CN117550911B - Corundum spinel slit type air brick airway surface modification method - Google Patents
Corundum spinel slit type air brick airway surface modification method Download PDFInfo
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- 239000011449 brick Substances 0.000 title claims abstract description 140
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 57
- 239000011029 spinel Substances 0.000 title claims abstract description 57
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 54
- 239000010431 corundum Substances 0.000 title claims abstract description 54
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920000742 Cotton Polymers 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000012047 saturated solution Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 229960003390 magnesium sulfate Drugs 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims 1
- 239000002893 slag Substances 0.000 abstract description 13
- 230000003628 erosive effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 24
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000011065 in-situ storage Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- -1 magnesium zinc aluminum Chemical compound 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0003—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof containing continuous channels, e.g. of the "dead-end" type or obtained by pushing bars in the green ceramic product
-
- 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
- C04B35/10—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 aluminium oxide
-
- 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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a corundum spinel slit type air brick air flue surface modification method, which is characterized in that corundum spinel castable is used as a raw material, the corundum spinel castable is subjected to casting forming and curing, then is demoulded, a demoulded blank is baked in a drying kiln at 120-300 ℃ for 24 hours, then is heated to 500-600 ℃ and is kept warm for 12 hours, a slit precursor is completely burned off, a slit air flue is generated, and a corundum spinel slit type air brick blank is obtained; then the air brick blank body after the slit precursor material is burnt out is immersed into saturated salt solution or combined with zinc vapor treatment, so that a new crystalline phase is formed on the surface of the air passage micro-area of the air brick, and the surface of the air passage micro-area is completely modified, thereby solving the problems that the material on two sides of an air passage has good performance, such as loose, low strength, poor slag resistance, poor erosion resistance and the like, due to the filling and burning out of a slit filler in the preparation process of the conventional slit air brick.
Description
Technical Field
The invention relates to a preparation method of an air brick for ladle refining, in particular to a method for modifying the surface of an air passage of a corundum-spinel slit air brick.
Background
The air brick is an indispensable functional element for external refining, and has decisive influence on the quality of molten steel. The service life of the air brick is a key factor for limiting the service life of the steel ladle. According to the type of the air flow channel, the air brick is mainly slit type and dispersive type at present, and mainly slit type; the slit channel is arranged in the slit type air brick of the finished product and is used for blowing argon into the ladle. The air brick materials are generally classified into corundum spinel materials and chrome corundum materials, wherein the corundum spinel materials are good in thermal shock resistance and the chrome corundum materials are better in slag erosion resistance. However, chromium-containing materials have the problem of hexavalent chromium pollution, so that the main research should be based on corundum spinel. The existing slit type air brick process comprises the following steps: preparing a mould, casting, curing, demoulding, baking at 300 ℃ and sintering at a high temperature above 1500 ℃, wherein in the sintering process, a slit channel is generated by the burning-out of a slit precursor material. However, the material micro-areas on both sides of the air brick slit channel are free of aggregate due to boundary effects, so that the strength is lower compared with the air brick body material. In addition, due to the existence of the slit, high-temperature slag and molten steel are liable to infiltrate along the slit and attack the slit surface first. Under the high-temperature service condition, the most prominent region of the air brick with concentrated stress is around the air passage outlet, and one of the main damage modes is that the slit is blocked, so that the ventilation quantity cannot meet the smelting requirement, and the service life of the air brick and the normal turnover of a ladle are affected. Based on the analysis, aiming at the short plates of the existing corundum spinel slit-type air brick, the slit airway micro-area material is required to be purposefully reinforced by fine design and control so as to improve the scouring resistance, slag resistance, high-temperature melt invasion resistance, thermal shock resistance and the like.
