CN100528807C - Ceramic batch and associated product for fireproof applications - Google Patents
Ceramic batch and associated product for fireproof applications Download PDFInfo
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- CN100528807C CN100528807C CNB2005800144882A CN200580014488A CN100528807C CN 100528807 C CN100528807 C CN 100528807C CN B2005800144882 A CNB2005800144882 A CN B2005800144882A CN 200580014488 A CN200580014488 A CN 200580014488A CN 100528807 C CN100528807 C CN 100528807C
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- 239000000919 ceramic Substances 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 77
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 70
- 239000000395 magnesium oxide Substances 0.000 claims description 42
- 230000009970 fire resistant effect Effects 0.000 claims description 39
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 38
- 239000011029 spinel Substances 0.000 claims description 19
- 229910052596 spinel Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000011044 quartzite Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 229910001677 galaxite Inorganic materials 0.000 claims description 2
- 239000010443 kyanite Substances 0.000 claims description 2
- 229910052850 kyanite Inorganic materials 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229910052851 sillimanite Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000011269 tar Substances 0.000 claims description 2
- -1 andaluzite Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 238000004079 fireproofing Methods 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 86
- 238000007669 thermal treatment Methods 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 208000037656 Respiratory Sounds Diseases 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 230000001464 adherent effect Effects 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011449 brick Substances 0.000 description 7
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052863 mullite Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 210000003041 ligament Anatomy 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- 229910021493 α-cristobalite Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910021494 β-cristobalite Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 241000294743 Gamochaeta Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910000500 β-quartz Inorganic materials 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 101100129500 Caenorhabditis elegans max-2 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910000754 Wrought iron Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012628 flowing agent Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229920003986 novolac Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910021489 α-quartz Inorganic materials 0.000 description 1
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- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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Abstract
Ceramic batch for fireproofing applications comprises (wt.%):at least one refractory base (83-99.5) in a grain fraction of less than 8mm, at least one separate SiO2 carrier (0.5-12) and other constituents. The invention also relates to a product based on the batch.
Description
The present invention relates to a kind of ceramic batch and be suitable for the related products of refractory applications.
The ceramic batch that contains fire-resistant base material is used to prepare refractory ceramic product, and can be used for many technical fields, especially for the lining of lining cutting and repairing metallurgic furnace or industrial furnace.In addition, this class base material also is used to prepare so-called functional product, for example is used for mouth mouth, dipping tube, blind pipe, flashboard etc., and it is required in described melting plant and smelting furnace.
Fire-resistant base material is that alkaline species also can be non-alkaline species.MgO, particularly MgO sinter are the main components of all MgO products and MgO-spinel product.The principal constituent periclasite of MgO sinter.The main basic raw material of preparation MgO sinter is that magnesite is magnesiumcarbonate or synthetic magnesium oxide source.
For regulating some material behavior, special agent is for improving the chemical resistance to slag, improve ductility and resisting temperature alternation performance and thermotolerance, the various refractory batchings that known and various additives are combined can be produced product corresponding non-shaping or that be shaped by these batchings.
Comprising the chrome ore that for example is used to prepare so-called magnesium ferrochrome brick (Magnesiachromitsteine).Its advantage is that comparing with pure magnesia brick has lower fragility (or higher ductility).But more and more need not contain Cr
2O
3The fire-resistive construction material, to avoid forming toxicity Cr
6+Possibility.
The various batchings of oxygen-free chromium have been proposed for this reason.Disclosed this batching is made up of the spinel of the Herzynit type of the MgO sinter of 50-97 weight % and 3-50 weight % among the DE 4403869C2.Compare with pure MgO product, the product that is fired into by this batching has the fragility that reduces.
The product of non-shaping is formed by batching as the casting material, and this batching is by water or other liquid and randomly form the required processing denseness with certain viscosity by additive (as binding agent, liquefying agent, dispersion agent).Then this material is directly processed with monoblock material form, as be processed into the lining of metallurgic furnace, or use this material and prepare so-called finished product member.In the case, this batching also can itself or process with some additive is combined, as be molded into mould.
Comprise also under the situation of refractory concrete material that at above-mentioned casting material can crack when then carrying out drying and/or contraction in sintering process subsequently, this crackle has reduced the work-ing life of furnace lining or finished product member.
This crackle often occurs under the situation of the casting hot metal ladle of using with non-alkalescence casting material lining cutting Iron And Steel Industry.For resisting this crackle, the material that forms spinel is used in suggestion in the prior art.Cause that when forming spinel volume increases, thereby hinder drying shrinkage.But being everlasting, the formation of crackle just takes place under the temperature that is lower than spinel formation.Can not reach required than the long life.
Basically be suitable for based on MgO and the combined the said products of various spinel.But introduced additional oxide compound by introducing spinel in this batching, this causes the thermotolerance of roasting product to descend.For example containing additive MgAl
2O
4The situation of magnesia brick under, the invariant point i.e. temperature that forms mutually of first melt only is 1325 ℃.Particularly rich calcium penetrant such as basic slag or concrete slag can reduce thermotolerance and work-ing life.
