WO2001040136A2 - Refractory insulating construction element - Google Patents

Refractory insulating construction element Download PDF

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Publication number
WO2001040136A2
WO2001040136A2 PCT/GB2000/004565 GB0004565W WO0140136A2 WO 2001040136 A2 WO2001040136 A2 WO 2001040136A2 GB 0004565 W GB0004565 W GB 0004565W WO 0140136 A2 WO0140136 A2 WO 0140136A2
Authority
WO
WIPO (PCT)
Prior art keywords
construction element
binder
hollow microspheres
refractory material
refractory
Prior art date
Application number
PCT/GB2000/004565
Other languages
French (fr)
Other versions
WO2001040136A3 (en
Inventor
John Francis Coyne
Sasha Radwan
Emad Eldemallawy
Christopher Charles Nail
Gregory John Connor
Original Assignee
Foseco International Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foseco International Limited filed Critical Foseco International Limited
Priority to AU18706/01A priority Critical patent/AU1870601A/en
Publication of WO2001040136A2 publication Critical patent/WO2001040136A2/en
Publication of WO2001040136A3 publication Critical patent/WO2001040136A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to refractory insulating bricks, panels and other construction elements, for example used in the construction of furnace walls or other high temperature construction applications, for example heat resistant panels for fire protection and kiln furniture
  • refractory insulating bricks are often formed from clay mixed with sawdust or a polymer powder, the sawdust or polymer powder is burned away during the firing of the brick, thereby rendering the brick porous and hence insulating
  • the inventors of the present invention have found, however, that it is possible to produce exceptionally high quality refractory insulating bricks and other construction elements by adopting an entirely different approach to the materials and manufacturing techniques used for the construction elements
  • the present invention provides a refractory insulating construction element, comprising hollow microspheres of a refractory material bonded together by means of a binder
  • a method of producing a refractory insulating construction element comprising mixing together hollow microspheres of a refractory material and a binder, forming the mixture into the desired shape of the construction element, and firing the formed mixture at an elevated temperature
  • refractor/ is meant the ability to withstand high temperatures, for example temperatures of 800°C or more, preferably 1000°C or more, more preferably 1400°C or more.
  • insulating in the context of the present invention means a thermal conductivity at 1000°C of less than 1.0 W/mK, preferably less than 0.8 W/mK, more preferably less than 0.6 W/mK.
  • the present invention relates to bricks and other construction elements.
  • Such other construction elements include blocks, boards, panels, slabs, posts, and the like.
  • a typical use for construction elements according to the invention is in furnace walls and furnace internal constructions, but the invention is applicable to generally any construction application which requires the use of insulating construction elements which can withstand elevated temperatures.
  • the invention is applicable to heat resistant panels for fire protection, and kiln furniture.
  • the hollow microspheres used in the invention are normally formed as fly ash, and are often known as "fly ash floaters" since they are generally separated from the remainder of the fly ash by flotation in water tanks or dams.
  • Most microspheres are formed from alumina and/or silica - they normally comprise aluminosilicate, possibly with additional constituents.
  • the particle size (diameter) of the particles is normally in the range 5-500 ⁇ m, more commonly in the range 10-350 ⁇ m, and the shell thickness of each microsphere is normally in the range 5-15% (e.g. approximately 10%) of the diameter of the microsphere.
  • the hardness of the microspheres is generally 5 or 6 on the Mohs scale.
  • the hollow refractory microspheres are bonded together by means of a binder.
  • a particularly preferred binder is disclosed in co-pending international patent application no. PCT/GB00/03284, the entire disclosure of which is incorporated herein by reference.
  • the binder disclosed in that document comprises: (a) a particulate metal oxide that is capable of forming a metalate in the presence of an alkali, (b) an alkali, and (c) water.
  • An especially preferred form of the binder comprises silica (especially silica fume) as the metal oxide and sodium hydroxide as the alkali.
  • the construction element is generally produced by mixing together the refractory material and the binder, forming the mixture into the desired shape, for example in a mould, and allowing the binder to cure.
  • the construction element is preferably fired at an elevated temperature, for example 1000°C or higher.
  • a particularly preferred binder is the silica fume / sodium hydroxide binder disclosed in co-pending international patent application no. PCT/GB00/03284.
  • this binder is cured preferably by heating the formed mixture in an oven or furnace, either a conventional oven or furnace, or a microwave oven. If desired, the construction element may then be fired at a high temperature, for example 1000°C or higher.
  • the inventors have found that it is possible to tailor the qualities of the construction elements to meet particular requirements, by tailoring the composition of the construction element and/or its manufacturing method.
  • One of the qualities of the construction element which may be tailored is its density; low density, and hence lightweight, construction elements are often desirable, especially for use in furnaces, for example, because low density construction elements require less heat energy (and therefore time) to be heated to the working temperature of the furnace.
  • the construction elements tend to have a low density, preferably less than 500 kg/m 3 .
  • the density of the construction elements may be reduced by modifying their composition and/or their manufacturing technique.
  • one or more low density refractory materials may be used in addition to the hollow microspheres.
  • Preferred low density refractory materials include laminar materials, e.g. mica, perlite, vermiculite, etc.
  • the composition from which the construction element is formed may include one or more particulate combustible materials, e.g. sawdust and/or polymer powder (especially polyolefin, e.g. polyethylene, powder).
  • the average size of the particles of combustible materials is similar to that of the hollow microspheres, e.g. in the range 5-500 ⁇ m, more commonly in the range 10-350 ⁇ m.
  • the relative proportions of the refractory material (i.e. the hollow microspheres and the additional low density refractory material, where present) and the binder may be varied depending upon the application. However, preferably there is at least 5% binder, more preferably at least 8% binder (by weight, based on the total amount of binder plus refractory material only). Preferably there is no more than 25% binder, more preferably no more than 20% binder, for example 10-15% binder (by weight, based on the total amount of binder plus refractory material only).
  • Binder was made from equal parts (by weight) of silica fume powder and a 25% aqueous solution of sodium hydroxide.
  • a "binder premix” (the "Binder” referred to in Table 1 ) was made by mixing together equal parts of silica fume powder and a 25% aqueous solution of sodium hydroxide.
  • a refractory insulating brick according to the invention was then prepared by mixing together the aluminosilicate microspheres (also known as “cenospheres” or “flyash floaters”) with the binder premix. This mixture was then shaped (by means of a simple mould) into bricks and was dried in an air oven at 175°C for 90 minutes. The brick was then placed in a furnace and fired to 1000 °C.
  • the firing cycle was as follows: 200 °C for five hours, then 400 °C for five hours, then 600 °C for five hours, then 900 °C for five hours, and then 1000 °C for five hours. Finally the bricks were cooled to ambient temperature in three hours.
  • compositions B-D the perlite was mixed with the water. This was added after the binder premix and the alumino-silicate microspheres had been thoroughly mixed together.
  • the shaping, drying and firing processes were as descibed above.
  • Sample Bricks E-H are prior art samples, as follows:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