Disclosure of Invention
The invention aims to provide a corundum spinel slit type air brick airway surface micro-area modification method, which solves the problems of low strength, high-temperature molten steel and slag are easy to infiltrate into slits and erode to cause the air brick air function to be damaged and the service life to be lower due to no aggregate in micro-areas of materials on two sides of a slit channel in the existing slit type air brick preparation process.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a method for modifying the airway surface of corundum spinel slit-type air brick comprises the following steps:
firstly, preparing a mould, namely taking corundum spinel castable as a raw material, demoulding after casting forming and curing, baking a demoulded blank in a drying kiln at 120-300 ℃ for 24 hours, heating to 500-600 ℃ and preserving heat for 12 hours, and completely burning out a slit precursor at the temperature to generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
the method for modifying the airway surface of the corundum spinel slit-type air brick comprises the following steps:
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking the used saturated salt solution into the whole air brick body by utilizing a pipeline, immersing the whole air brick body in the saturated solution, standing for 3-4h, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out the redundant solution by using cotton cloth, naturally airing, then baking at 120-150 ℃, and then sintering at high temperature to obtain the corundum spinel slit air brick with the modified airway surface.
Wherein the high-temperature sintering equipment is a high-temperature gas kiln or a high-temperature electric kiln or a high-temperature tunnel kiln; firing temperature: 1500-1680 ℃.
Wherein the saturated salt solution is magnesium salt solution, or calcium salt solution, or aluminum salt solution, or zirconium salt solution;
wherein the magnesium salt is any one or mixture of magnesium sulfate, magnesium chloride, magnesium phosphate, magnesium nitrate and magnesium citrate;
wherein the saturated salt solution is magnesium salt, and the invention uses the magnesium salt solution to form Mg (OH) in the drying process 2 Then decomposing at higher temperature to generate nano MgO reaction source on the surface of slit air passage and Al in air brick material matrix at firing temperature 2 O 3 The components react in situ to form magnesia-alumina spinel phase (chemical formula: mgAl) 2 O 4 ). Thereby improving the slag resistance of the micro-area on the surface of the slit airway by using the magnesia alumina spinel formed in situ; the volume expansion effect accompanied by spinel generation reaction is utilized, so that not only can the width of the slit airway be subjected to negative micro-adjustment, but also the micro-roughness of the surface micro-area can be increased, the wetting difficulty of molten steel and slag on the airway surface can be improved, and the probability of blocking the airway by clamping steel can be reduced; in addition, the MgO component introduced in the form of a saturated solution can penetrate into the body of the air brick along the interface and pores and cause in-situ reactionIt should also have the effect of improving the overall performance of the air brick.
Wherein the calcium salt is any one or the mixture of a plurality of calcium chloride and calcium nitrate;
wherein the saturated salt solution is calcium salt, and the invention utilizes the calcium salt solution to form Ca (OH) in the drying process 2 Then decomposing at higher temperature to generate nano CaO reaction source on the surface of slit air passage and Al in air brick material matrix at firing temperature 2 O 3 The components react in situ to generate calcium hexaaluminate phase (chemical formula: caO.6Al) 2 O 3 Abbreviated as CA 6 ). Thereby utilizing in situ generated CA 6 The wetting angle of the micro-zone material on the surface of the slit airway and the high-temperature molten steel is increased, so that the blockage of the slit by clamping the steel is prevented; and utilize CA 6 The volume expansion effect accompanied by the generation reaction can not only carry out negative micro-adjustment on the width of the slit airway, but also increase the micro-roughness of the surface micro-area, further improve the wetting difficulty of molten steel and slag on the airway surface, and reduce the probability of blocking the airway by clamping steel; in addition, caO component introduced in the form of saturated solution can permeate into the air brick body along interfaces and air holes to generate in-situ reaction, and has an effect of improving the overall performance of the air brick.
Wherein the aluminum salt is any one or a mixture of a plurality of aluminum dihydrogen phosphate, aluminum sulfate and aluminum formate;
wherein the saturated salt solution is aluminum salt, and the invention utilizes the aluminum salt solution to form Al (OH) in the drying process 3 Then decomposing at higher temperature to generate nano Al on the surface of the slit airway 2 O 3 At the firing temperature, nano-scale Al is utilized 2 O 3 The high reactivity of the material promotes the high-temperature sintering of the airway surface micro-area material, thereby improving the flushing resistance of the airway surface micro-area.