Under the shaping prod situation of roasting, above-mentioned influence (as the erosion of slag, temperature variation etc.) also regular meeting causes refractory products insufficient work-ing life.This is specially adapted to for example estimate to have the application of mechanical stress or thermal and mechanical stress.It comprises device that periodically alternately distortion the occurs refractory liner as the revolvig tubular kiln that is used to prepare cement.But in the furnace apparatus of steel metal industry and non-ferrous metal industry, also need to have the refractory products of the fragility that reduces " flexible " of raising (or have).
These problems are more serious than non-basic material under basic material.This mainly is because non-basic prod have lower thermal expansion and certain glassy phase content usually.
At last, fragility is known can sneak into the stabilized zirconium white (zirconium dioxide of granulous in batching in order to reduce; ZrO
2).Its shortcoming is that the fragility that only reaches less reduces, and ZrO
2The price height.
The object of the present invention is to provide a kind of ceramic batch and its related products, this product has above-mentioned required characteristic concurrently.Particularly the product of being made by this batching should have the fragility (improved ductility) that reduces, good thermal shocking, favourable thermotolerance and most probable erosion resistance when using, and the while low cost of manufacture.Term " product " particularly comprises deformed product and shaping prod (before application through thermal treatment with without thermal treatment), sintered products and in use through the product of thermal treatment (heating) herein.
The present invention is based on following discovery, make it only in structure, form tiny crack, then can obviously reduce the fragility of refractory products or be intended for the fragility of the product of refractory applications if promptly avoid forming visible (big) crackle of macroscopic view and regulate this system for this reason.This can be by adding independent SiO in batching
2Carrier reaches.Though this method has increased crack density (for example the crackle numerical table with single every square metre of surface shows), this crackle has much smaller crackle width (particularly＜20 μ m), and is therefore obviously little than macroscopical visible crack of prior art products.These tiny cracks are not to having a negative impact equally the work-ing life of product.These products also more tolerate the thermal and mechanical stress when using, as the thermal and mechanical stress that produces by thermal shocking.Because SiO
2Carrier also remains independent basically component and does not form the melt phase after thermal treatment, so still kept the effect that tiny crack forms after thermal treatment.
By the present invention, the physics of structure changes can be by adding the independent granular SiO of a certain amount of ratio
2Carrier reaches.Term " SiO herein
2Carrier " comprise all crystalline SiO that at room temperature has enough stability
2Variant.Mainly comprise cristobalite (β-shape) and tridymite (γ-tridymite).The SiO that another is possible
2Variant is a coesite.Quartzy (β-shape) or quartz ware also can be used as SiO
2Carrier.Also can use by described SiO
2The material that base material was handled by physics and/or chemical technology (preprocessing).For example quartz can be ground, closely knit, sintering and then be processed into suitable granularity.Can be to SiO
2Carrier carries out pre-treatment or processing, and crude density is reduced to＜2.65g/cm
3, for example be reduced to 2.2-2.5g/cm
3Can further change this SiO by sneaking into as CaO
2The chemical constitution of carrier.
Tiny crack forms by crystalline SiO
2The Nonlinear thermal of carrier when changing mutually expands and causes.This change mutually be for example in the time of 573 ℃ β-quartz to the transformation mutually of alpha-quartz and above 1050 ℃, through the β-quartz under 1250 ℃ of being everlasting to the transformation mutually of α-cristobalite, β-cristobalite has been transformed into α-cristobalite in the time of 270 ℃, at this moment also with volumetric expansion.Therefore after the drying under 380 ℃, just see required effect in the product of embodiment 5 below.
In the most common embodiment, the present invention relates to comprise the ceramic batch that is suitable for refractory applications of following component:
The fire-resistant base material of at least a grade＜8mm of A:83-99.5 weight %,
At least a independent granular SiO of B:0.5-12 weight %
2Carrier and
C: possible rest materials; Other component.
This batching can only be made up of component A and B.
Described fire-resistant base material can be alkaline matter such as calcined dolomite (being the rhombspar after the roasting) or magnesium oxide (being MgO), or nonbasic substances is as based on Al
2O
3Or ZrO
2Material.
By a kind of embodiment, the content of fire-resistant base material is 90-99 weight %.Granular SiO
2The content of carrier by total proportion meter for example be 〉=1 and/or≤7 weight %, its upper limit also can be＜5 weight % or＜4 weight %.
By existing result of study, by fire-resistant base material such as MgO base material and crystalline SiO
2During the thermal treatment (particularly roasting) of the mixture that carrier is formed after batching is shaped at SiO
2The variation of carrier can cause when changing expanding, and produces the tiny crack in the structure thus.This tiny crack is the reason that fragility reduces.
Different with the magnesium oxide product that contains spinel additive such as Herzynit, adding crystalline SiO
2It is to take place between the heating period of sintering procedure that tiny crack during carrier forms, and in the prior art, tiny crack forms and during cooling finds.
Using glassy SiO
2During carrier (quartz ware), crackle forms the big drying shrinkage that is based on fire-resistant basal component when firing postcooling.
By independent granular SiO
2It is irrelevant with raw material (fire-resistant basal component) basically that carrier causes the principle of tiny crack, thus this principle can be applicable to ceramic adherent, chemical adhesion, carbon adherent, water adherent, fire-resistant batching and product shaping and deformed, annealed, roasting and not roasting.
Temperature can be to select SiO
2The criterion of carrier.
