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EP1044177A1 - Materiaux refractaires denses presentant une resistance amelioree aux chocs thermiques - Google Patents

Materiaux refractaires denses presentant une resistance amelioree aux chocs thermiques

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Publication number
EP1044177A1
EP1044177A1 EP98960906A EP98960906A EP1044177A1 EP 1044177 A1 EP1044177 A1 EP 1044177A1 EP 98960906 A EP98960906 A EP 98960906A EP 98960906 A EP98960906 A EP 98960906A EP 1044177 A1 EP1044177 A1 EP 1044177A1
Authority
EP
European Patent Office
Prior art keywords
zirconia
spinel
micro
matrix
crack
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP98960906A
Other languages
German (de)
English (en)
Inventor
Mark Trigg
Chull Hee Oh
Claude Urbani
Richard Hannink
Robert O'donnell
Merchant Yousuff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commonwealth Scientific and Industrial Research Organization CSIRO
Original Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO
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 Commonwealth Scientific and Industrial Research Organization CSIRO filed Critical Commonwealth Scientific and Industrial Research Organization CSIRO
Publication of EP1044177A1 publication Critical patent/EP1044177A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel

Definitions

  • a simple definition of a refractory material is one which resists the effects of high temperatures.
  • the term refractory material is applied to relatively low cost products that are used in many industrial processes, typically operating at high temperatures, to contain corrosive materials, such as molten metal and slags. As such refractories are an important class of materials .
  • Thermal Shock Dam ge Resistance Parameters (R) , a measure of a material's resistance to the above types of failure, were proposed by Hasselman (see Introduction to Ceramics, Kingery 2 nd edition 1976 pp 825-30) .
  • the physical properties required to compute Thermal Shock Damage Resistance Parameters are thermal conductivity k, thermal expansion coefficient ⁇ , Young's Modulus E, effective fracture energy ⁇ ⁇ £f , and strength (MOR) ⁇ .
  • the Thermal Shock Damage Resistance Parameters R' and R' ⁇ ⁇ can be expressed as:
  • R 1 is the parameter for the resistance to crack initiation and R' ' ' ' is the parameter for the resistance to crack propagation.
  • the material characteristics for inhibiting crack formation are high strength with respect to elastic modulus.
  • the requirements for minimising the extent of crack propagation are a high product of work of fracture and elastic modulus with respect to strength.
  • the design requirements for a material for inhibiting crack formation and crack propagation are different.
  • resistance to catastrophic failure which is required in refractory applications, can be improved by the introduction of enough cracks of sufficiently large size so that crack propagation takes place semi-statically. It is also known that, alternatively, resistance to catastrophic failure can be achieved by the introduction of micros ructural inhomogenieties in any form which serve as stress concentrators in the material . In this way, cracks will form locally, but catastrophic failure is avoided as a result of the small average stress in the material.
  • refractory materials are designed for chemical stability, thermal shock resistance, and cost. This is achieved through a compromise between reducing the effective surface area for attack and increasing resistance to crack propagation.
  • a conventional refractory material has an open structure with between 15 and 20% porosity. The open structure allows rapid penetration of slags and gases but inhibits crack propagation.
  • a schematic representation is shown in Fig. 1.
  • the essential features of the composite material disclosed in ⁇ S Patent 5,334,563 are that the material have less than 12% porosity and comprise:
  • each dispersed particle comprising an agglomerate of microcrystals which;
  • the alumina and the monoclinic zirconia being chemically inert with respect to each other within the temperatures used in practice.
  • the Garvie US Patent also discloses a number of other combinations, such as: mullite as the matrix and zirconia as the dispersed material; silicon nitride as the matrix and boron nitride as the dispersed material; barium titanate as the matrix and zirconia as the dispersed material; silicon carbide as the matrix and boron nitride as the dispersed material; alumina as the matrix and aluminium titanate as the dispersed material; spinel as the matrix and zirconia as the dispersed material; and fosterite as the matrix and zirconia as the dispersed material.
  • the basis of the Garvie ⁇ S Patent is the addition of a dispersed second phase in a continuous dense matrix with very particular inter-dependence of the respective thermal expansion coefficients of the phases.
  • the use of specific grades of monoclinic zirconia as the dispersed phase produced an enhanced dilatational/contractional mismatch in a number of matrices such as alumina or zircon.
  • An optimised composition, with respect to thermal shock damage resistance was determined empirically by Garvie to be 8% by weight of zirconia in alumina and 10% by weight in zircon.
  • substantially equal mechanical strength This is achieved by the addition of from 4 to 25 volume % zirconia grains ("embedment material") with a diameter from 0.3 to 1.25 ⁇ m in an anisotropic ceramic matrix, such as alumina.
