CN114853485A - Ladle down nozzle and preparation method thereof - Google Patents
Ladle down nozzle and preparation method thereof Download PDFInfo
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- CN114853485A CN114853485A CN202210311072.2A CN202210311072A CN114853485A CN 114853485 A CN114853485 A CN 114853485A CN 202210311072 A CN202210311072 A CN 202210311072A CN 114853485 A CN114853485 A CN 114853485A
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- Prior art keywords
- ladle
- parts
- nozzle
- raw materials
- bauxite
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 polysiloxane Polymers 0.000 claims abstract description 69
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 239000010431 corundum Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 50
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 48
- 229910000831 Steel Inorganic materials 0.000 claims description 33
- 239000010959 steel Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 11
- 229910002601 GaN Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 238000009434 installation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 2
- 238000009628 steelmaking Methods 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 42
- 230000035939 shock Effects 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 13
- 230000002035 prolonged effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 238000009991 scouring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 229910026551 ZrC Inorganic materials 0.000 description 4
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/50—Pouring-nozzles
- B22D41/52—Manufacturing or repairing thereof
- B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3839—Refractory metal carbides
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—Aluminium
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The application relates to the technical field of metallurgical casting equipment, and particularly discloses a ladle down nozzle and a preparation method thereof. The ladle nozzle comprises a granular material, a fine powder material and a binding agent for combining the granular material and the fine powder material, wherein the granular material comprises the following raw materials in parts by weight: high bauxite; the fine powder comprises the following raw materials in parts by weight: sintered corundum powder, metal aluminum powder, graphite powder, Guangxi white mud and polysiloxane; the binding agent comprises the following raw materials in parts by weight: a high temperature resistant resin; the preparation method comprises the following steps: premixing, mixing, secondary mixing, ageing, blank making, drying, shell filling and secondary drying. The ladle down nozzle can be used for ladle steelmaking, and has the advantages of reducing the probability of cracks in the ladle down nozzle and prolonging the service life of the ladle down nozzle.
Description
Technical Field
The application relates to the technical field of metallurgical casting equipment, in particular to a ladle down nozzle and a preparation method thereof.
Background
Ladles are commonly used in steel plants and foundries for receiving molten steel in front of an open hearth furnace, an electric furnace or a converter and performing pouring operation, and common structural forms include a stopper rod type ladle and a sliding gate type ladle, wherein the sliding gate is an important system for controlling the flow of the molten steel in the ladle.
The ladle nozzle is one of the components of the sliding nozzle, usually the ladle nozzle is made of aluminum carbon, and in the process of smelting molten steel, high-temperature molten steel continuously passes through and erodes the ladle nozzle, so that cracks are easily generated in the ladle nozzle, and the service life of the ladle nozzle is shortened.
Disclosure of Invention
In order to reduce the probability of cracks in the ladle drain opening and prolong the service life of the ladle drain opening, the application provides the ladle drain opening and the preparation method thereof.
In a first aspect, the present application provides a ladle nozzle, which adopts the following technical scheme:
a ladle nozzle comprises a granular material, a fine powder material and a binding agent for combining the granular material and the fine powder material, wherein the granular material comprises the following raw materials in parts by weight: 63-71 parts of high-alumina bauxite;
the fine powder comprises the following raw materials in parts by weight: 12-18 parts of sintered corundum powder, 2-6 parts of metal aluminum powder, 1-3 parts of graphite powder, 1-4 parts of Guangxi white mud and 2-8 parts of polysiloxane;
the binding agent comprises the following raw materials in parts by weight: 3-6 parts of high-temperature resistant resin.
By adopting the technical scheme, the high bauxite has strong chemical stability and high refractoriness as a basic framework of the ladle drain nozzle, so that the ladle drain nozzle can be normally used at high temperature, the stability and the strength of the ladle drain nozzle can be improved, and the ladle drain nozzle is not easy to explode under the scouring of molten steel when contacting high-temperature molten steel; the sheet crystal structure of the sintered corundum has the advantages that the sintered corundum is large in volume density, low in porosity and more in internal closed air holes, and has thermal shock resistance and peeling resistance at high temperature, and the well-developed crystal structure in the sintered corundum improves the creep resistance of a ladle nozzle and improves the strength of the ladle nozzle.
