Refractory

A refractory material or refractory is a material that is resistant to decomposition by heat, pressure, or chemical attack, and retains strength and form at high temperatures.[1] Refractories are inorganic, nonmetallic, porous, and heterogeneous. They are typically composed of oxides of the following materials: silicon, aluminium, magnesium, calcium, and zirconium.[2]

This article is about heat resistance. For other uses, see Refractory (disambiguation).

Refractory bricks in a torpedo car used for hauling molten iron

ASTM C71 defines refractories as "...non-metallic materials having those chemical and physical properties that make them applicable for structures, or as components of systems, that are exposed to environments above 1,000 °F (811 K; 538 °C)."[3]

Refractory materials are used in furnaces, kilns, incinerators, and reactors. Refractories are also used to make crucibles and moulds for casting glass and metals and for surfacing flame deflector systems for rocket launch structures.[4] Today, the iron- and steel-industry and metal casting sectors use approximately 70% of all refractories produced.[5]

Refractory materials

Refractory materials must be chemically and physically stable at high temperatures. Depending on the operating environment, they must be resistant to thermal shock, be chemically inert, and/or have specific ranges of thermal conductivity and of the coefficient of thermal expansion.

The oxides of aluminium (alumina), silicon (silica) and magnesium (magnesia) are the most important materials used in the manufacturing of refractories. Another oxide usually found in refractories is the oxide of calcium (lime).[6] Fire clays are also widely used in the manufacture of refractories.

Refractories must be chosen according to the conditions they face. Some applications require special refractory materials.[7] Zirconia is used when the material must withstand extremely high temperatures.[8] Silicon carbide and carbon (graphite) are two other refractory materials used in some very severe temperature conditions, but they cannot be used in contact with oxygen, as they would oxidize and burn.

Binary compounds such as tungsten carbide or boron nitride can be very refractory. Hafnium carbide is the most refractory binary compound known, with a melting point of 3890 °C.[9][10] The ternary compound tantalum hafnium carbide has one of the highest melting points of all known compounds (4215 °C).[11][12]

Uses

Refractory materials are useful for the following functions:[13][2]

1. Serving as a thermal barrier between a hot medium and the wall of a containing vessel
2. Withstanding physical stresses and preventing erosion of vessel walls due to the hot medium
3. Protecting against corrosion
4. Providing thermal insulation

Refractories have multiple useful applications. In the metallurgy industry, refractories are used for lining furnaces, kilns, reactors, and other vessels which hold and transport hot mediums such as metal and slag. Refractories have other high temperature applications such as fired heaters, hydrogen reformers, ammonia primary and secondary reformers, cracking furnaces, utility boilers, catalytic cracking units, air heaters, and sulfur furnaces.[13]

Classification of refractory materials

Refractories are classified in multiple ways, based on:

1. Chemical composition
2. Method of manufacture
3. Fusion temperature
4. Refractoriness
5. Thermal conductivity

Based on chemical composition

Acidic refractories

Acidic refractories are generally impervious to acidic materials but easily attacked by basic materials, and are thus used with acidic slag in acidic environments. They include substances such as silica, alumina, and fire clay brick refractories. Notable reagents that can attack both alumina and silica are hydrofluoric acid, phosphoric acid, and fluorinated gases (e.g. HF, F₂).[14] At high temperatures, acidic refractories may also react with limes and basic oxides.

• Silica refractories are refractories containing more than 93% silicon oxide (SiO₂). They are acidic, have high resistance to thermal shock, flux and slag resistance, and high spalling resistance. Silica bricks are often used in the iron and steel industry as furnace materials. An important property of silica brick is its ability to maintain hardness under high loads until its fusion point.[2]
• Zirconia refractories are refractories primarily composed of zirconium oxide (ZrO₂). They are often used for glass furnaces because they have low thermal conductivity, are not easily wetted by molten glass and have low reactivity with molten glass. These refractories are also useful for applications in high temperature construction materials.
• Aluminosilicate refractories mainly consist of alumina (Al₂O₃) and silica (SiO₂). Aluminosilicate refractories can be semiacidic, fireclay composite, or high alumina content composite.[15]

Basic refractories

Basic refractories are used in areas where slags and atmosphere are basic. They are stable to alkaline materials but can react to acids. The main raw materials belong to the RO group, of which magnesia (MgO) is a common example. Other examples include dolomite and chrome-magnesia. For the first half of the twentieth century, the steel making process used artificial periclase (roasted magnesite) as a furnace lining material.