  • the improvement in the properties of the fabricated products resulted, by way of example in the case of alumina with unstabilised zirconia, from the production of extremely fine micro-fissures and a high fissure density in the products. This was reported to significantly increase the toughness, thermal shock resistance and impact strength as compared to products prepared without the zirconia addition.
  • US Patent 4,804,644 of Anseau, Lawson and Slasor also discloses a material which includes dispersion of zirconia in a matrix, in this case an O'-sialon matrix.
  • O'-sialon is a solid solution based on silicon oxynitride (Si 2 N 2 0) where there is substitution of Al and 0 for Si and N respectively.
  • the US Patent discloses a number of methods for the preparation of such materials. However, for materials produced according to the methods the zirconia is in the tetragonal form. It is stated that improvements in properties would result from the transformation of meta- stable tetragonal zirconia to the monoclinic form in response to a tensile stress typically caused by an advancing crack tip.
  • the transformation results in the formation of compressive stresses that tend to close the cracks.
  • the zirconia is reported to be in the tetragonal form at room temperature.
  • the size of the particles must remain small to prevent spontaneous transformation on cooling. There is no report of the physical properties such as strength and thermal shock resistance of such bodies formed.
  • An object of the present invention is to provide a refractory material with enhanced corrosion, erosion and thermal shock resistance which alleviates the disadvantages of the known refractory materials discussed above.
  • the term "dense” is understood herein to mean that the refractory material has limited open porosity, typically less than 5% by volume.
  • a dense refractory material which includes a spinel matrix.
  • the spinel group of materials is understood herein to mean materials that are described by the general formula:
  • a 2+ is typically is either singly or in combination Mg, Fe, Zn and Mn and B 3+ is typically either singly or in combination Al, Fe, Cr and Mn.
  • spinels examples include magnesium aluminium oxide MgAl 2 0 4 , magnetite Fe 3 0 4 , and chromite FeCr 2 0 4 .
  • An example of a "mixed" spinel is Mg(Al,Fe) 2 0 4 .
  • the spinel group of materials have a cubic crystal structure and, therefore, are isotropic. As a consequence, the spinal microstructure is relatively stress-free.
  • the spinel group of materials is relatively stable at high temperatures and while maintained at temperature.
  • the spinel may include one or more additional elements.
  • the additional elements may include Li, Mg, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sr and Ba, for divalent cations and Al, Cr, Fe, and Mn as the trivalent cations.
  • spinel phases can exist over a range of compositions with respect to the ratio of the divalent to trivalent cations .
  • the additional elements may depend on a wide range of factors.
  • one factor is the environment in which the refractory material will be used. Specifically, in situations where the refractory material will be in contact with molten slag in metal smelting operations, the additional elements may be selected to optimise the chemical stability of the refractory materials with respect to the slag.
  • another factor is to include additional elements to assist in the manufacture of the refractory material as a dense refractory material .
  • spinels can exist over a range of composition without a change in phase.
  • magnesium aluminate spinel can be magnesium rich, stoichiometric (Mg to Al ratio of 1:2) or aluminium rich. This allows the loss of an element from the crystal lattice without decomposition to form a new phase or compound.
  • the formation of new phases can result in physical disruption of the refractory body or the formation of less refractory phases.
  • the ability of the spinel to adapt to the environment without a change in phase enhances the stability of the products.
  • spinels such as magnesium aluminium oxide MgAl 2 0 4 and chromite FeCr 2 0 4 spinels
  • MgAl 2 0 4 and chromite FeCr 2 0 4 spinels have excellent corrosion resistance to slags in metal smelting operations.
  • the spinels are coarse and are used as grits or aggregate in refractory bodies for many metal making and cement making operations and not as the matrix of a dense refractory material.
  • the refractories that incorporate these spinels are in the form of traditional refractories that are characterised by open porosity and are not dense refractory materials.
  • the disclosure is speculative and not supported by examples . It is preferred that the refractory material further comprises a micro-crack initiating phase dispersed in the matrix.
  • micro-crack initiating phase be no more than 15% by volume of the material.
  • micro-crack initiating phase be no more than 10% by volume of the material.
  • the spinel matrix be at least 80% by volume of the material.
  • micro-crack initiating phase comprises a dispersion of single crystals.
  • micro-crack initiating phase be formed from zirconia.
  • the zirconia have a particle size in the range of 5 to 50 ⁇ m.
  • the zirconia be fused zirconia.
  • the micro-crack initiating phase may be formed from any other suitable material, such as boron nitride and silicon carbide.
  • the spinel be manufactured from low cost precursors .
  • a dense refractory material which includes a spinel matrix and a micro-crack initiating phase dispersed in the matrix.
  • the method further includes the step of mixing the spinel material produced in step (ii) with an additive, such as zirconia, selected to form a micro-crack initiating phase dispersed in the fired product.