The graphite powder has the advantages that the strength of the graphite powder is enhanced along with the rise of the temperature, the thermal shock resistance is good, when the temperature changes rapidly, the volume change is not large, the side wall of the ladle drain nozzle is not easy to crack due to the extrusion of high-temperature molten steel, meanwhile, the situation that the ladle drain nozzle is cracked due to the temperature change when the high-temperature molten steel flows through the ladle drain nozzle is avoided as much as possible, the graphite has lubricating property, and in the process of mixing raw materials, the graphite has a lubricating effect, so that all the raw materials are dispersed more uniformly, and the density of all parts of the ladle drain nozzle is uniform and stable.
The metal aluminum powder is used as an antioxidant and reacts with oxygen, calcium and the like in high-temperature molten steel to form a compact oxide film, other raw materials in the ladle nozzle are wrapped in the oxide film, the condition that the ladle nozzle is corroded due to the reaction of the raw materials such as high bauxite and the like and the molten steel is avoided as much as possible, and the corrosion resistance of the ladle nozzle is improved; the Guangxi white mud serving as soft clay has binding force, can wrap and bind all raw materials, and enhances the binding force of a ladle nozzle.
The polysiloxane has flexibility, wraps the polysiloxane outside the raw materials of the ladle nozzle, can reduce the brittleness of the ladle nozzle while enhancing the strength and hardness of the ladle nozzle by each raw material, ensures that the ladle nozzle is not easy to break under the scouring of high-temperature molten steel, prolongs the service life of the ladle nozzle, has binding force, and enhances the bonding stability of the ladle nozzle.
Preferably, the granular materials comprise the following raw materials in parts by weight: 65-69 parts of high-alumina bauxite;
the fine powder comprises the following raw materials in parts by weight: 14-16 parts of sintered corundum powder, 3-5 parts of metal aluminum powder, 1.5-2.5 parts of graphite powder, 2-3 parts of Guangxi white mud and 4-6 parts of polysiloxane;
the binding agent comprises the following raw materials in parts by weight: 4-5 parts of high-temperature resistant resin.
By adopting the technical scheme, the proportion among the raw materials is optimized, so that the polysiloxane is further uniformly mixed with the raw materials, the brittleness of the ladle drain nozzle is reduced while the hardness and the strength of the ladle drain nozzle are improved, the ladle drain nozzle is not easy to break under the action of high-temperature molten steel scouring, and the service life of the ladle drain nozzle is prolonged.
Preferably, the granule consists of bauxite with the particle size of 0-1mm and bauxite with the particle size of 1-3mm, and the weight ratio of the bauxite with the particle size of 0-1mm to the bauxite with the particle size of 1-3mm is (14-16): (50-54).
By adopting the technical scheme, the high bauxite consists of the raw materials with the grain sizes of 0-1mm and 1-3mm, the high bauxite with the grain sizes of two kinds are mutually combined in the process of producing the ladle nozzle, the high bauxite with the grain size of small grain is filled between the high bauxite with the grain size of large grain, the density and the strength of the ladle nozzle are increased, the ladle nozzle is not easy to burst due to the scouring of high-temperature molten steel, and the service life of the ladle nozzle is prolonged.
Preferably, the polysiloxane is polydimethylsiloxane.
By adopting the technical scheme, the polydimethylsiloxane is added in the raw material species, and the polydimethylsiloxane has hydrophobicity and high and low temperature resistance while having flexibility, can further disperse all the raw materials of the ladle drain nozzle when being added into the raw materials of the ladle drain nozzle, reduces the condition of uneven density of all parts of the ladle drain nozzle, ensures that the ladle drain nozzle is not easy to crack due to scouring of high-temperature molten steel, and prolongs the service life of the ladle drain nozzle.