Therefore, for example under the finished product member of stating, casting material or carbon adherent refractory products situation, user's spar is as SiO
2Carrier is suitable.With this method, for example when casting material, heating can form required tiny crack at low-down temperature levels.Can avoid deleterious cup shake thus.
This for example also is applicable to the drying or the sclerosis (annealing) synthetic resin-bound or pitch adherent refractory products of monoblock material.
The important kind that is suitable for the present invention's application is non-shaping prod, for example is used to prepare the concrete materials or the casting material of refractory liner or finished product member.These materials can promptly for example be based on the material of cement, particularly high-alumina cement through water hardening or half water hardening.The present invention also can be applicable to the casting material of poor-water mud or non-cement, as based on the material of bauxitic clay as the fire-resistant base material of non-alkalescence.
For reaching required processing denseness, can mix with the required water yield doing batching (as the batching of forming by alumina and cristobalite).Add additive such as flowing agent when needing.Promptly taken place described between dry epoch from of the transformation of β-cristobalite to α-cristobalite since 270 ℃.
The grade of the described mode of action and fire-resistant basal component is irrelevant substantially.But the low levels of little maximum particle size (as 2mm) or coarse fraction (as 2-4mm) may be unfavorable to reducing fragility.However, if SiO
2The granularity d of carrier
50Or d
05Largest particle (or greater than at least 95 weight %) greater than particulate part of this fire-resistant base material then proves favourable.It is corresponding to the SiO of 50 or 95 weight %
2Carrier is greater than the fine particle of this fire-resistant base material of 95 or 100 weight %.
This fire-resistant base material is used with the particle spectrum of broad usually.Except that coarse particles part (＜8mm) as the 1-6mm, this component also can contain medium grain part such as 0.25-＜1mm and＜fine particle part (powder composition) of 0.25mm.
Granularity limit value between coarse particles and the medium grain also can be 1.5 or 2mm.Powder grain part also can for example be defined as＜particle size fraction of 0.125mm (125 μ m).
By various embodiments, the aforementioned fine particle content of fire-resistant base material is counted 10-30 weight %, 15-25 weight % or 25-30 weight % by total batching.The order of magnitude of foregoing medium grain content can for example be 5-30 weight %, 10-25 weight % or 10-20 weight % by total proportion meter.Content by above-mentioned fine particle or medium grain can corresponding calculating coarse particles content.
By another embodiment, the suggestion of the size distribution of fireproof, particularly oxidisability base material is as follows:
50-60 weight % is 1-6mm,
10-25 weight % is 0.25-＜1mm,
25-30 weight % is＜0.25mm,
Total amount is 100 weight %.
By a kind of embodiment, granular SiO
2The granularity of carrier is no more than 6mm, and this particulate higher limit also is chosen as 3.0 or 1.5mm, and the particle lower limit also is chosen as 0.25,0.50,1 or 2mm.SiO
2The grade of carrier is generally 0.5-3mm.Compare with particle less than 1mm, the increase of granularity under the same amount situation (＞1mm) can cause more high-efficiency among the present invention.Therefore the particle of 1-2mm is more effective than the particle of 0.5-1mm.
Can select at least a in the following component for use as the fire-resistant base material of non-alkalescence: fireclay, sillimanite, andaluzite, kyanite, mullite, bauxitic clay, corundum starting material such as white fused alumina or brown corundum, tabular alumina, Calcined polishing aluminum oxide, contain zirconic base material such as zirconium mullite, zircon corundum, zirconium silicate or zirconium white, titanium oxide (TiO
2), Mg-Al spinel, silicon carbide.
Also can use quartzite as fire-resistant base material, at this moment user's diamond stone, tridymite, coesite and/or above-mentioned through pretreated SiO
2Carrier is as additive.
Use the MgO base material of the MgO content that contains 83-99.5 weight % as the fire-resistant base material ad hoc proposal of alkalescence.By various embodiments, following 85,88,93,94,95, the 96 or 97 weight % that are limited to of MgO content, on be limited to 97,98 or 99 weight %.
By a kind of embodiment, MgO content is 94-99 weight %, or 96-99 weight %.
The MgO base material can be made up of sintered magnesia, melt oxidation magnesium or its mixture.
By a kind of embodiment, the MgO content of batching can be provided by Herzynit type spinel, galaxite type spinel or its mixture of 3-20 weight % (or 3-10 weight %) by total mixture.In the case, by granular SiO
2The tiny crack that carrier caused in heating period can be replenished by other tiny crack that spinel components in the cooling stage of pyroprocess produces.
In addition, described batching can contain more a spot of other composition, for example at least a following component: (element) carbon, graphite, resin, pitch, carbon black, coke, tar.
Therefore, this batching can be used for preparing carbon adherent product.The product that particularly this batching can be used for carbon adherent product or tar dipping.
So-called ASC product belongs to this row, and its name is to be derived from principal constituent A (expression Al
2O
3Carrier), S (expression SiC and/or Si metal) and C (expression carbon support).Magnesium oxide carrier (being used for spinel forms) and Mg-Al spinel also can be the compositions of this prescription.This batching is bonding as tackiness agent with synthetic resins such as resol.It for example is used for pig iron hot metal ladle, but also can be used for blind pipe, dipping tube etc.
