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CN111116195A - Immersion nozzle zirconium metal ceramic combined erosion-resistant material - Google Patents

Immersion nozzle zirconium metal ceramic combined erosion-resistant material Download PDF

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Publication number
CN111116195A
CN111116195A CN201911333272.2A CN201911333272A CN111116195A CN 111116195 A CN111116195 A CN 111116195A CN 201911333272 A CN201911333272 A CN 201911333272A CN 111116195 A CN111116195 A CN 111116195A
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zirconia
zirconium
powder
resistant material
metal
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CN201911333272.2A
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Inventor
徐磊
鲍颢文
鲍志
周文春
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Jiangsu Oner Refractories Co ltd
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Jiangsu Oner Refractories Co ltd
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Priority to CN201911333272.2A priority Critical patent/CN111116195A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped 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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482Refractories from grain sized mixtures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40Metallic constituents or additives not added as binding phase
    • C04B2235/402Aluminium
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40Metallic constituents or additives not added as binding phase
    • C04B2235/404Refractory metals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428Silicon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a metal zirconium ceramic combined erosion-resistant material for a submerged nozzle, which comprises the following raw materials, by mass, 40-60% of zirconium oxide particles, 15-45% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 3-8% of a metal powder additive, 5-10% of a binder and 2-4% of metal zirconium. The metal zirconium can generate zirconia ceramic combination under the low temperature (400 ℃), the chemical stability of the metal zirconium is superior to that of resin-combined carbon-containing materials, the problem of carbon oxidation does not exist even in a high-oxygen use environment, and the corrosion resistance effect is obvious compared with that of the original aluminum zirconium carbon material.