Preferably, the polydimethylsiloxane is modified polydimethylsiloxane, and the modified polydimethylsiloxane is prepared from gallium nitride, a zirconate coupling agent and polydimethylsiloxane in a weight ratio of (1-2): (0.5-1.5): (2-3), and the preparation steps of the modified polydimethylsiloxane are as follows:
a1, heating and dispersing gallium nitride at the temperature of 110-130 ℃, and adding a zirconate coupling agent to obtain a dispersed mixture;
a2, adding polydimethylsiloxane to the mixture prepared in A1 and dispersing to obtain modified polydimethylsiloxane.
By adopting the technical scheme, the polydimethylsiloxane is modified by utilizing the gallium nitride, so that the hardness of the polydimethylsiloxane is improved while the flexibility of the polydimethylsiloxane is kept, and the modified polydimethylsiloxane can form a protective layer outside an oxide film formed by metal aluminum powder, so that a ladle drain nozzle is not easily corroded by high-temperature molten steel, the service life of the ladle drain nozzle is prolonged, and the gallium nitride can also react with calcium, oxygen and the like in the molten steel to generate compact oxides and attach to the surfaces of other raw materials in the ladle drain nozzle, so that the consumption of other raw materials in the ladle drain nozzle is reduced, and the service life of the ladle drain nozzle is prolonged; the zirconate coupling agent can form zirconium dioxide and finally form zirconium carbide, so that the erosion resistance and the strength of the ladle nozzle are enhanced.
Preferably, the high-temperature resistant resin is phenolic resin.
By adopting the technical scheme, the phenolic resin is selected as the binding agent, has high temperature resistance, can keep the integrity and the dimensional stability of the structure of the ladle drain nozzle wood, is compatible with various organic matters and inorganic fillers, can bond polydimethylsiloxane and other raw materials in the ladle drain nozzle to form a stable structure, has high carbon residue rate at high temperature, can maintain the stability of the phenolic resin, increases the stability of the ladle drain nozzle, can resist the decomposition of chemical substances, ensures that the ladle drain nozzle is not easily corroded by high-temperature molten steel, and prolongs the service life of the ladle drain nozzle.
In a second aspect, the application provides a method for preparing a ladle down nozzle, which adopts the following technical scheme:
a preparation method of a ladle down nozzle comprises the following steps:
s1, premixing: stirring and mixing sintered corundum powder, metal aluminum powder, graphite powder and Guangxi white mud to prepare a premix;
s2, mixing materials: stirring the high-alumina bauxite, adding high-temperature-resistant resin, stirring, adding the premix prepared in the step S1, and stirring to obtain a mixture;
s3, secondary mixing: adding polysiloxane into the mixture prepared in the S2 and stirring to prepare a secondary mixture;
s4, ageing: placing the secondary mixture prepared in the step S3 at constant temperature to prepare an ageing mixture;
s5, blank making: pressing the mixture after ageing the mixture prepared in the S4, and placing the pressed mixture at room temperature to prepare a pressed blank;
s6, drying: drying the pressed blank prepared in the step S5, and cooling the dried pressed blank;
s7, shell installation: filling the cooled pressing blank in the step S6 into a steel shell, and cooling at room temperature to obtain a prefabricated ladle down nozzle;
s8, secondary drying: and (4) secondarily drying the prefabricated ladle down nozzle prepared in the S7 to prepare the ladle down nozzle.
By adopting the technical scheme, through the steps of premixing, mixing, secondary mixing and the like, the high-alumina bauxite and the high-temperature-resistant resin are uniformly mixed, fine powder materials such as sintered corundum powder, metal aluminum powder, graphite powder, Guangxi white mud and the like are uniformly mixed and then are wrapped outside the high-alumina bauxite and the high-temperature-resistant resin, the fine powder materials and the high-alumina bauxite are wrapped by polysiloxane, all raw materials are dispersed more uniformly in the material trapping process, volatile gas escapes at the same time, all raw materials are combined through the processes of pressing and the like through the processes of blank making, drying, shell filling, secondary drying and the like to form the ladle drain outlet, the strength of the ladle drain outlet and the erosion resistance of the ladle drain outlet are improved, and the service life of the ladle drain outlet is further prolonged.