Wherein the zirconium salt is ZrOCl 2 ·8H 2 O or ZrOCl 2 ·8H 2 O is a zirconia solution prepared by the starting materials;
wherein the saturated salt solution is zirconium salt, and Zr is formed in the drying process by using the zirconium salt solutionOH) 4 Then decomposing at higher temperature to generate nano ZrO on the surface of the slit airway 2 The reaction source reacts with CaO component (from pure calcium aluminate cement) in the air brick material matrix at the firing temperature to generate calcium zirconate phase (chemical formula: caZrO) 3 ). Thereby utilizing in situ generated CaZrO 3 The wetting angle of the micro-zone material on the surface of the slit airway and the high-temperature molten steel is increased, so that the blockage of the slit by clamping the steel is prevented; by CaZrO 3 The dense pinning effect of the phases improves the slag resistance of the slit airway micro-region material.
A second method for modifying the airway surface of the corundum spinel slit-type air brick is as follows:
placing the air brick blank after the slit precursor material is processed in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking the used saturated salt solution into the whole air brick body by utilizing a pipeline, immersing the whole air brick body in the saturated solution, standing for 3-4 hours, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out the redundant solution by using cotton cloth, naturally airing, then baking at 120-150 ℃, then placing in a closed high-temperature furnace, placing metal zinc particles around the air brick blank, placing the metal zinc particles with the weight of 0.5-1 percent of the total weight of the air brick blank, firstly utilizing the vacuum pump to suck negative pressure in the furnace to 0.1 atmosphere, then raising the temperature to 950-1000 ℃, keeping the temperature constant, opening the air valve, enabling the air to enter the furnace until the pressure in the furnace reaches the normal atmosphere, continuing to keep the heat-preserving furnace for 3-4 hours, stopping naturally cooling to the room temperature, and then sintering at high temperature, thus obtaining the corundum slit-type air brick after surface modification.
The reaction of the second method is as follows: according to the invention, when the temperature of the metallic zinc is higher than 907 ℃, the zinc starts to gasify, and gaseous zinc migrates to the surface of the slit airway in the zinc vapor atmosphere; after opening the valve and allowing air to enter the furnace, zinc vapor in the slit airway area is rapidly oxidized into ZnO and deposited on the airway surface;
when the method of using the saturated salt solution as the magnesium salt solution, znO deposited on the surface of the airway can be deposited on the airway surfaceThe surface micro-area in-situ reaction generates the magnesia-zinc-aluminum complex phase spinel (chemical formula (Mg) 1-x Zn x )Al 2 O 4 ) A protective layer;
when the saturated salt solution is calcium salt solution, znO deposited on the airway surface can react in situ on the airway surface micro-region to generate calcium hexaluminate (chemical formula: caO.6Al) 2 O 3 ) And magnesium zinc aluminum complex phase spinel (chemical formula: (Mg) 1-x Zn x )Al 2 O 4 ) A composite protective layer;
when the saturated salt solution is aluminum salt solution, znO deposited on the surface of the airway can react in situ in the micro-area of the airway surface to generate magnesium zinc aluminum complex spinel (chemical formula (Mg) 1-x Zn x )Al 2 O 4 ) Protective layer and promoting sintering;
when the saturated salt solution is ZrOCl 2 ·8H 2 O or ZrOCl 2 ·8H 2 When the zirconia solution prepared by taking O as the initial raw material, znO deposited on the surface of the airway can react in situ on the micro-area of the surface of the airway to generate calcium zirconate (chemical formula: caZrO 3 ) Zinc zirconate (chemical formula: znZrO (ZnZrO) 3 ) And magnesium zinc aluminum complex phase spinel (chemical formula: (Mg) 1-x Zn x )Al 2 O 4 ) A composite protective layer;
the formed composite protective layers enable materials on two sides of the slit air passage of the air brick to be comprehensively and completely modified, not only can the strength and slag resistance of micro-area materials on the surface of the air passage be improved, but also the wetting angle with high-temperature molten steel can be improved by increasing the micro-roughness of the surface of the air passage, and the high-temperature melt is prevented from penetrating into and blocking the slit; the problems that in the existing slit type air brick preparation process, the strength of material micro areas on two sides of a slit channel is low due to no aggregate in the boundary effect, high-temperature molten steel and slag easily infiltrate into the slit and erode to cause the air brick to easily damage the air brick air permeability are solved, the overall performance and the use performance of the air brick are improved, the external refining effect can be effectively improved, the molten steel quality is ensured, and meanwhile, the service life of a ladle is prolonged.
