CN107827456B - Preparation method of zirconia hollow sphere heat insulation product - Google Patents

Preparation method of zirconia hollow sphere heat insulation product Download PDF

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CN107827456B
CN107827456B CN201711302276.5A CN201711302276A CN107827456B CN 107827456 B CN107827456 B CN 107827456B CN 201711302276 A CN201711302276 A CN 201711302276A CN 107827456 B CN107827456 B CN 107827456B
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zirconia
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CN107827456A (en
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潘建华
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Hunan Renhai Materials Science And Technology Development Co ltd
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    • CCHEMISTRY; METALLURGY
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    • 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
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63404Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416Polyvinylalcohols [PVA]; Polyvinylacetates
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    • 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
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63448Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63452Polyepoxides
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    • 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
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C04B35/803
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    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5236Zirconia
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    • 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

Abstract

The invention discloses a preparation method of a zirconia hollow sphere heat insulation product, which comprises the following components in percentage by weight: 60-75% of zirconia hollow spheres with the granularity of 0.2-3 mm; 15-30% of fused zirconia fine powder with the particle size of less than or equal to 0.044 mm; 5-10% of chemical method zirconia micro powder with the granularity less than or equal to 2 um; 5-10% of zirconia fiber; using PVA or water-soluble epoxy resin as a binding agent, adding 4-8% of the total mass of the solid raw materials, using water-soluble zirconium salt as a burning promoter, adding 5-10% of the total mass of the solid raw materials, fully wetting zirconia hollow spheres and the binding agent, then adding electric melting zirconia fine powder, zirconia micro powder and zirconia fibers, uniformly mixing, adding the burning promoter, uniformly mixing, pressing the mixture into a green body, drying at 120 ℃ for 24-36 hours, and then keeping the temperature in a high-temperature kiln at 1700-1750 ℃ for 4-8 hours to burn. The invention reduces the sintering temperature, improves the mechanical strength of the product and ensures the good thermal shock resistance of the product.

Description

Preparation method of zirconia hollow sphere heat insulation product
Technical Field
The invention relates to a preparation method of a refractory material, in particular to a preparation method of a zirconium oxide hollow sphere heat insulation product.
Background
The zirconia hollow ball thermal insulation product is usually used as a tungsten-molybdenum sintered intermediate frequency furnace lining. The tungsten-molybdenum smelting furnace has high use temperature (up to 2300 ℃), and can run intermittently, and the temperature is quickly increased and decreased (increased to about 2000 ℃ in 24 hours), so the tungsten-molybdenum smelting furnace has the performances of high temperature resistance, high strength, high thermal shock resistance, low thermal expansion and the like as a lining material. However, the traditional zirconia hollow ball brick has the problems of high firing temperature (1800 ℃), low strength, poor thermal shock resistance, large thermal expansion coefficient and the like, is easy to break or peel in the using process, causes lower service life of a furnace lining, and causes high production and operation cost and high energy consumption due to pollution to produced alloy materials.
Disclosure of Invention
The invention aims to develop a high-strength and high-thermal-shock-resistance zirconia hollow sphere heat-insulating product which can be sintered at a lower temperature so as to meet the urgent need of the ultrahigh-temperature processing industry for high-performance refractory materials.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a zirconium oxide hollow sphere heat insulation product comprises the following components in percentage by weight: 60-75% of zirconia hollow spheres with the granularity of 0.2-3 mm; 15-30% of fused zirconia fine powder with the particle size of less than or equal to 0.044 mm; 5-10% of chemical method zirconia micro powder with the granularity less than or equal to 2 um; 5-10% of zirconia fiber; using PVA or water-soluble epoxy resin as a binding agent, adding 4-8% of the total mass of the solid raw materials, using water-soluble zirconium salt as a burning promoter, wherein the addition amount of the water-soluble zirconium salt is 5-10% of the total mass of the solid raw materials, fully wetting zirconia hollow spheres and the binding agent, then adding electric melting zirconia fine powder, zirconia micro powder and zirconia fibers, fully mixing uniformly, adding the burning promoter, mixing uniformly, pressing the mixture into a green body by adopting a vibration and pressurization mode, drying for 24-36 hours at 120 ℃, and then sintering at 1700-1750 ℃ for 4-8 hours in a high-temperature kiln to obtain the product.
Further, the burning promoter is one or more of zirconia sol, zirconium oxychloride and zirconium nitrate.
According to the invention, one or more of zirconia sol, zirconium oxychloride, zirconium nitrate and other water-soluble zirconium salts are used as a burning promoter, the product is subjected to an activated sintering technology, a high-strength and high-purity zirconia product is sintered at a lower temperature, the energy consumption of an enterprise is reduced, the cost is saved, the toughness of the product is improved by adding zirconia fiber, and the good thermal shock resistance of the product is ensured. The invention provides a reliable, effective and long-life heat-insulating refractory material for the ultrahigh-temperature field of China, and makes a great contribution to the technical progress and development of refractory materials for the high-tech field of national defense and the like and the special metal smelting industry in the world.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
In one embodiment of the invention, the preparation method of the zirconia hollow sphere heat insulation product comprises the following components in percentage by weight: 70 percent of zirconia hollow spheres with the granularity of 0.2-3 mm, 15 percent of fused zirconia fine powder with the granularity of less than or equal to 0.044mm, 10 percent of chemical method zirconia micro powder with the granularity of less than or equal to 2um and 5 percent of zirconia fiber; PVA is used as a bonding agent, the addition amount of the PVA is 4% of the total mass of the solid raw materials, zirconia sol is used as a burning promoter, and the addition amount of the PVA is 5% of the total mass of the solid raw materials. Fully wetting zirconia hollow spheres and a binding agent, adding the fused zirconia fine powder, the zirconia micro powder and the zirconia fiber, fully and uniformly mixing, adding a burning promoter, and uniformly mixing. And pressing the mixture into a green body by adopting a vibration pressurizing mode. Drying at 120 ℃ for 24 hours, and then sintering at 1700 ℃ in a high-temperature kiln for 8 hours to obtain the product.
Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (1)