Preferably, in the step S4, the ageing time is 18-22 h.
By adopting the technical scheme, the ageing time is preferably 18-22h, so that all raw materials in the ladle nozzle are fully dispersed and mixed, volatile gas remained in the raw materials escapes, all the raw materials are combined more fully, the high bauxite has recombination time to form a basic skeleton, the strength of the ladle nozzle is increased, and meanwhile, the high bauxite and fine powder are fully wrapped by polysiloxane to form a protective layer; when the ageing time is less than 18h, all raw materials in the ladle drain nozzle are not uniformly dispersed, the density of the ladle drain nozzle is not uniform, and the steel ladle drain nozzle is easy to crack in the molten steel smelting process, so that the service life of the ladle drain nozzle is influenced; when the ageing time is longer than 22h, particles with large weight in the raw materials are easy to gradually deposit under the action of gravity, the density of the ladle nozzle is also uneven, the cracking condition is easy to occur in the process of smelting molten steel, and the service life of the ladle nozzle is influenced.
Preferably, in the step S6, the drying temperature is 330-370 ℃.
By adopting the technical scheme, the drying temperature is 330-370 ℃, in the drying process, the moisture remained in the raw materials is gradually volatilized, simultaneously the high-temperature resistant resin is gradually cured, the bonding force between the high-alumina and the fine powder is enhanced, at the moment, the zirconate coupling agent generates zirconium dioxide, the hardness and the strength of the ladle nozzle are increased, simultaneously, the polydimethylsiloxane is decomposed and polymerized to form the polycarboxyane, when the ladle nozzle is contacted with the high-temperature molten steel, the zirconium dioxide generates zirconium carbide, the strength of the ladle nozzle is further increased, the high-alumina and the fine powder are wrapped, the possibility of the reaction between the high-alumina and the fine powder and the molten steel is reduced, the gallium nitride forms an oxidation film at high temperature, the high-alumina and the fine powder are further wrapped, nitrogen is released simultaneously, and the metal aluminum powder can be used as an activating agent, so that the polycarboxyane generates silicon carbide, the hardness and the strength of the ladle nozzle are increased, the possibility of explosion cracking when the ladle down nozzle contacts molten steel is reduced, meanwhile, the ladle down nozzle is prevented from being corroded as much as possible, and the service life of the ladle down nozzle is prolonged; when the drying temperature is less than 330 ℃, the modified polydimethylsiloxane is difficult to generate an oxide film and polycarbosiloxane, and the erosion resistance of a ladle drain nozzle is influenced; when the drying temperature is higher than 370 ℃, energy waste is easily caused, and meanwhile, the high-temperature resistant resin generates volatile gas to influence the environment.
In summary, the present application has the following beneficial effects:
1. the high-alumina bauxite is a basic framework, has strong chemical stability, and can improve the stability and strength of a ladle nozzle; because of the plate-shaped crystal structure and the well-developed crystal structure of the sintered corundum, the creep resistance of the ladle drain nozzle is improved; the tensile strength of the graphite powder at high temperature is enhanced, the thermal shock resistance is good, the ladle nozzle is not easy to crack, and the density of each part of the ladle nozzle is uniform and stable due to the lubricating property of the graphite; the metal aluminum powder is an antioxidant and reacts with oxygen, calcium and the like in the high-temperature molten steel to form a compact oxide film, so that the erosion resistance of the ladle nozzle is improved; guangxi white mud enhances the binding power of a ladle down nozzle; the flexibility of the polysiloxane reduces the brittleness of the ladle drain, so that the ladle drain is not easy to break under the washing of high-temperature molten steel, and the service life of the ladle drain is prolonged.