Detailed Description
The practice and characteristics of the present invention are illustrated below, but the present invention is not limited to the following examples, in which "raw materials" are air bricks in the prior art.
Example 1:
firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 200 ℃ for 24 hours after demoulding, and then baking at 500 ℃ for 12 hours at high temperature to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking a saturated magnesium sulfate solution into the whole air brick body by utilizing a pipeline until the whole air brick body is not in the saturated solution, standing for 3 hours, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out the redundant solution by using cotton cloth, naturally airing, baking at 120 ℃, and then sintering at a high temperature to obtain the corundum spinel slit air brick with the air passage surface modified.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 1:
table 1: example 1 Key index of materials before and after modification and use effect of air brick
Example 2:
firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 200 ℃ for 24 hours after demoulding, and then baking at 600 ℃ for 12 hours at high temperature to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking a saturated magnesium sulfate solution into the container through a pipeline until the whole air brick body is not in the saturated solution, standing for 4 hours, opening an air valve to balance the pressure inside and outside the container, taking out the air brick, wiping out redundant solution by cotton cloth, naturally airing, baking at 150 ℃, then placing in a closed high-temperature furnace, placing metal zinc particles around the air brick blank body, placing the weight of the metal zinc particles into the air brick blank body to be 1 percent of the total weight of the air brick blank body, firstly utilizing the vacuum pump to make the negative pressure in the furnace to be 0.1 atmosphere, then raising the temperature to 950 ℃, preserving heat, gasifying the metal zinc in the closed furnace and keeping the temperature constant, opening the air valve until the pressure in the furnace body reaches normal atmosphere after preserving heat for 3 hours, stopping the furnace after continuing to preserve heat and naturally cooling to the room temperature, and then firing at high temperature to obtain the corundum slit air brick with modified surface.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 2:
table 2: example 2 Key index of materials before and after modification and use effect of air brick
Example 3:
firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 300 ℃ for 24 hours after demoulding, and then baking at 600 ℃ for 12 hours at high temperature to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking saturated calcium chloride solution into the whole air brick body by utilizing a pipeline until the whole air brick body is not in the saturated solution, standing for 3 hours, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out excessive solution by using cotton cloth, naturally airing, baking at 120 ℃, and then sintering at high temperature to obtain the corundum spinel slit air brick with the air channel surface modified.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 3:
table 3: example 3 Key index of materials before and after modification and use effect of air brick
Example 4: firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 300 ℃ for 24 hours after demoulding, and then baking at 500 ℃ for 12 hours at high temperature to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking saturated aluminum formate solution into the whole air brick body by utilizing a pipeline until the whole air brick body is not in the saturated solution, standing for 3 hours, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out excessive solution by using cotton cloth, naturally airing, baking at 150 ℃, and then sintering at high temperature to obtain the corundum spinel slit air brick with the air flue surface modified.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 4:
table 4: example 4 Key index of materials before and after modification and use effect of air brick
Example 5: firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 300 ℃ for 24 hours after demoulding, and then baking at 500 ℃ to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking zirconia solution into the whole air brick body by utilizing a pipeline until the whole air brick body is not in saturated solution, standing for 4 hours, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out excessive solution by using cotton cloth, naturally airing, baking at 120 ℃, and then sintering at high temperature to obtain the corundum spinel slit air brick with the air passage surface modified.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 5.