A refractory insulating construction element, for example a brick, comprises hollow microspheres of a refractory material, for example aluminosilicate, bonded together by means of a cured binder. The binder may be formed from silica fume and sodium hydroxide solution. The construction element may be used in the construction of furnace walls, for example.

Description

Refractory Insulating Construction Element
The present invention relates to refractory insulating bricks, panels and other construction elements, for example used in the construction of furnace walls or other high temperature construction applications, for example heat resistant panels for fire protection and kiln furniture
Conventionally, refractory insulating bricks are often formed from clay mixed with sawdust or a polymer powder, the sawdust or polymer powder is burned away during the firing of the brick, thereby rendering the brick porous and hence insulating
The inventors of the present invention have found, however, that it is possible to produce exceptionally high quality refractory insulating bricks and other construction elements by adopting an entirely different approach to the materials and manufacturing techniques used for the construction elements
According to a first aspect, the present invention provides a refractory insulating construction element, comprising hollow microspheres of a refractory material bonded together by means of a binder
According to a second aspect of the invention, there is provided a method of producing a refractory insulating construction element, comprising mixing together hollow microspheres of a refractory material and a binder, forming the mixture into the desired shape of the construction element, and firing the formed mixture at an elevated temperature
The inventors have found that by using hollow microspheres of a refractory material and a binder, it is possible to produce a construction element having exceptional qualities, for example crush strength, insulation and density Furthermore, the inventors have found that it is possible to tailor the qualities of the construction elements to meet particular requirements, by tailoring the composition of the construction element and/or its manufacturing method By the term "refractor/" is meant the ability to withstand high temperatures, for example temperatures of 800°C or more, preferably 1000°C or more, more preferably 1400°C or more. The term "insulating", in the context of the present invention means a thermal conductivity at 1000°C of less than 1.0 W/mK, preferably less than 0.8 W/mK, more preferably less than 0.6 W/mK.
As mentioned previously, the present invention relates to bricks and other construction elements. Such other construction elements include blocks, boards, panels, slabs, posts, and the like. A typical use for construction elements according to the invention is in furnace walls and furnace internal constructions, but the invention is applicable to generally any construction application which requires the use of insulating construction elements which can withstand elevated temperatures. For example, the invention is applicable to heat resistant panels for fire protection, and kiln furniture.
The hollow microspheres used in the invention are normally formed as fly ash, and are often known as "fly ash floaters" since they are generally separated from the remainder of the fly ash by flotation in water tanks or dams. Most microspheres are formed from alumina and/or silica - they normally comprise aluminosilicate, possibly with additional constituents. The particle size (diameter) of the particles is normally in the range 5-500 μm, more commonly in the range 10-350 μm, and the shell thickness of each microsphere is normally in the range 5-15% (e.g. approximately 10%) of the diameter of the microsphere. The hardness of the microspheres is generally 5 or 6 on the Mohs scale.
As already mentioned, the hollow refractory microspheres are bonded together by means of a binder. A particularly preferred binder is disclosed in co-pending international patent application no. PCT/GB00/03284, the entire disclosure of which is incorporated herein by reference. The binder disclosed in that document comprises: (a) a particulate metal oxide that is capable of forming a metalate in the presence of an alkali, (b) an alkali, and (c) water. An especially preferred form of the binder comprises silica (especially silica fume) as the metal oxide and sodium hydroxide as the alkali.
The construction element is generally produced by mixing together the refractory material and the binder, forming the mixture into the desired shape, for example in a mould, and allowing the binder to cure. The construction element is preferably fired at an elevated temperature, for example 1000°C or higher.
As mentioned above, a particularly preferred binder is the silica fume / sodium hydroxide binder disclosed in co-pending international patent application no. PCT/GB00/03284. When this binder is used, it is cured preferably by heating the formed mixture in an oven or furnace, either a conventional oven or furnace, or a microwave oven. If desired, the construction element may then be fired at a high temperature, for example 1000°C or higher.