2. The gallium nitride modified polydimethylsiloxane improves the hardness of the polydimethylsiloxane, so that the modified polydimethylsiloxane can form a protective layer outside an oxide film formed by metal aluminum powder, a ladle drain is not easy to be corroded by high-temperature molten steel, the service life of the ladle drain is prolonged, the gallium nitride reacts with calcium, oxygen and the like in the molten steel to generate compact oxides and the compact oxides are attached to the surfaces of other raw materials of the ladle drain, the consumption of the other raw materials in the ladle drain is reduced, zirconium carbide is formed by a zirconate coupling agent at high temperature, the erosion resistance and the strength of the ladle drain are enhanced, and the service life of the ladle drain is prolonged.
3. The drying temperature is 330-370 ℃, the moisture remained in the raw material is volatilized, the high-temperature resistant resin is solidified, the binding force between the high-alumina bauxite and the fine powder is enhanced, the zirconium dioxide is generated by the zirconate coupling agent, the hardness and the strength of the ladle nozzle are increased, meanwhile, the polydimethylsiloxane forms the polycarboxyalkane, when the ladle nozzle contacts with the high-temperature molten steel, the zirconium dioxide generates zirconium carbide and wraps the high-alumina bauxite and the fine powder, the gallium nitride forms an oxide film at high temperature, simultaneously nitrogen is released, the metal aluminum powder is used as an active agent, the polycarboxyalkane generates silicon carbide, the hardness and the strength of the ladle nozzle are increased, and the service life of the ladle nozzle is prolonged.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
The raw materials used in the examples were all commercially available, wherein the alumina content in the high alumina bauxite was 85%, the calcium oxide content was 0.6%, the alumina content in the sintered corundum powder was 99%, the zirconate coupling agent was 103455-10-3 from golden jele chemical co., ltd, the polydimethylsiloxane was PHR1518-1G from sigma aldrich trade ltd, and the aluminate coupling agent was yc-2020 from carge, su.
Preparation example
Preparation example 1
The preparation method of the modified polydimethylsiloxane comprises the following steps:
a1, heating and dispersing 1Kg of gallium nitride at 110 ℃, and adding 1.5Kg of zirconate coupling agent to obtain a dispersed mixture;
a2, 2Kg of polydimethylsiloxane was added to the mixture obtained in A1 and dispersed to obtain a modified polydimethylsiloxane.
Preparation examples 2 to 3
Different from preparation example 1, the raw material ratios and heating temperatures of the modified polydimethylsiloxane prepared in preparation examples 2-3 are different, and the details are shown in Table 1.
TABLE 1 raw material compounding ratio and heating temperature of preparation examples 2 to 3
| Silicon nitride/Kg | Zirconate coupling agent/Kg | polydimethylsiloxane/Kg | Heating temperature/. degree.C | |
| Preparation example 1 | 1 | 1.5 | 2 | 110 |
| Preparation example 2 | 1.5 | 1 | 2.5 | 120 |
| Preparation example 3 | 2 | 0.5 | 3 | 130 |
Preparation example 4
Unlike preparation example 2, preparation example 4 uses an equivalent amount of aminosilane instead of the zirconate coupling agent.
Preparation example 5
Unlike preparation example 2, preparation example 5 used an equivalent amount of an aluminate coupling agent instead of a zirconate coupling agent.