To synthetic resins adherent product, its process of setting can followingly be carried out, and promptly for example can meet or exceed the transition temperature that is transformed into α-cristobalite from β-cristobalite, thereby makes had tiny crack when preformed moulded piece is provided in product.Perhaps, also can harden (annealing) down at lesser temps (as 160-220 ℃), and in the use after passing the process that tiny crack forms.Being formed on when product is installed this product of post-heating of this fine fisssure strand takes place.
Mention that described batching also is particularly useful for preparing the fire-resistant moulded piece of the refractory products of roasting, particularly roasting.At this moment as usual can be with tackiness agent, particularly temporary transient tackiness agent such as lignosulfonic acid salts solution are sneaked in the batching, for example this mixture are pressed into brick then, and carry out drying and roasting.Typical maturing temperature is 1300-1700 ℃.Be suitable for containing the MgO of 96 weight % and the granular SiO of 4 weight %
2The typical maturing temperature of the batching of carrier is 1400 ℃ (± 50 ℃).When selecting maturing temperature, following experience is suitable for: too high maturing temperature or use temperature can be because too strong sintering (being attended by the fusion phase usually) cause SiO
2The effect of carrier reduces, and fragility is increased.To consider like this at SiO
2Response characteristic between carrier and the fire-resistant base material, the formation of particularly fusion phase can not hinder enough sintering again simultaneously.Thus, maturing temperature is relevant with concrete selected furnish component accurately, and is determined by experience.
Followingly will the present invention be described in detail in detail with various embodiments.Describe 5 kinds of Comparative Examples (Nr.6,8) by prior art that contain under the batching (Nr.1-5) of non-alkaline basal component, a kind of batching based on MgO (Nr.7) and each situation below altogether, wherein raw material composition and chemical constitution provide with the oxide analysis form.
The batching of embodiment 1-3 is used to prepare the shaping prod based on the roasting of non-alkaline base material.Certainly must in this food ingredient, sneak into temporary transient tackiness agent.These can comprise for example sulfite waste lye, phosphoric acid or single aluminate or phosphate.Also can in prescription, add the tackiness agent clay.Under common press pressure (as 65-130MPa), make brick or other moulded piece by this batching, and then carry out roasting.The selection of maturing temperature should make sintering abundant, but temperature can not highly be an impediment to brittle reduction effect to producing too strong sintering.Be grouped into down at given one-tenth, the size-grade distribution and the tackiness agent of particulate part of non-alkaline base material will especially play a decisive role for this reason.
The maturing temperature of embodiment 1 is elected 1450 ℃ as.By the batching 2 and 3 the preparation (compacting) brick 1550 ℃ of following roastings.
Batching Nr.4 is used to prepare so-called ASC product, the promptly aforesaid carbon adherent product that contains the additive cristobalite.Change by cristobalite, the product of being made by this batching causes the tiny crack in the structure when annealing (400 ℃).
What embodiment 5 illustrated a kind of salic cement is suitable for casting the batching of material.This batching is mixed with water, and makes moulded piece by it, and this moulded piece is 380 ℃ of dry down or annealing.In addition, preparation does not contain the contrast material (Nr.6) of cristobalite additive, and makes similar sample, 380 ℃ of dry or annealing down yet.In order to compensate the square English right side of the 4 weight % that lacked among the Nr.6 in batching, all the other basal components of the Nr.5 for preparing burden are all increased by 4% relatively.
Embodiment (1)
| Fire-resistant base material | Granularity | Weight % | Oxide compound is formed | Weight % |
| Andaluzite | 1-3mm | 55 | SiO 2 | 40.4 |
| Andaluzite | 125μm-＜ 1mm | 16 | Al 2O 3 | 58.0 |
| Andaluzite | ＜125μm | 25 | Fe 2O 3 | 0.8 |
| Quartzite | 0.5-1mm | 4 | TiO 2 | 0.2 |
| CaO+MgO | 0.2 | |||
| K 2O+Na 2O | 0.3 |
Embodiment (2)
| Fire-resistant base material | Granularity | Weight % | Oxide compound is formed | Weight % |
| The fusion mullite | 2-4mm | 18 | SiO 2 | 24.3 |
| The fusion mullite | 0.3-＜2mm | 51 | Al 2O 3 | 74.3 |
| The fusion mullite | ＜125μm | 22 | Fe 2O 3 | 0.8 |
| Calcined polishing aluminum oxide | ＜0.1 |
5 | TiO 2 | 0.1 |
| Cristobalite | 1-3mm | 4 | CaO+MgO | 0.1 |
| K 2O+Na 2O | 0.4 |
Embodiment (3)
| Fire-resistant base material | Granularity | Weight % | Oxide compound is formed | Weight % |
| White fused alumina | 3-5mm | 13 | SiO 2 | 5.0 |
| White fused alumina | 1-＜3mm | 42 | Al 2O 3 | 94.6 |
| White fused alumina | ＜1mm | 15 | Fe 2O 3 | 0.1 |
| Tabular alumina | ＜125μm | 15 | TiO 2 | 0.1 |
| Calcined polishing aluminum oxide | ＜0.1 |
10 | CaO+MgO | 0.1 |
| Coesite | 1-3mm | 3 | K 2O+Na 2O | 0.2 |
| Coesite | 3- |
2 |
Embodiment (4)
| Fire-resistant base material | Granularity | Weight % | Oxide compound is formed * | Weight % |
| White fused alumina | 2-4mm | 15 | SiO 2 | 20.2 |
| White fused alumina | 0.3-＜2mm | 30 | Al 2O 3 | 78.7 |
| Bauxitic clay | 0.3-2mm | 20 | Fe 2O 3 | 0.4 |
| Cristobalite | 0.5- |
4 | TiO 2 | 0.5 |
| Tabular alumina | ＜ |
10 | CaO+MgO | 0.1 |
| Calcined polishing aluminum oxide | ＜250μm | 5 | K 2O+Na 2O | 0.1 |
| SiC | ＜ |
5 | ||
| The Si metal | ＜ |
3 | ||
| Graphite | ＜0.5mm | 8 | ||
| The novolac resin that contains stiffening agent | +1.5 | |||
