Non-cement refractory castable containing Nano-silica Sol

1. Most castable and gun mixes use calcium aluminate cement (CAC) to bond the refractory
aggregate together. The amount of CAC in the mix can vary from relatively low quantities to 10%
or more, depending on the manufacturer and the mix. The presence of CAC is evident by CaO in
the chemical composition of the material. For most CAC products, the CaO content will be in the
range of 0.8 to 3.0%. These castable and gun mixes are blended with water to a proper consistency
and installed in place. The added water reacts with the CAC, forming hydrated phases that provide
low-temperature bonding of the refractory material.
2. At low temperatures, the CAC materials are very dense and have very low permeability. As the
refractory is heated, the physically bonded water is first driven off, followed by the chemically
bonded hydrated water. Because several hydration phases are present, the complete dehydration
process occurs over a broad temperature range (210 to 620°C). As each of these phases gives up
its chemically bonded water, bonding strength decreases, and permeability and porosity increase
until all water has been removed.
3. Sol-gel bonding Nano technology containing no CAC. Nano-silica is one of the most popular
binders for refractory, monolithic and castable applications. Nano-silica sol or colloidal silica
containing up to 40 wt. % of Nano-metric spherical amorphous silica particles (3-15 nm diameter).
4. These materials have been broadly used in the formulations of coatings, catalysts as well as high
temperature binders for fibrous isolating.
5. The water-based colloid (colloid silica) surrounds the refractory particles and, after gelling, forms
a network encapsulating the refractory particles. During the drying step, the hydroxyl groups (Si-
OH) on the surface of the particles generate siloxane bonds (Si-O-Si), which results in a three-
dimensional network.
6. Gelation can also be induced by pH changes and a salt or water-miscible organic solvent addition,
named gelling agents. With the proper selection of these agents or the pH variation, the colloid is
gelled around the solid particles providing mechanical strength to the system after drying. The
resulting structure is highly permeable and allows the composition to be easily dried, reducing
cracks and explosive spalling. Therefore, the use of Nano-silica in refractory castable may reduce
the problems presented by the current hydraulic binders.
7. Nano-silica sol content has a great effect on the self-flow characteristics and other properties of
gel-bonded self-flowing castable. The Nano-silica sol addition can increase the working time of
castable. By increasing of the Nano-silica, and thus liquid, in the batch the strength is decreased
because of increasing porosity in the dried body. If the Nano-silica sol content in the castable
composition be used in the range of 10-11 %, a gel-bonded high alumina castable with adequate
working time and reasonable strength will be obtained.
 8. Complete dehydration of hydroxyl groups after firing up to 1000 ºC leads to a decrease of
apparent porosity and an increase of strength. This shows the advantage of using sol bonding
instead of cement bonding. Also, the high surface area of nano-silica leads to low sintering
temperatures of castable and a considerable increase of mechanical strength. In samples fired at
1300°C mullite phase was detected that can increase the compressive strength of the castable.

References.

1. Ismael M.R., dos Anjos R.D., Salomao R., Pandolfelli V.C.: Refractories Applications and News 11, 16
(2006). 2. Gerotto M.V., Studart A.R., Pileggi R.G., Pandolfelli V.C.: Am. Ceram. Soc. Bull. 79, 75 (2000). 3.
Mukhopadhyay S., Pai P., Nag B.: Ceramic International 33, 175 (2007). 4. Oliveira l.R., Studart A.R.,
Pandolfelli V.C.: Am. Ceram. Soc. Bull. 81, 27 (2002). 5. Das S., Sarkar R., Mandal P., Mukherjee S.: Am.
Ceram. Soc. Bull. 82, 55 (2003).

INFLUENCE OF MINERAL PURITY ON MULLITE AND ANDALUSITE BASED REFRACTORIES

1. Andalusite and mullite are well known to provide high thermo-mechanical stability, therefore
enhancing key properties such as thermal shock resistance and refractoriness under load.
However, the performance of the refractory products based on mullite and andalusite can be
strongly affected by the amount and the type of impurities associated with the main mineral.
2. Andalusite Among the aluminosilicate raw materials, andalusite is one of the best natural source
of mullite, as it is available in sizes up to 8 mm and can be beneficiated in order to achieve a very
high degree of purity.
3. Andalusite transforms into mullite at relative low temperature, with a minor volume expansion
(+4.5%). For this reason, andalusite in refractory products can be used as fired (fired bricks) or
unfired (unfired, bricks, castable, plastic mixes) therefore taking advantage of the expansion
resulting from the mullitization stage.
4. Unlike most of the other aluminosilicates, the mullitization of andalusite does not involve any
dehydration stage and therefore does not generate intrinsic porosity. For this reason, refractory
materials based on andalusite, either raw or calcined, exhibit porosity significantly lower than
bauxite or chamotte.
5. When applied in castable, this specific behavior of andalusite results in an improved corrosion
resistance as well as a lower water demand.
 6. Mullite, which is a mineral existing under the form of 3Al2O3 2SiO2 (typical of sintered mullite) or
2Al2O3 SiO2 (typical form of fused mullite), provides attractive properties for refractory systems
7. Which include low thermal expansion, low thermal conductivity, good chemical stability, and
excellent thermo-mechanical stability. Unfortunately, mullite rarely occurs as natural raw
material. Consequently, the development of mullite in commercial refractory has to be achieved
by firing various aluminosilicate, with suitable chemical composition, involving clays, calcined
kaolin and various fine silica and alumina

References.

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Rebouillat. L.; Daniellou, P.; Dubreuil, P.: Mullitization of andalusite in bricks and castable, UNITEECR 1997,
Proccedings, Vol 2, New Orleans, 899–907 [3] Bouchetou, M.L.; Poirier, J.P.; Ildefonse, H. P.: Kinetic of
Mullitization of Andalusite Crystals, UNITECR 2005, Proceedings, Orlando 2005, 360–364 [4] Kingery,
W.D.: Factors affecting thermal stress resistance of ceramic materials. J. Am Ceram. Soc. 38 (1955) [1] 3–
15 [5] Kakroudi, M.G.; et al.: Anisotropic behaviour of andalusite particles used as aggregates on refractory
castables. J. Eur. Cerm. Soc. (2008), doi:10.1016/j.Jeurceramsoc 2008.07.043 [6] Hubert, P.: Relation
between microstructure and refractory properties in andalusite based low cement castable. X Int.
Metallurgical Conf., Polish Ceramic Bulleting 75 (2003) 43–55 [7] Buhr, A.; Koltermann, M.: Neue
feuerfeste Rohund Werkstoffe mit mehr als 60 % Al2 O3 . Entwicklungsrichtungen und Versuche in
Torpedound Stahlgiesspfannen, Aachen, 1996, 161–165 [8] Huber, P.; Walz, W.: Application of andalusite
based refractory in steel industry, IREFCON Pro