Examples
Example 1
A ladle down nozzle, its preparation method is:
s1, premixing: stirring and mixing 12Kg of sintered corundum powder, 6Kg of metal aluminum powder, 1Kg of graphite powder and 4Kg of Guangxi white mud to prepare a premix;
s2, mixing materials: stirring 71Kg of high bauxite with the particle size of 1-3mm, adding 6Kg of phenolic resin, stirring, adding the premix prepared in S1, and stirring to obtain a mixture;
s3, secondary mixing: adding 2Kg of polydimethylsiloxane into the mixture prepared in S2 and stirring to prepare a secondary mixture;
s4, ageing: placing the secondary mixture prepared in the S3 for 18h at constant temperature to prepare a mixture after ageing;
s5, blank making: pressing the mixture after ageing the mixture prepared in the S4, and placing the pressed mixture at room temperature to prepare a pressed blank;
s6, drying: drying the pressed blank prepared in the S5 at 330 ℃, and cooling the dried pressed blank to 90 ℃;
s7, shell installation: filling the cooled pressing blank in the step S6 into a steel shell, and cooling at room temperature to obtain a prefabricated ladle down nozzle;
s8, secondary drying: and (4) secondarily drying the prefabricated ladle down nozzle prepared in the S7 to prepare the ladle down nozzle.
Examples 2 to 7
Different from the embodiment 1, the ladle nozzle in the embodiments 2 to 7 has different raw material ratios, ageing time and drying temperature, and the details are shown in the table 2.
TABLE 2 ladle down nozzle raw material ratio, ageing time and drying temperature
Example 8
Unlike example 6, in example 8, the same amount of high alumina having a particle size of 0 to 1mm was used in place of the high alumina.
Example 9
Different from the embodiment 6, in the embodiment 9, the weight ratio of the equivalent 0-1mm particle size and 1-3mm particle size is 7: the high bauxite of 27 replaced the high bauxite.
Example 10
Different from the embodiment 6, in the embodiment 10, the weight ratio of the equivalent 0-1mm particle size and 1-3mm particle size is 15: bauxite of 52 is substituted for the bauxite.
Example 11
Unlike example 6, in example 11, the weight ratio of the particle size of 0 to 1mm to that of 1 to 3mm in the same amount was 8: 25 of bauxite instead of bauxite.
Example 12
In contrast to example 10, in example 12, the polydimethylsiloxane was replaced by the same amount of polydiethylsiloxane.
Examples 13 to 17
In contrast to example 10, modified polydimethylsiloxanes prepared in preparation examples 1 to 5 were used in place of polydimethylsiloxanes in examples 13 to 17 in the same amounts.
Comparative example
Comparative example 1
Unlike example 6, no polydimethylsiloxane was added in comparative example 1.
Comparative example 2
Unlike example 6, the polydimethylsiloxane was added in an amount of 15Kg in comparative example 2.
Performance test
The following performance tests were performed for the ladle shroud manufactured in examples 1 to 17 and comparative examples 1 to 2. The performance detection comprises the breaking strength, the thermal shock resistance and the use times of the ladle nozzle, and the detection data are shown in table 3.
1. Compressive strength
And (3) detecting the breaking strength of the manufactured ladle drain according to the detection standard of GB/T5072 + 2008 'test method for normal temperature compressive strength of refractory material'. Detecting the environment: at 25 ℃.
2. Thermal shock resistance
And detecting the thermal shock resistance of the manufactured ladle drain according to the detection standard of the thermal shock resistance test method of refractory materials in the national standard GB/T30873 and 2014.
3. Number of times of use
The ladle down nozzle prepared in the embodiment 1-17 and the comparative example 1-2 of the application is used in the same ladle for smelting molten steel, and the using times of the ladle down nozzle are detected.
TABLE 3 Performance test data sheet
The present application is described below with reference to the test data in table 3.
Combining examples 1-17 and comparative examples 1-2, it was found that the ladle shroud made in examples 1-17 of the present application was superior to comparative examples 1-2 in compressive strength, thermal shock resistance, and number of uses, indicating that the ladle shroud made in the present application performed better in compressive strength, thermal shock resistance, and number of uses.
The comparison of the addition ratios of the raw materials of the ladle nozzle in examples 1 to 5 shows that the ladle nozzle prepared in example 3 is superior in compressive strength, thermal shock resistance and use frequency, which indicates that the raw material addition ratio of the ladle nozzle in example 3 is superior.