| Resole | +3.5 |
*By oxidisability calcination sample
Embodiment (5)
| Fire-resistant base material | Granularity | Weight % | Oxide compound is formed | Weight % |
| Bauxitic clay | 1-3mm | 44 | SiO 2 | 14.9 |
| Bauxitic clay | 125μm-＜ 1mm | 22 | Al 2O 3 | 81.0 |
| Bauxitic clay | ＜ |
10 | Fe 2O 3 | 1.3 |
| Cristobalite | 0.5-1.5 |
4 | TiO 2 | 1.6 |
| Calcined polishing aluminum oxide | ＜250μm | 8 | CaO+MgO | 1.2 |
| Reactive oxidants aluminium | ＜125μm | 4 | K 2O+Na 2O | 0.1 |
| Little silicon-dioxide | ＜ |
4 | ||
| |
4 | |||
| Dispersion agent | +0.2 | |||
| Citric acid | +0.1 |
The mechanical breaking check shows that the initiation of tiny crack can reduce fragility.The brittle numerical value of product can obtain in a different manner.For example this numerical value is characteristic length:
In this equation, G
FFor than energy-to-break (N/m), E is Young's modulus (Pa), f
t(Pa) be tensile strength.This characteristic length is big more, and the fragility of fire-resistant engineering materials is more little.Usually find that fragility is with than energy-to-break G
FWith tensile strength f
tRatio G
F/ f
tRise and descend.For characterizing product of the present invention, use ratio G
F/ σ
KZMensuration is than energy-to-break G
FWith nominal nmotch tensile strength σ
KZThe basic function principles illustrated of key joint test in people such as K.Rieder " Bruchmechanische Kalt-und Heisspr ü fung feuerfestergrobkeramischer Werkstoffe ", Fortschrittsberichte der DeutschenKeramischen Gesellschaft, Werkstoffe-Verfahren-Anwendung-Band 10 (1995), Heft 3, ISSN 0177-6983,62-70.This method of inspection is further described below:
The key joint test is at room temperature carried out after product being heat-treated (for example drying, annealing or calcination product).
The tabular that specification sheets provides is at last enumerated the condition of the key joint test relevant with original prod." unshaped product " is meant batching, optionally is the batching that is added with tackiness agent and/or modulation liquid.Term " shaping prod " comprises all shapes and manufacturing process, and at this moment this product must have the size of check body described below at least.Here differentiate without the shaping prod after thermal treatment and the thermal treatment with and corresponding different adhesive type." original unshaped product " for example cast material or injection moulding material can solidify after making entire object (as furnace lining) in use, and can therefore be called " moulded piece ".This also is applicable to the finished product member that stands comparatively high temps at least in use.
Each product is checked three samples at least, get its as a result mean value be used for the evaluation.The shape of sample is shown in Fig. 1.Rectangular specimen is of a size of: wide B:110mm, long L:75mm, high H:100mm.As seen the groove A that has following size above it: wide b:24mm, long l:75mm, high h:22mm.This groove A is used to hold bar rod, roller and the wedge that is used for power transmission.To be 3mm and high h ' extend to basal plane G direction downwards from the bottom of groove A for the otch K1 of 2mm wide b '.Always connect on the end face of otch K1 by another otch K2, K3, K2, K3 extend to the basal plane G of sample.The wide b of K2, K3 " be 3mm, high h " be 6mm.For testing, two handful LS are being from the outside the mirror image introducing groove A, the shape and the size of this rod are shown in Fig. 2.The center between the bar rod LS place Fig. 3 (on) shown in wedge Kl, (Fig. 3 supports this excellent LS down), as shown in Figure 4 to this wedge through two roller R.If the forming process of product preparation is to finish by the single shaft press, then the taking-up mode of this sample is to make the direction of pressing force be parallel to the plane of ligament area (it is for producing the face of fracture when the check).The length of wedge K and bar rod LS is 75mm corresponding to specimen length.Roller R is a little longer.Wedge Kl, bar rod LS and roller R are formed from steel.Sample support is on linear bearing during check.This bearing is that the length of side is the tetragonal rod iron S of 5mm, and its length is 75mm corresponding to specimen width at least, and extends to the total length of sample.Rod S covers the width of otch K2, K3 equably with both sides.The process of this check is shown in Fig. 5.Ergometer KM can be seen in top toward this figure.Load the vertical power that produces by checking machine to wedge Kl and cause producing horizontal force, this horizontal force causes the crackle of steady progression to form in checkout procedure.Period detecting normal load F
VWith vertical translation δ
VWrite down this measured value, drop to 10% or less than fully-factored load up to load.Energy-to-break G
FDetermine by the area under the load/displacement diagram.Therefore be:
In this equation (II), A is that the ligament area is 66x 63mm
2[(100-22-12) x (75-6-6)], δ
MaxIt is the maximum displacement in the measuring process.The nominal nmotch tensile strength is by following Equation for Calculating:
In this equation (III), B is tough belt length (63mm), and W is ligament height (66mm).Value y represents the horizontal line of action of force that produces by the roller vertical range from the center of gravity of this ligament area.For this reason, as enough being similar to use value 62mm (Fig. 1 and 4).The horizontal maximum load F that in relational expression (III), uses
H maxCan be by following formula by vertical maximum load F
V maxTry to achieve:
In this formula (IV), α means key groove, elects 10 ° as.It is to carry out under the 0.5mm/min that this check is controlled at checking machine drift vertical speed.
