is formed that has a
composition close to 50 mass% 70% CA-cement in
combination with 50 mass% microsilica. So if e.g. a
castable with 5 mass% microsilica and 5 mass%
cement is tested, then 10 mass% liquid forms at
1500C. The result is a catastrophic failure of the
castable when temperature reaches 1500C This may
be seen in Figure 9 as the almost vertical drop at
1500C.
Fig. 19: Effect of cement on RUL for WFA based
castables with 8 mass% microsilica. LCC has
6 mass% cement.
Compared to microsilica free castables, the
microsilica-gel bond shows similar refractoriness,
Figure 20. When using the microsilica-gel bond it is
possible to obtain a refractoriness equal to or even
above the microsilica-free LCC alternative.
Fig. 20: Comparison of RUL for WFA based
microsilica-gel bond NCC (0.5 mass% cement) with 8
mass% microsilica, LCC (6 mass% cement) with 8
mass% microsilica and LCC (6 mass% cement)
without microsilica
Conclusion:
For castables are based on gelation of microsilica as
bond system, several attractive properties have been
identified. These are; very good placing properties
combined with high refractoriness and hot strength.
The green strength is low but sufficient, and the dried
strength is good. Further, the bond contains only
small amounts of bonded water, so once the free
water is removed, the castable tolerates very high
heating rates. If silica sol is used complementary to
the microsilica, improved strength was seen for the
dried samples. The green strength did not benefit
however.
In general, the gel-bond offer attractive possibilities
for advanced refractories, opportunities that may be
difficult to match with alternative bond-systems.
References:
1
K. Heggestad, J.L. Holm, K. Lnvik and B.
Sandberg, "Investigations of Elkem Microsilica by
Thermosonimetry", Thermochimica Acta, 72 (1984),
205-212
2
E.Dingsyr, M. Dstl and C. Wedberg, in "Preprint
of the Fifth European Symposium Particle
Characterization, 24-26 March 1992, Nrnberg,
Germany. publ. by Nrnberg Messe GMBH
3
R.K. Iler, The chemistry of silica, John Wiley &
Sons, New York 1979.
4
B. Myhre and K. Sunde, "Alumina based castables
with very low contents of hydraulic compound. Part I:
The effect of binder and particle-size distribution on
flow and set.", Proc. UNITECR95, Kyoto, Japan,
Nov. 19-22 1995, p. II/309-16
5
B. Myhre and K. Sunde, "Alumina based castables
with very low contents of hydraulic compound. Part
II." Strength and High-Temperature Reactions of No-
cement Castables with Hydraulic Alumina and
Microsilica, Proc. UNITECR95, Kyoto, Japan,
Nov. 19-22 1995, p. II/317-24
6
B. Myhre and H. Fan, Gel Bonded Castables
Based on Microsilica as Binder, proc.
UNITECR2011
7
M. A. L. Braulio*, V. C. Pandolfelli and C. Tontrup,
Colloidal Alumina as a Novel Refractory Castable
Binder proc. 53rd Int. Coll. on Ref. Aachen 2010 p.
111-114
8
B. Myhre and Aase M. Hundere: Substitution of
Reactive Alumina with Microsilica in Low Cement
and Ultra Low Cement Castables. Part I: Properties
Related to Installation and Demoulding Proc.
UNITECR97, New Orleans, USA, Nov. 4-7 1997, p.
43-52
9
Aase M. Hundere and B. Myhre: Substitution of
Reactive Alumina with Microsilica in Low Cement
and Ultra Low Cement Castables. Part II: The Effect
of Temperature on Hot Properties Proc.
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0 500 1000 1500 2000
Temperature [C]
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LCC (70% CAC)
LCC (84% CAC)
0.5% (70%CAC)
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0 500 1000 1500 2000
Temperature [C]
E
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0.5% cement 8% MS
6% cement 8% MS
6% cement , 0% MS
UNITECR97, New Orleans, USA, Nov. 4-7 1997, p.
91-100
10
Bjrn Myhre and Haibing Fan, Microsilica-gel
bond for explosion proof castables proc. IREFCON
2012, Kolkata 2012 p 71-76
11
US pat. 5147830 Composition and method for
manufacturing steel-containment equipment
Subrata Banerjee et al
12
J.E. Funk and D. R. Dinger:"Particle Size Control
for High-Solids Castable Refractories", Am. Ceram.
Soc. Bull.73[10],66-69, (1994)
13
ALBIN KLINT, Amphiphilic surface modification
of colloidal silica sols, Master of Science Thesis in
the Master Degree Programme Chemistry and
Bioscience, Department of Chemical and Biological
Engineering, Division of Applied Surface Chemistry
CHALMERS UNIVERSITY OF TECHNOLOGY,
SWEDEN
14
Li Zaigeng et al., Phase Compositions and Setting
Mechanisms of Low Cement, Ultra-low Cement and
Cement-free Castables in Proc. 2nd Int. Symp on
Refr. Beijing China, Oct. 30 - Nov. 2 1992, p.
540-547
15
B. Myhre: Lets Make a Mullite Matrix! Ref.
Appl. and News, vol 13, No 6, 2008