It was also mentioned above that the inventors have found that it is possible to tailor the qualities of the construction elements to meet particular requirements, by tailoring the composition of the construction element and/or its manufacturing method. One of the qualities of the construction element which may be tailored is its density; low density, and hence lightweight, construction elements are often desirable, especially for use in furnaces, for example, because low density construction elements require less heat energy (and therefore time) to be heated to the working temperature of the furnace.
Because the invention uses hollow microspheres, the construction elements tend to have a low density, preferably less than 500 kg/m3. However, the density of the construction elements may be reduced by modifying their composition and/or their manufacturing technique. For example, one or more low density refractory materials may be used in addition to the hollow microspheres. Preferred low density refractory materials include laminar materials, e.g. mica, perlite, vermiculite, etc. Additionally or alternatively, the composition from which the construction element is formed may include one or more particulate combustible materials, e.g. sawdust and/or polymer powder (especially polyolefin, e.g. polyethylene, powder). When such compositions are fired, t e combustible material is burned away, leaving a network of pores in the finished construction element, in addition to the cavities present inside the hollow microspheres. Preferably, the average size of the particles of combustible materials is similar to that of the hollow microspheres, e.g. in the range 5-500 μm, more commonly in the range 10-350 μm.
The relative proportions of the refractory material (i.e. the hollow microspheres and the additional low density refractory material, where present) and the binder may be varied depending upon the application. However, preferably there is at least 5% binder, more preferably at least 8% binder (by weight, based on the total amount of binder plus refractory material only). Preferably there is no more than 25% binder, more preferably no more than 20% binder, for example 10-15% binder (by weight, based on the total amount of binder plus refractory material only).
The invention will now be described with reference to the following non-limiting examples.
Table 1
Figure imgf000005_0001
Note: Binder was made from equal parts (by weight) of silica fume powder and a 25% aqueous solution of sodium hydroxide.
Description of construction element (brick) production
A "binder premix" (the "Binder" referred to in Table 1 ) was made by mixing together equal parts of silica fume powder and a 25% aqueous solution of sodium hydroxide. A refractory insulating brick according to the invention was then prepared by mixing together the aluminosilicate microspheres (also known as "cenospheres" or "flyash floaters") with the binder premix. This mixture was then shaped (by means of a simple mould) into bricks and was dried in an air oven at 175°C for 90 minutes. The brick was then placed in a furnace and fired to 1000 °C. (The firing cycle was as follows: 200 °C for five hours, then 400 °C for five hours, then 600 °C for five hours, then 900 °C for five hours, and then 1000 °C for five hours. Finally the bricks were cooled to ambient temperature in three hours.)
For compositions B-D; the perlite was mixed with the water. This was added after the binder premix and the alumino-silicate microspheres had been thoroughly mixed together. The shaping, drying and firing processes were as descibed above.
Table 2 - Comparison of Density and Crush Strength of Fired Bricks
Figure imgf000006_0001
Sample Bricks E-H are prior art samples, as follows:
E: Thermal Ceramics K23
F: BNZ 23L
G: lsolite LBK 23 M
H: HRW Greenlite 23L
It can be seen from Table 2 that for Brick Samples A, B and C according to the invention, their cold crush strengths (as measured according to ASTM C 133 at 20°C) are very much greater than those of the prior art Sample Bricks E, F, G and H, even though the densities of Samples A, B and C are lower than those of the prior art samples. For Sample Brick D according to the invention, its cold crush strength is similar to those of the prior art samples, despite having a significantly lower density than the prior art samples. A low density is advantageous because the lower the density of a brick, the less heat energy is required in order to heat the brick to a particular temperature. Also, lower density bricks tend to have lower thermal conductivities, i.e. they tend to be more insulating. For example, Sample Brick A and prior art Sample Brick G have similar densities (470 kg/cubic metre and 500 kg/cubic metre, respectively) and their thermal conductivities are as follows:
Table 3 - Comparison of Thermal Conductivity of Fired Bricks
Figure imgf000007_0001
As can be seen from Table 2, however, the cold crush strength of Sample Brick A according to the invention is four times that of prior art Sample Brick G.