Table 5: example 5 Key index of materials before and after modification and use effect of air brick
Example 6:
firstly, preparing a mould, namely casting and forming by taking corundum spinel castable as a raw material, baking at 120 ℃ for 24 hours after demoulding, and then baking at 500 ℃ for 12 hours at high temperature to completely burn out a slit precursor and generate a slit air passage to obtain a corundum spinel slit-type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking saturated calcium chloride solution into the whole air brick body by utilizing a plastic pipeline until the saturated calcium chloride solution is not in the solution, standing for 3.5h, opening an air valve to balance the pressure inside and outside the container, taking out the air brick, wiping out redundant solution by cotton cloth, naturally airing, baking at 120 ℃, then placing in a closed high-temperature furnace, placing metal zinc particles around the air brick blank body, placing the metal zinc particles with the weight of 0.5 percent of the total weight of the air brick blank body, firstly utilizing the vacuum pump to make the negative pressure in the furnace to 0.1 atmosphere, then raising the temperature to 1000 ℃, keeping the temperature constant, opening the air valve after keeping the temperature constant, making the air enter the furnace until the pressure in the furnace body reaches the normal atmosphere, continuing to keep the temperature for 3h, stopping the furnace, naturally cooling to the room temperature, and then burning at high temperature to obtain the corundum spinel slit air brick with the modified air passage surface.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 6.
Table 6: example 6 Key index of materials before and after modification and use effect of air brick
Example 7:
firstly, preparing a mould, namely taking corundum spinel castable as a raw material, demoulding after casting forming and curing, baking a demoulded blank in a drying kiln at 120 ℃ for 24 hours, heating to 600 ℃ and preserving heat for 12 hours, and completely burning out a slit precursor at the temperature to generate a slit air passage to obtain a corundum spinel slit type air brick blank;
placing the air brick blank body treated with the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, and then sucking saturated ZrOCl through a pipeline 2 ·8H 2 O solution until the whole air brick body is not in solution, standing for 4 hours, opening an air valve to balance the internal pressure and the external pressure of a container, taking out the air brick, wiping out the redundant solution by cotton cloth, naturally airing, baking at 120 ℃, then placing in a closed high-temperature furnace, placing metal zinc particles around the air brick body, wherein the weight of the metal zinc particles placed in the air brick body is 0.6 percent of the total weight of the air brick body, firstly utilizing a vacuum pump to make the internal pressure of the furnace negative to 0.1 atmosphere, then raising the temperature to 1000 ℃, preserving heat, gasifying the metal zinc in the closed furnace and keeping the temperature constant, after preserving heat for 4 hours, opening the air valve, making the air enter the furnace until the internal pressure of the furnace body reaches normal atmospheric pressure, continuously preserving heat for 3 hours, stopping the furnace, naturally cooling to room temperature, and then sintering at high temperature, thus obtaining the corundum spinel slit air brick with the air passage surface modified.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 7.
Table 7: example 7 Key index of materials before and after modification and use effect of air brick
Example 8:
firstly, preparing a mould, namely taking corundum spinel castable as a raw material, demoulding after casting forming and curing, baking a demoulded blank in a drying kiln at 150 ℃ for 24 hours, heating to 600 ℃ and preserving heat for 12 hours, and completely burning out a slit precursor at the temperature to generate a slit air passage to obtain a corundum spinel slit type air brick blank;
placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking saturated aluminum phosphate solution into the container through a pipeline until the whole air brick body is not in the solution, standing for 3 hours, opening an air valve to balance the pressure inside and outside the container, taking out the air brick, wiping out redundant solution by cotton cloth, naturally airing, baking at 120 ℃, then placing in a closed high-temperature furnace, placing metal zinc particles around the air brick blank body, placing the metal zinc particles in a weight which is 0.8 percent of the total weight of the air brick blank, firstly utilizing the vacuum pump to enable the negative pressure in the furnace to be 0.1 atmosphere, then raising the temperature to 980 ℃, keeping the temperature constant, opening the air valve until the pressure in the furnace body reaches normal atmosphere, continuously keeping the temperature for 3 hours, stopping the furnace, naturally cooling to the room temperature, and then sintering at high temperature to obtain the corundum spinel slit type air brick with the modified air passage surface.