  • an additive such as zirconia
  • the spinel material is formed by reaction of the precursor oxides . This is typically carried out in the temperature range of 800°C to 1600°C and preferably in the range of 1000°C to 1400°C for dwell times at temperature ranging up to at least 10 hours. Longer times are generally preferred for lower calcination temperatures and shorter times for temperatures in the upper reaches of the range. Dwell times of 1 hour or less are possible for higher temperatures in the range.
  • the spinel material formed is then milled (if necessary) to form a finely divided powder suitable for densification in the secondary heat treatment of step (iv).
  • the average particle size should be less than 10 ⁇ , preferably less than 5 ⁇ m and more preferably less than 2 ⁇ m.
  • the additive which forms the dispersed phase is then added to the spinel powder.
  • the spinel powder and the additive are then moulded or formed into the desired shape in a green form in step (iii) .
  • This can be done with and without the use of additives to increase the plasticity of the powder facilitating forming into the desired "green" shapes.
  • the green shape is then heated to effect densification in the firing step (iv) .
  • This is typically carried out in the temperature range of 1000°C to 1800°C and preferably in the range of 1400°C to 1600°C for dwell times at temperature ranging up to at least 10 hours . Longer times are generally preferred for lower secondary heating temperatures and shorter times for temperatures in the upper reaches of the range. Dwell times of 1 hour or less are possible for higher temperatures in the range. Temperatures can also be reduced by use of sintering assists that can be incorporated into the structure of the spinel. However, it is preferable that the firing temperature used in the manufacture be at least as high as the expected operating temperature where the refractory is to be used.
  • Appropriate sintering aids may be used to promote densification at lower temperatures without a loss of performance.
  • the firing cycle of refractory materials can represent a substantial proportion of the cost to manufacture products . Reducing the firing temperature can result in a lower cost to manufacture products.
  • improved chemical stability is obtained by using a matrix material that contains the main elements of the slag in a solid solution within the crystal structure of the matrix phase or where stable phases are produced as a result of the interaction of elements in the slag with the matrix.
  • the additional elements may include Li, Mg, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sr and Ba, for divalent cations and Al, Cr, Fe, and Mn as the trivalent cations.
  • spinel phases can exist over a range of compositions with respect to the ratio of the divalent to trivalent cations.
  • the present invention overcomes the problems of obtaining low cost refractory materials with high erosion and corrosion stability.
  • a feature of the present invention is the tolerance to impurities and the fact that low cost refractory grade precursors can be used. This allows the use of low cost refractory precursors. It is speculated that the finer fractions of the zirconia materials used are able to react with impurities to produce more refractory phases .
  • the body disclosed by Claussen and Steeb is substantively different to that in the present invention.
  • the Claussen and Steeb body retains high fracture strength and fracture toughness . This is achieved by the requirement for the use of a large vol% of micron and preferably sub- micron zirconia material .
  • the materials produced according to the teachings of the present invention are for refractory type applications. A requirement for this type of material is relatively low cost. This typically means below US$5,000 per tonne for the finished product. Such a final price requires the use of inexpensive raw materials. Sub-micron zirconia powders are expensive.
  • the object of the Examples 1-9 was to compare the performance of a micro-crack toughened refractory material in accordance with the present invention which includes a low cost single crystal fused zirconia (AFM Grade 3) dispersed phase with a known micro-crack toughened composite material based on agglomerates of monoclinic zirconia (MEL S) proposed by Garvie.
  • AFM Grade 3 low cost single crystal fused zirconia
  • MEL S monoclinic zirconia
  • the batch size was a nominal 200g.
  • the batches containing MEL S were designated Examples 1-5 and 6-9 for the AFM containing range.
  • the starting compositions are given in the following table.
  • the alumina powder was combined with zirconia in the proportions given using the milling conditions as outlined in the following table.
  • the objective for all batches was to thoroughly distribute the Zr0 2 rather than reduce the particle size. See the following table for details. Ball Milling Conditions
  • the resultant slurries were dried at 80°C. Segregation of the constituents was avoided by ensuring that slurry viscosity remained high and by use of a shallow drying pan. Bars were pressed from the dried powder with a geometry suitable for strength testing (MOR) , Young's Modulus and work of fracture testing (WOF) . These were formed by die pressing at a pressure of 55MPa with a bar die of dimensions 5 x 51mm for MOR bars and 7.5 x 102mm for WOF bars . The bars were then bagged and cold isostatically pressed to a pressure of 210MPa. The samples were fired in air on an alumina setter plate. The firing cycle used is given in the following table:
  • Young's Modulus For the determination of Young's Modulus, the ends of the WOF bars were ground square . Young ' s Modulus was determined by a Transient Vibration Method (ASTM Standard C1259-94) of a right prismatic beam in the flexural mode. Densities were determined by the direct measurement method. The results are presented in the following table.
  • the MEL S material was more effective in forming micro-cracks at lower levels of addition as compared to the AFM ZC03 material.
  • the particle size of the two zirconias was determined (see following table) .
  • Examples 10/11 was to investigate the performance of a micro-crack toughened refractory material having a spinel matrix in accordance with the present invention produced by the method of the present invention from relatively low cost raw materials.
  • a cup test was used to evaluate the material in contact with both metal and slag.
  • the raw materials used to manufacture the cups are given in the following table.
  • KA13 alumina is also a refractory grade precursor.
  • the price of KA13 alumina is roughly an order of magnitude less than A1000 alumina as used in Examples 1 to 9.
  • the starting compositions are given in the following table.
  • Mg source was added as MgC0 3
  • the alumina and magmesite were ball milled (see table)
  • the water was removed by pan drying at 80°C.
  • the dried cake of agnesite and alumina were calcined at 1400°C to decompose any carbonates or hydroxides present (see table) and to form a spinel.
  • the zirconia was added to the slurry after milling and immediately prior to spray drying.
  • the zirconia addition to the slurry was at a level of 4 volume % (6.3 weight %) .
  • the slurry was continuously stirred prior to spray drying to minimise the effects of settling.
  • the performance of these materials was excellent with very low dimensional change observed after the test.
  • the cups were essentially single phase materials with the iron incorporated into the crystal structure of the spinel. There was little slag penetration into the crucibles. Both metal and slag were detected after the test.
  • Examples 12/13 was to investigate the effect on performance of variations in composition of the spinel matrix of micro-crack toughened refractory materials in accordance with the present invention.
  • the raw materials used were as follows:
  • the Causmag was crushed in a ring mill to produce an agglomerated powder less than 75 ⁇ m in size.
  • the starting compositions are given in the following table.
  • the final composition after the total process is given under the "Comments" column.
  • the alumina and magnesite were mixed in a ball mill (see table) .
  • the water was removed by pan drying.
  • the dried cake of magnesite and alumina were calcined at 1400°C to decompose any carbonates or hydroxides present and to form a spinel using the conditions as disclosed in Examples 10 and 11.
  • the spinel was crushed to produce a powder with a d 50 less than 5 ⁇ m.
  • the milling conditions used were as follows:
  • the slurry was spray dried. During spray drying, the slurry was continuously stirred to minimise the effects of settling.
  • Wet bag cold isostatic pressing (CIP) techniques were used to fabricate the cups and lids as described in Examples 10 and 11 from the dried powder. The firing cycle used to densify the test cups and lids was the same as described for Examples 10 and 11.
  • the raw materials used were as follows :
  • the Causmag was used as supplied.
  • the particle size of the as-received powder was less than 75 ⁇ m in size.
  • the starting composition is given in the following table.
  • the composition after calcination is also given in brackets.
  • the alumina and magnesite were mixed in a ball mill (see table) .
  • the water was removed by pan drying.
  • the dried cake of magnesite and alumina was calcined at 1400°C to decompose any carbonates or hydroxides present and to form a spinel .
  • the firing cycle used was the same as disclosed in Examples 10 and 11.
  • the powder was milled using the following conditions:
  • the zirconia was added to the slurry after milling and immediately prior to spray drying.
  • the zirconia addition to the slurry was at a level of 8 weight%.
  • the slurry was continuously stirred prior to spray drying to minimise the effects of settling.
  • Examples 15-17 was to investigate the chemical stability of refractory materials having a spinel matrix in accordance with the present invention.
  • the calcined magnesite, alumina and silica precursors were mixed in a ball mill (see table) .
  • the powder was pan dried at 80°C to remove the fluid. Bars of nominal fired dimensions 20 mm long and with a square cross section of 5 mm were fabricated by uniaxial pressing the powder in a steel die followed by cold isostatic pressing using wet bag techniques at a pressure of 210 MPa. Samples were densified using the firing cycle as outlined in Examples 10 and 11. The fired bulk densities obtained after firing are given in the following table.
  • the test consisted of placing a sample in a crucible and surrounding with pre- mixed slag. The crucible was removed and the sample extracted from the slag at temperature. Details of the test are summarised in the following table.
  • the slag was the same as used in Examples 10 and 11. After the slag test, the degree of slag penetration increased in the order of Example 17 > Example 16 > Example 15.
  • the objective of the example was to investigate the firing temperature required to produce a refractory material having a spinel matrix in accordance with the present invention.
  • the magnesium carbonate was calcined at 900°C to decompose the carbonate and hydroxides present before use.