For the situation of failing to follow these inspection parameters in certain product, for example because can not prepare enough big sample or owing to other reasons such as accuracy of the absolute value that is derived from doubt mensuration, that then measures product of the present invention and similar preparation and check does not contain SiO
2The ratio G of the product of carrier
F/ σ
KZAt this moment, the SiO that lacks
2Content joins in all other components of this product in proportion.Therefore, fragility reduces the ratio G with product of the present invention
F/ σ
KZWith similar preparation do not contain SiO
2The ratio G of the product of carrier
F/ σ
KZrecently determine.This is than＞1, usually＞1.5 or＞1.8.Make every effort to this ratio＞2.The value of the following examples (7), (8) almost reaches 3.
Bear than energy-to-break G in the following table
F, nominal nmotch tensile strength σ
KZAnd both ratio.The feature of product of the present invention is ratio G
F/ σ
KZ＞40.Make every effort to＞50 value.
| Embodiment (5) | Comparative Examples (6) | |
| G F[N/m] | 243 | 255 |
| σ KZ[MPa] | 4.6 | 10.7 |
| G F/σ KZ[μm] | 52.8 | 23.8 |
The ratio energy-to-break of product of the present invention and the ratio of nominal nmotch tensile strength will exceed more than one times, can obviously reduce fragility thus.
| Embodiment (7) | Comparative Examples (8) | |
| Magnesium oxide sinter 1-5mm | 55 | 55 |
| Magnesium oxide sinter 0.125-1mm | 14 | 18 |
| Magnesium oxide sinter＜0.125mm | 27 | 27 |
| Quartzite 0.5- |
4 | |
| Maturing |
1400 | 1400 |
| SiO 2[weight %] | 4.13 | 0.18 |
| Fe 2O 3[weight %] | 0.48 | 0.49 |
| Al 2O 3[weight %] | 0.10 | 0.09 |
| CaO [weight %] | 0.78 | 0.8 |
| MgO (pact) [weight %] | 94.5 | 98.4 |
| E dyn[GPa] | 14.9 | 75.8 |
| G F[N/m] | 210 | 264 |
| σ KZ[MPa] | 4.6 | 14.8 |
| G F/σ KZ[μm] | 45.6 | 17.9 |
| σ KZ/E dyn[10 -3] | 0.31 | 0.20 |
For descending, proof fragility also carried out described key joint examination danger.
Fig. 6 illustrates the load/displacement diagram of key joint test (at room temperature carrying out), and show the present invention prepare burden (7) obviously little fragility is arranged.This can by in the above-mentioned table than energy-to-break G
FWith nominal nmotch tensile strength σ
KZHigher ratio find out.
In addition, the dynamic elasticity amount of touching E
DynCan measure [Hennicke, Leers:Die Bestimmung elastischer Konstanten mit dynamischenMethoden, Tonindustrie-Zeitung 89Nr.23/24,539-543 (1976)] by the resonant frequency of extension ripple.
As above shown in the table, in the magnesium oxide component, add granular SiO
2Carrier can obviously reduce Young's modulus, promptly drops to 14.9Gpa from 75.8Gpa.
From table, find out that also in the present invention program, the nominal nmotch tensile strength is obviously higher with the ratio of dynamic elastic modulus.Press people such as Kingery[W.D.Kingery: Introduction toCeramics, John Wiley﹠amp; Sons, 1960; ISBN 0-471-47860-1], can infer that the thermal stresses parameters R increases.
Though the present invention removes additive (the granular SiO of fire-resistant basal component external application simple and inexpensive
2Therefore carrier) solved problem, described batching turns out to be and is used to prepare the good basis with less brittle refractory products, shows good resistance to sudden heating, and is corrosion resistant, reduces thermotolerance not yet but compare with the other products of prior art.The selection of furnish component and preparation condition will make the G of product
F/ σ
KZRatio＞40.