Claims

Claims
1. A refractory insulating construction element, comprising hollow microspheres of a refractory material bonded together by means of a cured binder.
2. A method of producing a refractory insulating construction element, comprising mixing together hollow microspheres of a refractory material and a binder, forming the mixture into the desired shape of the construction element, and allowing the binder to cure.
3. A method according to Claim 2, further comprising the step of firing the formed mixture at an elevated temperature.
4. A method according to Claim 3, in which the firing temperature is at least 1000 °C.
5. A method according to any one of claims 2 to 4, in which the binder is cured by heating the mixture to at least 150 °C.
6. A construction element or method according to any preceding claim, in which the hollow microspheres comprise alumina and/or silica, preferably aluminosilicate.
7. A construction element or method according to any preceding claim, in which the binder is formed from a metal oxide, an alkali, and water.
8. A construction element or method according to Claim 7, in which the metal oxide comprises silica, preferably silica fume.
9. A construction element or method according to Claim 7 or Claim 8, in which the alkali comprises sodium hydroxide.
10. A construction element or method according to any preceding claim, further comprising a low density refractory material in addition to the hollow microspheres.
11. A construction element or method according to Claim 11 , in which the low density refractory material comprises perlite.
12. A construction element or method according to any preceding claim, in which the construction element comprises a brick, a board, a panel, a block, a slab, or a post.
PCT/GB2000/004565 1999-12-02 2000-11-30 Refractory insulating construction element WO2001040136A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18706/01A AU1870601A (en) 1999-12-02 2000-11-30 Refractory insulating construction element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU6303999 1999-12-02
AU63039/99 1999-12-02