  • the starting compositions are given in the following table:
  • a vibro milling techniqrue was used for mixing and particle size reduction of the alumina, (see table) .
  • the powder was pan dried at 80°C to remove the fluid. Discs with a nominal green diameter of 25 mm and mass of 10 g were fabricated. Samples were produced using uniaxial pressing in steel dies followed by cold isostatic pressing using wet bag techniques at a pressure of 210 MPa. The firing cycle as described in Examples 10 and 11 was used for the densification of the samples with the exception of the maximum temperature and dwell times.
  • the objective of the example was to investigate the density of micro-crack toughened refractory materials having a dispersed single crystal phase in a spinel matrix in accordance with the present invention.
  • the raw materials used were as follows:
  • the Causmag was used as supplied.
  • the particle size of the as-received powder was less than 75 ⁇ m in size.
  • the starting composition is given in the following table.
  • the composition after calcination is also given in brackets.
  • the alumina and magnesite were mixed in a ball mill (see table) .
  • the water was removed by pan drying.
  • the dried cake of magnesite and alumina was calcined at 1400°C to decompose any carbonates or hydroxides present and to form a spinel .
  • the calcination cycle used was the same as used in Examples 10 and 11. After calcination, the powder was milled using the following conditions :
  • the zirconia was added to the slurry after milling and immediately prior to spray drying.
  • the zirconia addition to the slurry was at a level of 5.1 volume % (8.0 weight%) .
  • the slurry was continuously stirred prior to spray drying to minimise the effects of settling.
  • Examples 20/21 was to investigate the effect of variations in composition of the spinel matrix and firing temperature on the density of micro-crack toughened refractory materials in accordance with the present invention.
  • the Causmag was crushed in a ring mill to produce a powder with a particle size less than 75 ⁇ m.
  • the final composition after the total process is given under the Comments column.
  • the magnesite, alumina and ferric oxide were ball milled (see table) .
  • the zirconia was added to the slurry after milling and immediately prior to spray drying.
  • the zirconia addition to the slurry was at a level of 4 volume % (6.3 weight%) .
  • the slurry was continuously stirred prior to spray drying to minimise the effects of settling.
  • the overall starting compositions are given in the following table: Overall Compositions in Weight Percent%
  • Discs were fabricated by die pressing followed by bagging and wet bag cold isostatic pressing at pressure of 210 MPa. The samples were fired using the following firing cycle except for 2Of and 2If which used the firing cycle as disclosed for Examples 10 and 11.
  • Examples 22 to 40 was to investigate the beneficial effect on densification of selected sintering aids for the spinel matrix of micro-crack toughened refractory materials in accordance with the present invention.
  • the Causmag was crushed in a ring mill to produce an agglomerated powder less than 75 ⁇ m in size.
  • the starting compositions are given in the following table. Starting Composition of the Spinel in Parts
  • the alumina and magnesite were mixed in a ball mill (see table) .
  • the water was removed by pan drying.
  • the dried cake of magnesite and alumina were calcined at 1400°C to decompose any carbonates or hydroxides present and to form a spinel using the conditions as disclosed in Examples 10 and 11.
  • the spinel was crushed to produce a powder with a d 50 less than 5 ⁇ m.
  • the milling conditions used were as follows:
  • the zirconia powder was added just 15 minutes before the end of milling to prevent any decrease of zirconia particle size.
  • the concentration of zirconia was 8 wt% of the total batch. Milling Conditions for Mixing Powders
  • the slurry including the media was poured from the milling containers into glass containers .
  • the liquid was removed by pan drying in vacuum at 70 °C for 20 h.
  • the powder was passed through two sieves with a grid size of 4000 ⁇ m and 600 ⁇ m.
  • Pellets were fabricated from the granulated powder batches.
  • the fired pellets were a nominal 20 mm in diameter with a nominal mass of 10 g for densification studies and bars nominally 20mm long by 5 mm by 5mm.
  • the samples were uniaxially pressed followed by wet bag cold isostatic pressing at 210 MPa.
  • the maximum temperatures evaluated for the density studies were 1400°C, 1500°C, 1600°C and 1700°C. Samples for the dip test were sintered at 1700°C.
  • the raw materials were treated prior to use.
  • the alumina powder was dried at 120°C for approximately 16 hours.
  • the magnesite was calcined to remove any carbonates and hydroxides present .
  • the dried alumina powder was combined with the magnesium oxide produced from the calcination process in proportions given in the following table.
  • the mills were removed from the rack, opened and the Zr0 2 added.
  • the mills were then returned to the rack and given an additional 30 minutes of rotation, the objective being to thoroughly distribute the Zr0 2 rather than reduce the particle size.
  • the quantities of the MEL Grade S Zr0 2 added are given in the table.
  • the slurries were separated from their respective milling and the slurries dried in a vacuum oven at 80°C and 200kPa. Segregation of the constituents was avoided by ensuring that the slurry viscosity remained high and by use of a shallow drying pan. Drying time was ⁇ 24hours for all batches .