• Magnesite refractories are composed of ≥ 85% magnesium oxide (MgO). They have high slag resistance to lime and iron-rich slags, strong abrasion and corrosion resistance, and high refractoriness under load, and are typically used in metallurgical furnaces.[16]
• Dolomite refractories mainly consist of calcium magnesium carbonate. Typically, dolomite refractories are used in converter and refining furnaces.[17]
• Magnesia-chrome refractories mainly consist of magnesium oxide (MgO) and chromium oxide (Cr₂O₃). These refractories have high refractoriness and have a high tolerance for corrosive environments.

Neutral refractories

These are used in areas where slags and atmosphere are either acidic or basic and are chemically stable to both acids and bases. The main raw materials belong to, but are not confined to, the R₂O₃ group. Common examples of these materials are alumina (Al₂O₃), chromia (Cr₂O₃) and carbon.[2]

• Carbon graphite refractories mainly consist of carbon. These refractories are often used in highly reducing environments, and their properties of high refractoriness allow them excellent thermal stability and resistance to slags.
• Chromite refractories are composed of sintered magnesia and chromia. They have constant volume at high temperatures, high refractoriness, and high resistance to slags.[18]
• Alumina refractories are composed of ≥ 50% alumina (Al₂O₃).

Based on method of manufacture

1. Dry press process
2. Fused cast
3. Hand molded
4. Formed (normal, fired or chemically bonded)
5. Un-formed (monolithic-plastic, ramming and gunning mass, castables, mortars, dry vibrating cements.)
6. Un-formed dry refractories.

Shaped

These have standard size and shapes. These may be further divided into standard shapes and special shapes. Standard shapes have dimension that are conformed by most refractory manufacturers and are generally applicable to kilns or furnaces of the same types. Standard shapes are usually bricks that have a standard dimension of 9 × ​4 ¹⁄₂ × ​2 ¹⁄₂ inches (230 × 114 × 64 mm) and this dimension is called a "one brick equivalent". "Brick equivalents" are used in estimating how many refractory bricks it takes to make an installation into an industrial furnace. There are ranges of standard shapes of different sizes manufactured to produce walls, roofs, arches, tubes and circular apertures etc. Special shapes are specifically made for specific locations within furnaces and for particular kilns or furnaces. Special shapes are usually less dense and therefore less hard wearing than standard shapes.

Unshaped (monolithic refractories)

These are without definite form and are only given shape upon application. These types are better known as monolithic refractories. The common examples are plastic masses, Ramming masses, castables, gunning masses, fettling mix, mortars etc.

Dry vibration linings often used in Induction furnace linings are also monolithic, and sold and transported as a dry powder, usually with a magnesia/alumina composition with additions of other chemicals for altering specific properties. They are also finding more applications in blast furnace linings, although this use is still rare.

Based on fusion temperature

Refractory materials are classified into three types based on fusion temperature (melting point).

• Normal refractories have a fusion temperature of 1580 ~ 1780 °C (e.g. Fire clay)
• High refractories have a fusion temperature of 1780 ~ 2000 °C (e.g. Chromite)
• Super refractories have a fusion temperature of > 2000 °C (e.g. Zirconia)

Based on refractoriness

Refractoriness is the property of a refractory's multiphase to reach a specific softening degree at high temperature without load, and is measured with a pyrometric cone equivalent (PCE) test. Refractories are classified as:[2]

• Super duty: PCE value of 33–38
• High duty: PCE value of 30–33
• Intermediate duty: PCE value of 28–30
• Low duty: PCE value of 19–28

Based on thermal conductivity

Refractories may be classified by thermal conductivity as either conducting, nonconducting, or insulating. Examples of conducting refractories are SiC and ZrC, whereas examples of nonconducting refractories are silica and alumina. Insulating refractories include calcium silicate materials, kaolin, and zirconia.