Description

Immersion nozzle zirconium metal ceramic combined erosion-resistant material
Technical Field
The invention relates to the technical field of refractory materials for continuous casting, in particular to a zirconium-ceramic combined erosion-resistant material for a submerged nozzle.
Background
In the continuously developing engineering of the steel industry, the aluminum-carbon refractory material for continuous casting is a novel refractory material which has emerged in the last century. The method is gradually popularized from the beginning of application to ladle bricks to tundish continuous casting. Provides technical support for the development of continuous casting technology.
The submerged nozzle material in the refractory material for continuous casting is generally designed by mainly using a resin-bonded Al2O3-C material, in order to strengthen the corrosion resistance, the slag line part is usually formed by bonding materials such as zirconia, graphite and the like into a zirconium-carbon material by resin, and additives (such as SiC, Si and Al) improve the oxidation resistance of the material and ensure that the product meets the requirements of molten steel continuous casting.
In recent years, the molten steel smelting rhythm is accelerated, and the requirements on the refractory materials for continuous casting are higher and higher. In the case of a submerged nozzle, particularly, at a nozzle slag line part (a joint of molten steel and casting powder), because the casting powder with an ultrahigh pulling speed is high in alkali and low in melting point, the zirconium oxide at the nozzle slag line part is inevitably increased, thermal shock of a nozzle is reduced, and an anti-cracking layer has to be arranged on the inner wall of the nozzle, so that the effective wall thickness of the nozzle is thinned, the service life of the nozzle is reduced, and the problem is a contradiction.
Under the condition of ultrahigh machine pulling speed production, in order to ensure the blank shell cooling effect, dissolve the covering slag and prevent slag entrapment and the like, the adjustment range of the immersion depth is only 20-30 mm, and the slag lifting is not obvious due to the deformation of a tundish and other reasons in actual production, so that the slag lifting is almost close to a slag line for use.
The conventional ZrO2-C material has not been able to meet the use requirements of the continuous casting process. When molten steel with high oxygen content is met, the oxidation of carbon of a zirconium carbon material is also accompanied, so that the original submerged nozzle material cannot meet the long-service-life requirement of continuous casting production.
Disclosure of Invention
The invention aims to provide a zirconium-ceramic combined erosion-resistant material for a submerged nozzle.
The metal zirconium can generate zirconia ceramic combination under the low temperature (400 ℃), the chemical stability of the metal zirconium is superior to that of resin-combined carbon-containing materials, the problem of carbon oxidation does not exist even in a high-oxygen use environment, and the corrosion resistance effect is obvious compared with that of the original aluminum zirconium carbon material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the immersion nozzle zirconium metal ceramic combined erosion-resistant material comprises, by mass, 40-60% of zirconium oxide particles, 15-45% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 3-8% of metal powder additive, 5-10% of binder and 2-4% of metal zirconium.
Further, the zirconia particles are composed of one or more of fused zirconia, fused stabilized zirconia or calcium yttrium composite stabilized zirconia.
Further, ZrO2 in the zirconia particles is greater than or equal to 94.0 wt%.
Further, the zirconia particles comprise 7-11 parts by weight of particles with the particle size grade of 0.125-0.4 mm and 2-5 parts by weight of particles with the particle size grade of 0.4-0.6 mm.
Further, the zirconia fine powder comprises, by weight, 4-7 parts of zirconia fine powder with a particle size grade of 0-0.044 mm and 2-5 parts of zirconia fine powder with a particle size grade of 0.074-0.044 mm.
Further, the particle size of the zirconia micropowder is <1 μm.
Further, the metal powder additive is aluminum powder, silicon powder or aluminum-silicon alloy powder.
Further, the binder is an organic binder or an inorganic binder, the organic binder is resin or asphalt, and the inorganic binder is water glass or aluminum phosphate.
The invention has the beneficial effects that: the zirconium metal in the invention can generate zirconia ceramic combination under the low temperature (400 ℃), the chemical stability of the zirconium metal is superior to that of resin-combined carbon-containing materials, the problem of carbon oxidation does not exist even in the high-oxygen use environment, and the anti-corrosion effect is obvious.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1: the zirconium metal ceramic combined erosion-resistant material for the submerged nozzle comprises, by mass, 40% of zirconium oxide particles, 45% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 3% of metal powder additive, 5% of binder and 2% of metal zirconium. The zirconia particles are fused zirconia, and ZrO2 accounts for 94.0 wt% of the zirconia particles; the zirconia particles comprise 7 parts of particles with the granularity grade of 0.125-0.4 mm and 2 parts of particles with the granularity grade of 0.4-0.6 mm in parts by weight; the zirconia fine powder comprises 4 parts of zirconia fine powder with the granularity grade of 0-0.044 mm and 2 parts of zirconia fine powder with the granularity grade of 0.074-0.044 mm in parts by weight; the granularity of the zirconia micro powder is less than 1 mu m; the metal powder additive is aluminum powder; the binder is an organic binder, and the organic binder is resin.
Example 2: the zirconium metal ceramic combined erosion-resistant material for the submerged nozzle comprises, by mass, 60% of zirconium oxide particles, 15% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 8% of metal powder additive, 10% of binding agent and 2% of metal zirconium. The zirconia particles are electrofusion stabilized zirconia, and ZrO2 accounts for 96.0 wt% of the zirconia particles; the zirconia particles comprise 9 parts of zirconia particles with the granularity grade of 0.125-0.4 mm and 3 parts of zirconia particles with the granularity grade of 0.4-0.6 mm in parts by weight; the zirconia fine powder comprises 5 parts of zirconia fine powder with the granularity grade of 0-0.044 mm and 3 parts of zirconia fine powder with the granularity grade of 0.074-0.044 mm in parts by weight; the granularity of the zirconia micro powder is less than 1 mu m; the metal powder additive is silicon powder; the binder is an organic binder, and the organic binder is asphalt.
Example 3: the zirconium metal ceramic combined erosion-resistant material for the submerged nozzle comprises the following raw materials, by mass, 50% of zirconium oxide particles, 30% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 5% of metal powder additive, 6% of binding agent and 4% of metal zirconium. The zirconia particles consist of fused zirconia and fused stable zirconia, and the zirconia particles are ZrO 2; the zirconia particles comprise 10 parts of zirconia particles with the granularity grade of 0.125-0.4 mm and 4 parts of zirconia particles with the granularity grade of 0.4-0.6 mm in parts by weight; the zirconia fine powder comprises 6 parts of zirconia fine powder with the granularity grade of 0-0.044 mm and 4 parts of zirconia fine powder with the granularity grade of 0.074-0.044 mm in parts by weight; the granularity of the zirconia micro powder is less than 1 mu m; the metal powder additive is aluminum-silicon alloy powder; the binding agent is an inorganic binding agent, and the inorganic binding agent is water glass.
Example 4: the zirconium metal ceramic combined erosion-resistant material for the submerged nozzle comprises, by mass, 51% of zirconium oxide particles, 28% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 6% of metal powder additive, 7% of binder and 3% of metal zirconium. The zirconia particles are one or more of fused zirconia, fused stabilized zirconia or calcium yttrium composite stabilized zirconia, and the zirconia particles are ZrO 2; the zirconia particles comprise 11 parts of particles with the granularity grade of 0.125-0.4 mm and 5 parts of particles with the granularity grade of 0.4-0.6 mm in parts by weight; the zirconia fine powder comprises 7 parts of zirconia fine powder with the granularity grade of 0-0.044 mm and 5 parts of zirconia fine powder with the granularity grade of 0.074-0.044 mm in parts by weight; the granularity of the zirconia micro powder is less than 1 mu m; the metal powder additive is aluminum-silicon alloy powder; the binding agent is an inorganic binding agent, and the inorganic binding agent is aluminum phosphate.
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (8)