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Abstract

La présente invention décrit un matériau réfractaire dense qui comprend une matrice de spinelle et une phase d'initiation de micro-fissure dispersée dans la matrice. Le matériau d'initiation de la micro-fissure introduit des micro-fissures dans le matériau réfractaire ce qui inhibe toute défaillance catastrophique résultant des effets du choc thermique. L'invention concerne aussi un procédé de fabrication d'un matériau réfractaire dense qui comprend des étapes consistant à mélanger des oxydes précurseurs d'un matériau de spinelle, à calciner le matériau, à former le matériau de spinelle à l'état vert du produit et à cuire le matériau dans cet état pour obtenir le produit final.
EP98960906A 1997-12-18 1998-12-18 Materiaux refractaires denses presentant une resistance amelioree aux chocs thermiques Withdrawn EP1044177A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPP0990A AUPP099097A0 (en) 1997-12-18 1997-12-18 Dense refractories with improved thermal shock resistance
AUPP099097 1997-12-18
PCT/AU1998/001049 WO1999032417A1 (fr) 1997-12-18 1998-12-18 Materiaux refractaires denses presentant une resistance amelioree aux chocs thermiques

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EP1044177A1 true EP1044177A1 (fr) 2000-10-18

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EP (1) EP1044177A1 (fr)
JP (1) JP2001526175A (fr)
AU (1) AUPP099097A0 (fr)
CA (1) CA2315398A1 (fr)
WO (1) WO1999032417A1 (fr)
ZA (1) ZA9811550B (fr)

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KR102053603B1 (ko) 2015-06-01 2019-12-09 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 내화성 물품 및 이의 형성 방법
CN113061045B (zh) * 2021-04-21 2022-10-04 营口丰华耐火材料有限公司 一种水泥窑烧成带用镁铁锌铝复合尖晶石耐火砖及其制备方法
CN113526946B (zh) * 2021-08-27 2023-03-03 郑州中本耐火科技股份有限公司 高韧性的改性硅刚玉砖
CN115745598A (zh) * 2022-11-16 2023-03-07 浙江上硅聚力特材科技有限公司 一种钛酸铝陶瓷升液管的制作工艺

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JP2001526175A (ja) 2001-12-18
CA2315398A1 (fr) 1999-07-01

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