With do not contain granular SiO
2The magnesium oxide product of carrier is compared, and the advantage of product of the present invention is higher mechanical stability or hot machine stability or the tangible deformability under thermal shocking.Compare with the magnesium oxide ferrochrome product, it demonstrates is the advantage of Chrome-free lining material, can avoid forming Cr thus
6+Danger.Compare with the spinel product, on the one hand by the cheap SiO that can get
2Carrier reaches the advantage on the cost.On the other hand at CaO-MgO-SiO
2CaO and SiO in the system
2Weight ratio (C/S than) be lower than 0.93 engineering materials, estimate as product of the present invention, its not change point be at least 1502 ℃, when the C/S ratio is lower than about 0.25 (the forsterite mixed crystal exists as unique silicic acid parafacies), this not change point also can raise with the decline of C/S ratio up to the most about 1860 ℃.
In contrast, corresponding to the C/S of prior art than surpass 1.87 contain spinel (MgAl
2O
3) the invariant point of magnesia brick be 1325 ℃.Higher invariant point under product situation of the present invention can be used for improving thermal characteristics, as long as the fusion phasor also is more favourable under the actual infiltration situation in taking the product composition into account and using.With contain ZrO
2The product of additive is compared, because lower SiO
2The carrier cost is in any case be favourable economically.
Under non-basic prod situation, compare with using mullite or zirconium mullite, its advantage be do not introduce contain glassy phase and produce component thus to the harmful effect of softening performance.Product of the present invention can be a kind of material compositions of only being made up of crystalline phase.Another advantage is, when using cristobalite, has promptly begun to occur tiny crack and fragility is reduced under 270 ℃.So also can prepare or use the product that little brittle not roasting is just arranged at a lower temperature.As cast material and finished product member all belong to these row.Also can for example in this way reduce the not fragility of roasting product of carbon adherent.
Each symbolic significance is as follows in the table:
1: by batching, add tackiness agent and/or water (as chemical binder or aqueous adhesive) postforming sample when needing, and 350 ℃ of following thermal treatments.
2: by batching, add tackiness agent and/or water (as chemical binder or aqueous adhesive) postforming sample when needing, and at 650 ℃ or 〉=1350 ℃ of following thermal treatments.
3: cut out sample by product, and 350 ℃ of following thermal treatments, as long as this product not in advance under 〉=350 ℃ through thermal treatment.
4: cut out sample by product, and at 650 ℃ or 〉=1350 ℃ of following thermal treatments, as long as this product not in advance 〉=650 ℃ or under 〉=1350 ℃ through thermal treatment.
5: cut out sample by the product that forms in use, and 350 ℃ of following thermal treatments, as long as this product is in use without the thermal treatment under 〉=350 ℃.
6: cut out sample by the product that forms in use, and at 650 ℃ or 1350 ℃ of following thermal treatments, as long as this product is in use without 〉=650 ℃ or thermal treatment under 〉=1350 ℃.
7: cut out sample by product.
8: this SiO
2Carrier at least 50 weight % are made of cristobalite and/or tridymite.
9: this SiO
2Carrier is less than 50 weight % and is made of cristobalite and/or tridymite.
Under 4 and 6 situation, thermal treatment is carried out under 1350 ℃ usually.If 1350 ℃ too high and can not realize that fragility reduces, then thermal treatment is carried out under 650 ℃, this surpasses quartzy disruptive temperature.
*: when thermal treatment, reduce normal atmosphere.
Claims (21)
1. ceramic batch that is suitable for refractory applications, it contains:
The fire-resistant base material of at least a grade＜8mm of A:83-99.5 weight % and
At least a independent granular crystalline SiO of B:0.5-12 weight %
2Carrier, and
C: clout existence or non-existent: other component.
2. the batching of claim 1, its fire-resistant base material is to small part right and wrong alkalescence base material.
3. the batching of claim 1, its fire-resistant base material to small part is made up of calcined dolomite and/or magnesium oxide.
4. the batching of claim 1, it contains:
A) the fire-resistant base material of 90-99 weight % and
B) the granular SiO of 1-7 weight %
2Carrier.
5. the batching of claim 1, its granular SiO
2Carrier is by at least a following SiO
2Variant is formed: cristobalite, tridymite, coesite, crude density are less than 2.65g/cm
3Through pretreated product.
6. the batching of claim 1, its SiO
2The granularity d of carrier
50Granularity greater than the 95 weight % of fire-resistant base material particulate part.
7. the batching of claim 1, its SiO
2The granularity d of carrier
05Granularity greater than the 95 weight % of fire-resistant base material particulate part.
8. the batching of claim 1, the 95 weight % of particulate part of its fire-resistant base material＜250 μ m.
9. the batching of claim 1, the 95 weight % of particulate part of its fire-resistant base material＜125 μ m.
10. claim 8 or 9 batching, particulate part of its fire-resistant base material accounts for the 10-30 weight % of total batching.
11. the batching of claim 1, its SiO
2The granularity of carrier is no more than 6mm.
12. the batching of claim 1, its SiO
2The granularity of carrier is no more than 3mm.
13. the batching of claim 1, its SiO
2The granularity of carrier is 0.5-3mm.
14. the batching of claim 1, the granularity of its fire-resistant base material is less than 6mm.
15. the batching of claim 1, its fire-resistant base material has following size-grade distribution:
A) 50-60 weight % is 1-6mm,
B) 10-25 weight % be 0.25-less than 1mm,
C) 25-30 weight % is less than 0.25mm,
Wherein total amount is 100 weight %.