Publications (2)

Publication Number Publication Date
WO2001040136A2 true WO2001040136A2 (en) 2001-06-07
WO2001040136A3 WO2001040136A3 (en) 2002-10-17

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066916A2 (en) * 2001-02-19 2002-08-29 Dyson Industries Limited Kiln furniture
WO2007117225A1 (en) * 2006-04-11 2007-10-18 Trimo D.D. Inorganic filling for panel core and method for its manufacturing
WO2016145144A1 (en) 2015-03-10 2016-09-15 Pyrotek, Inc. Insulation material
CN107663085A (en) * 2016-07-29 2018-02-06 济源市涟源炉业有限公司 A kind of clay insulating refractory block NG120 0.6 and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1499804A (en) * 1974-12-17 1978-02-01 Hartfree A Thermally insulating and fire resistant compositions and articles made therefrom
GB1550184A (en) * 1976-07-13 1979-08-08 Redland Technology Ltd Method of forming a building product
EP0003403A1 (en) * 1978-01-31 1979-08-08 United Kingdom Atomic Energy Authority Thermally insulating, fire resistant material and its production
GB2041908A (en) * 1979-02-01 1980-09-17 Tarmac Building Products Ltd Insulating Material
GB2206345A (en) * 1987-07-01 1989-01-05 Applied Ultralight Technologie Lightweight fired building products
US5252526A (en) * 1988-03-30 1993-10-12 Indresco Inc. Insulating refractory
GB2348875A (en) * 1999-04-17 2000-10-18 Mahmoud Salem Lightweight composites containing cenospheres and a cementing agent or thermoplastic polymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1499804A (en) * 1974-12-17 1978-02-01 Hartfree A Thermally insulating and fire resistant compositions and articles made therefrom
GB1550184A (en) * 1976-07-13 1979-08-08 Redland Technology Ltd Method of forming a building product
EP0003403A1 (en) * 1978-01-31 1979-08-08 United Kingdom Atomic Energy Authority Thermally insulating, fire resistant material and its production
GB2041908A (en) * 1979-02-01 1980-09-17 Tarmac Building Products Ltd Insulating Material
GB2206345A (en) * 1987-07-01 1989-01-05 Applied Ultralight Technologie Lightweight fired building products
US5252526A (en) * 1988-03-30 1993-10-12 Indresco Inc. Insulating refractory
GB2348875A (en) * 1999-04-17 2000-10-18 Mahmoud Salem Lightweight composites containing cenospheres and a cementing agent or thermoplastic polymer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066916A2 (en) * 2001-02-19 2002-08-29 Dyson Industries Limited Kiln furniture
WO2002066916A3 (en) * 2001-02-19 2002-10-17 Dyson Ind Ltd Kiln furniture
WO2007117225A1 (en) * 2006-04-11 2007-10-18 Trimo D.D. Inorganic filling for panel core and method for its manufacturing
WO2016145144A1 (en) 2015-03-10 2016-09-15 Pyrotek, Inc. Insulation material
EP3268331A4 (en) * 2015-03-10 2019-01-23 Pyrotek, Inc. Insulation material
CN107663085A (en) * 2016-07-29 2018-02-06 济源市涟源炉业有限公司 A kind of clay insulating refractory block NG120 0.6 and preparation method thereof

Also Published As

Publication number Publication date
AU1870601A (en) 2001-06-12
WO2001040136A3 (en) 2002-10-17
ZA200204111B (en) 2003-07-30

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