1. The immersion nozzle zirconium metal ceramic combined erosion-resistant material is characterized by comprising, by mass, 40-60% of zirconium oxide particles, 15-45% of zirconium oxide fine powder, 5% of zirconium oxide micro powder, 3-8% of metal powder additives, 5-10% of binders and 2-4% of zirconium metal.
2. The submerged entry nozzle zirconium cermet bonded erosion resistant material of claim 1, characterized in that the zirconia particles are composed of one or more of electrofused zirconia, electrofused stabilized zirconia or calcium yttrium composite stabilized zirconia.
3. The submerged entry nozzle zirconium metal ceramic bonded erosion resistant material of claim 2, characterized in that ZrO2 ≥ 94.0 wt.% in the zirconia grains.
4. The immersion nozzle zirconium metal ceramic bonded erosion resistant material of claim 1, wherein the zirconia grains comprise 7 to 11 parts by weight of 0.125 to 0.4mm in grain size and 2 to 5 parts by weight of 0.4 to 0.6mm in grain size.
5. The immersion nozzle zirconium metal ceramic bonded erosion resistant material of claim 1, wherein the zirconia fine powder comprises 4 to 7 parts by weight of zirconia fine powder with a particle size grade of 0 to 0.044mm and 2 to 5 parts by weight of zirconia fine powder with a particle size grade of 0.074 to 0.044 mm.
6. The submerged entry nozzle zirconium cermet bonded erosion resistant material of claim 1, characterized in that the zirconia micro powder has a particle size <1 μm.
7. The submerged entry nozzle zirconium metal ceramic bonded erosion resistant material of claim 1, characterized in that the metal powder additive is aluminum powder, silicon powder or aluminum-silicon alloy powder.
8. The immersion nozzle zirconium metal ceramic bonded erosion resistant material of claim 1, wherein the binder is an organic binder or an inorganic binder, the organic binder is resin or asphalt, and the inorganic binder is water glass or aluminum phosphate.
CN201911333272.2A 2019-12-23 2019-12-23 Immersion nozzle zirconium metal ceramic combined erosion-resistant material Pending CN111116195A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608149A (en) * 2020-11-24 2021-04-06 阳春新钢铁有限责任公司 Ultrahigh-pulling-speed immersion type drain nozzle erosion-resistant material and preparation method thereof
CN113277846A (en) * 2021-05-27 2021-08-20 深圳市精而美精密陶瓷科技有限公司 Alumina in-situ composite zirconia ceramic powder, ceramic preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5732858A (en) * 1980-08-07 1982-02-22 Nippon Kokan Kk <Nkk> Immersion nozzle for continuous casting of molten steel
CN101851104A (en) * 2009-04-03 2010-10-06 吴钦合 Zirconium oxide ceramic composite material for continuous casting water gap and preparation method thereof
CN103922768A (en) * 2014-03-27 2014-07-16 中钢集团洛阳耐火材料研究院有限公司 Functional composite zirconium oxide refractory product and preparation method thereof
CN104058753A (en) * 2013-03-21 2014-09-24 宝山钢铁股份有限公司 Preparation method of zirconia zirconium diboride carbonaceous melt delivery tube
CN108164275A (en) * 2018-01-14 2018-06-15 江苏嘉耐高温材料有限公司 A kind of resistant to corrosion zirconium oxide nozzle brick and preparation method thereof
CN109422537A (en) * 2017-08-22 2019-03-05 宝山钢铁股份有限公司 Continuous casting is with exempting to toast refractory material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5732858A (en) * 1980-08-07 1982-02-22 Nippon Kokan Kk <Nkk> Immersion nozzle for continuous casting of molten steel
CN101851104A (en) * 2009-04-03 2010-10-06 吴钦合 Zirconium oxide ceramic composite material for continuous casting water gap and preparation method thereof
CN104058753A (en) * 2013-03-21 2014-09-24 宝山钢铁股份有限公司 Preparation method of zirconia zirconium diboride carbonaceous melt delivery tube
CN103922768A (en) * 2014-03-27 2014-07-16 中钢集团洛阳耐火材料研究院有限公司 Functional composite zirconium oxide refractory product and preparation method thereof
CN109422537A (en) * 2017-08-22 2019-03-05 宝山钢铁股份有限公司 Continuous casting is with exempting to toast refractory material and preparation method thereof
CN108164275A (en) * 2018-01-14 2018-06-15 江苏嘉耐高温材料有限公司 A kind of resistant to corrosion zirconium oxide nozzle brick and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李红霞: "《现代冶金功能耐火材料》", 28 February 2019 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608149A (en) * 2020-11-24 2021-04-06 阳春新钢铁有限责任公司 Ultrahigh-pulling-speed immersion type drain nozzle erosion-resistant material and preparation method thereof
CN113277846A (en) * 2021-05-27 2021-08-20 深圳市精而美精密陶瓷科技有限公司 Alumina in-situ composite zirconia ceramic powder, ceramic preparation method and application
CN113277846B (en) * 2021-05-27 2022-05-27 深圳市精而美精密陶瓷科技有限公司 Alumina in-situ composite zirconia ceramic powder, ceramic preparation method and application

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