16. the batching of claim 1, it contains the fire-resistant base material of at least a non-alkalescence in the following component: fireclay, sillimanite, andaluzite, kyanite, bauxitic clay, corundum starting material, tabular alumina, Calcined polishing aluminum oxide, quartzite, contain zirconic base material, titanium oxide, Mg-Al spinel, silicon carbide.
17. the batching of claim 1, it contains the MgO base material, and this MgO base material reaches 3-20 weight % by total mixture, and this MgO base material is made up of Herzynit type spinel, galaxite type spinel or its mixture.
18. the batching of claim 1, it contains at least a following component as all the other compositions: carbon.
19. the batching of claim 1, it contains at least a following component as all the other compositions: graphite, resin, pitch, carbon black, coke, tar.
20. the product based on the batching of one of claim 1-19, it is than energy-to-break G
FWith nominal nmotch tensile strength σ
KZRatio greater than 40 μ m, it all adopts the test determination of sample key joint.
21. the product based on the batching of one of claim 1-19, its all adopt the test determination of sample key joint than energy-to-break G
FWith nominal nmotch tensile strength σ
KZRatio, be to not containing independent granular SiO at least
21.5 times of the same ratio of measuring of the product of carrier, all the other basal components are in proportion by the SiO that lacks
2Content is adjusted to and is total up to 100 weight %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004010739.4 | 2004-03-05 | ||
| DE200410010739 DE102004010739B4 (en) | 2004-03-05 | 2004-03-05 | Process for the preparation of an unshaped or shaped, fired or unfired refractory product |
| DE102004010740.8 | 2004-03-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1950313A CN1950313A (en) | 2007-04-18 |
| CN100528807C true CN100528807C (en) | 2009-08-19 |
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| CNB2005800144882A Expired - Fee Related CN100528807C (en) | 2004-03-05 | 2005-03-03 | Ceramic batch and associated product for fireproof applications |
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| Country | Link |
|---|---|
| CN (1) | CN100528807C (en) |
| DE (1) | DE102004010739B4 (en) |
| UA (1) | UA90469C2 (en) |
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| FR2954768A1 (en) * | 2009-12-24 | 2011-07-01 | Saint Gobain Ct Recherches | POWDER FOR DRY CHEMICAL PISA |
| TWI557092B (en) | 2012-01-11 | 2016-11-11 | 聖高拜陶器塑膠公司 | Refractory object and process of forming a glass sheet using the refractory object |
| FR3008967B1 (en) * | 2013-07-26 | 2016-12-30 | Saint-Gobain Centre De Rech Et D'Etudes Europeen | HIGH ALUMINUM PRODUCT |
| EP3262011A4 (en) | 2015-02-24 | 2018-08-01 | Saint-Gobain Ceramics&Plastics, Inc. | Refractory article and method of making |
| CN104926322B (en) * | 2015-04-16 | 2017-07-25 | 李金盛 | A kind of SiC rings split renovation agent and preparation method thereof |
| CN104860656A (en) * | 2015-05-04 | 2015-08-26 | 安徽省亚欧陶瓷有限责任公司 | High fire resistance ceramic tile and production method thereof |
| CN104944926A (en) * | 2015-05-18 | 2015-09-30 | 浙江长兴银兴窑业有限公司 | Silicon carbide refractory material |
| CN104926323A (en) * | 2015-05-18 | 2015-09-23 | 浙江长兴银兴窑业有限公司 | Refractory material containing silicon carbide |
| CN105016745A (en) * | 2015-05-18 | 2015-11-04 | 浙江长兴银兴窑业有限公司 | Refractory material containing silicon carbide |
| CN112250455A (en) * | 2020-10-30 | 2021-01-22 | 德清县钢友耐火材料有限公司 | High-temperature refractory material and manufacturing process method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4391917A (en) * | 1980-10-27 | 1983-07-05 | Dresser Industries, Inc. | Alumino-silicate refractory brick |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2323486A1 (en) * | 1973-05-10 | 1974-11-21 | Bosch Gmbh Robert | PROCESS FOR THE PRODUCTION OF WHITE COMBUSTION CAPSULES FOR THE FIRING OF CERAMIC MOLDED PARTS |
| DE2605950B2 (en) * | 1976-02-14 | 1978-08-24 | Vereinigte Grossalmeroder Thonwerke, 3432 Grossalmerode | Refractory product with improved thermal shock resistance |
-
2004
- 2004-03-05 DE DE200410010739 patent/DE102004010739B4/en not_active Withdrawn - After Issue
-
2005
- 2005-03-03 UA UAA200610357A patent/UA90469C2/en unknown
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4391917A (en) * | 1980-10-27 | 1983-07-05 | Dresser Industries, Inc. | Alumino-silicate refractory brick |
Non-Patent Citations (2)
| Title |
|---|
| 耐火材料工艺学. 王维邦，104，冶金工业出版社. 1998 |
| 耐火材料工艺学. 王维邦，104，冶金工业出版社. 1998 * |
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| Publication number | Publication date |
|---|---|
| UA90469C2 (en) | 2010-05-11 |
| DE102004010739B4 (en) | 2006-05-18 |
| DE102004010739A1 (en) | 2005-09-22 |
| CN1950313A (en) | 2007-04-18 |
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