Insulating refractories are used to reduce the rate of heat loss through furnace walls. These refractories have low thermal conductivity due to a high degree of porosity, with a desired porous structure of small, uniform pores evenly distributed throughout the refractory brick in order to minimize thermal conductivity. Insulating refractories can be further classified into four types:[2]

1. Heat-resistant insulating materials with application temperatures ≤ 1100 ºC
2. Refractory insulating materials with application temperatures ≤ 1400 ºC
3. High refractory insulating materials with application temperatures ≤ 1700 ºC
4. Ultra-high refractory insulating materials with application temperatures ≤ 2000 ºC

Refractory anchorage

All refractories require anchorage systems such as wire formed anchors, formed metal (for example, hexmetal) or ceramic tiles to support the refractory linings. The anchorage used for refractories on roofs and vertical walls are more critical as they must remain able to support the weight of refractories even at the elevated temperatures and operating conditions.

The commonly used anchorages have circular or rectangular cross-sections. Circular cross-sections are used for low thickness refractory and they support less weight per unit area; whereas the rectangular cross-section is used for high thickness refractory and can support higher weight of refractory per unit area. The number of anchors depends on operating conditions and the refractory materials. The choice of an anchor's material, shape, quantity, and size has significant impact on the useful life of the refractory.

See also

• Fire brick
• Furnace
• Masonry oven
• Refraction (metallurgy)

References

1. Ailsa Allaby and Michael Allaby (1996). Concise Dictionary of Earth Sciences. Oxford Paperbacks Oxford University Press.
2. "Refractories and Classification of Refractories – IspatGuru". Retrieved 6 March 2020.
3. ASTM Volume 15.01 Refractories; Activated Carbon, Advanced Ceramics
4. Refractory Materials for Flame Deflector Protection System Corrosion Control: Similar Industries and/or Launch Facilities Survey - January 2009 - NASA
5. "How cool are refractory materials?" (PDF). The Journal of The Southern African Institute of Mining and Metallurgy. 106 (September): 1–16. 2008. Retrieved 22 April 2016.
6. Groover, Mikell P. (7 January 2010). Fundamentals of Modern Manufacturing: Materials, Processes, and Systems. John Wiley & Sons. ISBN 9780470467008.
7. Sonntag, Kiss, Banhidi, Weber (2009). "New Kiln Furniture Solutions for Technical Ceramics". Ceramic forum international. 86 (4): 29–34.CS1 maint: multiple names: authors list (link)
8. Roza, Greg (2009). Zirconium. The Rosen Publishing Group. ISBN 9781435850705.
9. Hugh O. Pierson (1992). Handbook of chemical vapor deposition (CVD): principles, technology, and applications. William Andrew. pp. 206–. ISBN 978-0-8155-1300-1. Retrieved 22 April 2011.
10. Hafnium, Los Alamos National Laboratory
11. McGraw-Hill encyclopedia of science and technology: an international reference work in fifteen volumes including an index. McGraw-Hill. 1977. p. 360. ISBN 978-0-07-079590-7. Retrieved 22 April 2011.
12. "Hafnium". Encyclopædia Britannica. Encyclopædia Britannica, Inc. Retrieved 17 December 2010.
13. Alaa, Hussein. "Introduction to Refractories" (PDF). University of Technology - Iraq.
14. "Accuratus". Aluminum Oxide, Al2O3 Ceramic Properties. 2013. Retrieved 22 November 2014.
15. Poluboiarinov, D. N. (1960). Vysokoglinozemistye keramicheskie i ogneupornye materialy. Moscow.
16. "Magnesite Refractories". www.termorefractories.com. Retrieved 6 March 2020.
17. "Dolomite brick and magnesia dolomite brick". www.ruizhirefractory.com. Retrieved 6 March 2020.
18. "Chromite Refractories". termorefractories.com. Retrieved 6 March 2020.