In comparison with example 3, the present inventors examined the effects of the aging time and the drying temperature on the ladle shroud in examples 6 and 7, and found that the ladle shroud obtained in example 6 performed better in compressive strength, thermal shock resistance and number of uses, which indicates that the aging time and the drying temperature used in example 6 were better.
In example 8, the influence of different particle sizes of bauxite on the ladle nozzle is examined by taking example 6 as a comparison, and as a result, the ladle nozzle prepared in example 8 is found to be poor in compressive strength, thermal shock resistance and use times, which indicates that the bauxite particle size selected in example 6 is better.
In comparison with example 6, the present inventors examined the effect of the bauxite with different particle sizes added to the raw materials on the ladle shroud in examples 9 to 11, and found that the ladle shroud prepared in examples 9 to 11 is superior to example 6 in compressive strength, thermal shock resistance and use frequency, probably because the bauxite with different particle sizes added to the raw materials combines with each other to form a basic skeleton, which enhances the strength and corrosion resistance of the ladle shroud.
In examples 9 to 11 of the present application, the influence of the addition ratios of the bauxite with different particle sizes was examined, and as a result, it was found that the ladle shroud prepared in example 10 is superior in compressive strength, thermal shock resistance and the number of times of use, which indicates that the bauxite with different particle sizes used in example 10 is superior in the addition ratio.
In comparison with example 10, in this application, example 12 examined the effect of different polysiloxanes, and as a result, it was found that the ladle nozzle prepared by using the same amount of polydiethylsiloxane as that used in example 12 instead of polydimethylsiloxane was inferior in compressive strength, thermal shock resistance and use frequency, which indicates that the use of polydimethylsiloxane in example 10 is superior in improving the compressive strength, thermal shock resistance and use frequency of the ladle nozzle.
In comparison with example 10, the present inventors examined the effect of modified polydimethylsiloxane in examples 13 to 15, and as a result, found that the ladle shroud prepared in examples 13 to 15 is superior to example 10 in compressive strength, thermal shock resistance and the number of times of use, which indicates that the addition of modified polydimethylsiloxane to the raw material is superior in improving the compressive strength, thermal shock resistance and the number of times of use of the ladle shroud.
In examples 13 to 15, the present inventors examined the influence of different ratios of raw materials in modified polydimethylsiloxane, and as a result, found that the ladle nozzle prepared in example 14 is superior in compressive strength, thermal shock resistance, and use frequency, which indicates that the ratio of raw materials in the modified polydimethylsiloxane selected in example 14 is superior in improving the compressive strength, thermal shock resistance, and use frequency of the ladle nozzle.
By taking the example 14 as a contrast, the application inspects the influence of different coupling agents in the examples 16 to 17, and as a result, the application discovers that the same amount of aminosilane is selected to replace the zirconate coupling agent in the example 16, and the manufactured ladle nozzle is poor in compressive strength, thermal shock resistance and use times; in example 17, the equivalent amount of aluminate coupling agent is selected to replace the zirconate coupling agent, and the prepared ladle nozzle is poor in compressive strength, thermal shock resistance and use times, which shows that the zirconate coupling agent selected in example 14 is better in improving the compressive strength, the thermal shock resistance and the use times of the ladle nozzle.
Combining example 6 and comparative example 1, it is found that the ladle nozzle prepared in comparative example 1 without adding polydimethylsiloxane is poor in compressive strength, thermal shock resistance and use times, which shows that the addition of polydimethylsiloxane to the raw materials is superior in improving the compressive strength, thermal shock resistance and use times of the ladle nozzle.