1. The preparation method of the zirconium oxide hollow sphere heat insulation product is characterized in that the components and weight percentages of solid raw materials are as follows: 60-75% of zirconia hollow spheres with the granularity of 0.2-3 mm; 15-30% of fused zirconia fine powder with the particle size of less than or equal to 0.044 mm; 5-10% of chemical method zirconia micro powder with the granularity less than or equal to 2 um; 5-10% of zirconia fiber; using PVA or water-soluble epoxy resin as a binding agent, wherein the addition amount of the PVA or water-soluble epoxy resin is 4-8% of the total mass of the solid raw materials, using water-soluble zirconium salt as a burning promoter, the addition amount of the water-soluble zirconium salt is 5-10% of the total mass of the solid raw materials, fully wetting zirconia hollow spheres and the binding agent, then adding electric melting zirconia fine powder, zirconia micro powder and zirconia fibers, fully mixing uniformly, adding the burning promoter, mixing uniformly, pressing the mixture into a green body in a vibration pressurization mode, drying at 120 ℃ for 24-36 hours, and then sintering at 1700-1750 ℃ for 4-8 hours in a high-temperature kiln to obtain the product; wherein the burning promoter is one or more of zirconia sol, zirconium oxychloride and zirconium nitrate.
CN201711302276.5A 2017-12-10 2017-12-10 Preparation method of zirconia hollow sphere heat insulation product Active CN107827456B (en)

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CN108517584A (en) * 2018-04-26 2018-09-11 南京理工大学 A method of obtaining hollow zirconium fiber using microwave sintering trailing plants Japonica fiber
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

Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101654366A (en) * 2009-09-10 2010-02-24 中国矿业大学(北京) Composite sintering agent and method for preparing nano crystalline ceramics at low temperature
CN101798230A (en) * 2010-03-09 2010-08-11 浙江大学 Preparation method of zirconium oxide toughening aluminum oxide hollow balls
CN102060554A (en) * 2010-11-30 2011-05-18 哈尔滨工业大学 High-strength high-toughness zirconium diboride-silicon carbide-zirconia ceramic-based composite material and preparation method thereof
CN104446459A (en) * 2014-12-15 2015-03-25 中钢集团洛阳耐火材料研究院有限公司 Preparation method of zirconium oxide hollow sphere heat-insulating product for tungsten-molybdenum sintering medium-frequency furnace
CN106316426A (en) * 2016-08-21 2017-01-11 长兴盟友耐火材料有限公司 Fracture-resistant refractory material and preparation process thereof

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Publication number Priority date Publication date Assignee Title
WO2012022025A1 (en) * 2010-08-17 2012-02-23 南京钛威科技有限公司 Preparation method of carbon modified filler

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654366A (en) * 2009-09-10 2010-02-24 中国矿业大学(北京) Composite sintering agent and method for preparing nano crystalline ceramics at low temperature
CN101798230A (en) * 2010-03-09 2010-08-11 浙江大学 Preparation method of zirconium oxide toughening aluminum oxide hollow balls
CN102060554A (en) * 2010-11-30 2011-05-18 哈尔滨工业大学 High-strength high-toughness zirconium diboride-silicon carbide-zirconia ceramic-based composite material and preparation method thereof
CN104446459A (en) * 2014-12-15 2015-03-25 中钢集团洛阳耐火材料研究院有限公司 Preparation method of zirconium oxide hollow sphere heat-insulating product for tungsten-molybdenum sintering medium-frequency furnace
CN106316426A (en) * 2016-08-21 2017-01-11 长兴盟友耐火材料有限公司 Fracture-resistant refractory material and preparation process thereof

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Denomination of invention: Preparation method of zirconia hollow sphere insulation product

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