The key indexes of the materials before and after modification and the using effect of the air brick are shown in table 8.
Table 8: example 8 Key index of materials before and after modification and use effect of air brick
The performance indexes of the materials before and after the process modification in examples 1 to 8, such as chemical composition, normal temperature compressive strength, high temperature flexural strength, surface hardness and other detection samples, are conventional standard size splines (25 mm by 150mm, 40mm by 160 mm) prepared in a laboratory with the same formulation, and the spline treatment conditions are the same as those of the corresponding air brick treatment and sintering process. After each cast crucible sample was added with 80g of steel slag and heat treated and naturally cooled at the firing temperature, the erosion area of the longitudinal section of the crucible was measured, and the ratio of the area to the original inner hole section of the crucible was the slag erosion index.
Claims (6)
1. A method for modifying the surface of a corundum spinel slit-type air brick airway is characterized by comprising the following steps: firstly, preparing a mould, namely taking corundum spinel castable as a raw material, demoulding after casting forming and curing, baking a demoulded blank in a drying kiln at 120-300 ℃ for 24 hours, heating to 500-600 ℃ and preserving heat for 12 hours, and completely burning out a slit precursor at the temperature to generate a slit air passage to obtain a corundum spinel slit-type air brick blank; placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking the used saturated salt solution into the whole air brick body by a pipeline until the saturated salt solution is immersed into the saturated solution, standing for 3-4h, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out the redundant solution by cotton cloth, naturally airing, baking at 120-150 ℃, and then sintering at high temperature to obtain the corundum spinel slit air brick with the air flue surface modified.
2. The method for modifying the airway surface of a corundum spinel slit-type air brick according to claim 1, characterized by: placing the air brick blank body of the slit precursor material in a closed plastic container, firstly reducing the pressure in the container to 0.1 atmosphere by utilizing a vacuum pump, then sucking saturated salt solution into the whole air brick body through a pipeline until the saturated salt solution is not in the saturated solution, standing for 3-4h, opening an air valve to balance the internal pressure and the external pressure of the container, taking out the air brick, wiping out redundant solution by cotton cloth, naturally airing, baking at 120-150 ℃, then placing in a closed high-temperature furnace, wherein the weight of the metal zinc particles around the air brick blank body is 0.5-1% of the total weight of the air brick blank, firstly utilizing the vacuum pump to suck negative pressure in the furnace to 0.1 atmosphere, then raising the temperature to 950-1000 ℃ and preserving heat, gasifying the metal zinc in the closed furnace and keeping the temperature constant, opening the air valve after preserving heat for 3-4h, enabling air to enter the furnace until the pressure in the furnace body reaches normal atmosphere, continuing to preserve heat for 3-4h, then naturally cooling to room temperature, and then stopping high-temperature sintering, thus obtaining the corundum slit type air brick after surface modification.
3. The method for modifying the airway surface of a corundum spinel slit-type air brick according to claim 1, characterized by: the magnesium salt is one or more of magnesium sulfate, magnesium chloride, magnesium phosphate, magnesium nitrate and magnesium citrate.
4. The method for modifying the airway surface of a corundum spinel slit-type air brick according to claim 1, characterized by: the calcium salt is one or more of calcium chloride and calcium nitrate.
5. The method for modifying the airway surface of a corundum spinel slit-type air brick according to claim 1, characterized by: the aluminum salt is any one or a mixture of more of aluminum dihydrogen phosphate, aluminum sulfate and aluminum nitrate.
6. The method for modifying the airway surface of a corundum spinel slit-type air brick according to claim 1, characterized by: wherein the zirconium salt is ZrOCl 2 ·8H 2 O or ZrOCl 2 ·8H 2 O is the zirconia solution prepared from the starting materials.
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