Combining example 6 and comparative example 2, it is found that the addition amount of the polydimethylsiloxane in the comparative example 2 is larger than that in the example 6, and the prepared ladle nozzle is poor in compressive strength, thermal shock resistance and use times, which shows that the addition amount of the polydimethylsiloxane selected in the example 6 is better in improving the compressive strength, thermal shock resistance and use times of the ladle nozzle.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The ladle nozzle comprises a granular material, a fine powder material and a binding agent for combining the granular material and the fine powder material, and is characterized in that the granular material comprises the following raw materials in parts by weight: 63-71 parts of high-alumina bauxite; the fine powder comprises the following raw materials in parts by weight: 12-18 parts of sintered corundum powder, 2-6 parts of metal aluminum powder, 1-3 parts of graphite powder, 1-4 parts of Guangxi white mud and 2-8 parts of polysiloxane; the binding agent comprises the following raw materials in parts by weight: 3-6 parts of high-temperature resistant resin.
2. The ladle nozzle as defined in claim 1, wherein: the granular material comprises the following raw materials in parts by weight: 65-69 parts of high-alumina bauxite; the fine powder comprises the following raw materials in parts by weight: 14-16 parts of sintered corundum powder, 3-5 parts of metal aluminum powder, 1.5-2.5 parts of graphite powder, 2-3 parts of Guangxi white mud and 4-6 parts of polysiloxane; the binding agent comprises the following raw materials in parts by weight: 4-5 parts of high-temperature resistant resin.
3. The ladle nozzle according to claim 1, wherein: the particle material consists of bauxite with the particle size of 0-1mm and bauxite with the particle size of 1-3mm, and the weight ratio of the bauxite with the particle size of 0-1mm to the bauxite with the particle size of 1-3mm is (14-16): (50-54).
4. The ladle nozzle according to claim 1, wherein: the polysiloxane is polydimethylsiloxane.
5. The ladle nozzle according to claim 4, wherein: the polydimethylsiloxane is modified polydimethylsiloxane, and the modified polydimethylsiloxane is prepared from gallium nitride, a zirconate coupling agent and polydimethylsiloxane in a weight ratio of (1-2): (0.5-1.5): (2-3), and the preparation steps of the modified polydimethylsiloxane are as follows:
a1, heating and dispersing gallium nitride at the temperature of 110-130 ℃, and adding a zirconate coupling agent to obtain a dispersed mixture;
a2, adding polydimethylsiloxane to the mixture prepared in A1 and dispersing to obtain modified polydimethylsiloxane.
6. The ladle nozzle according to claim 1, wherein: the high-temperature resistant resin is phenolic resin.
7. The method for manufacturing a ladle nozzle according to any one of claims 1 to 6, comprising the steps of:
s1, premixing: stirring and mixing sintered corundum powder, metal aluminum powder, graphite powder and Guangxi white mud to prepare a premix;
s2, mixing materials: stirring the high-alumina bauxite, adding high-temperature-resistant resin, stirring, adding the premix prepared in the step S1, and stirring to obtain a mixture;
s3, secondary mixing: adding polysiloxane into the mixture prepared in the S2 and stirring to prepare a secondary mixture;
s4, ageing: placing the secondary mixture prepared in the step S3 at constant temperature to prepare an ageing mixture;
s5, blank making: pressing the mixture after ageing the mixture prepared in the S4, and placing the pressed mixture at room temperature to prepare a pressed blank;
s6, drying: drying the pressed blank prepared in the step S5, and cooling the dried pressed blank;
s7, shell installation: filling the cooled pressing blank in the step S6 into a steel shell, and cooling at room temperature to obtain a prefabricated ladle down nozzle;
s8, secondary drying: and (4) secondarily drying the prefabricated ladle down nozzle prepared in the S7 to prepare the ladle down nozzle.
8. The method for preparing a ladle nozzle according to claim 7, wherein: in the step S4, the ageing time is 18-22 h.
9. The method for preparing a ladle nozzle according to claim 7, wherein: in the step S6, the drying temperature is 330-370 ℃.
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| CN115959920A (en) * | 2023-02-08 | 2023-04-14 | 江苏泰瑞耐火有限公司 | Toughened zirconia ceramic tundish nozzle for continuous casting of square and round billets and production process thereof |
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Application publication date: 20220805 |