CN111842870A - Al containing ZrO2O3-ZrO2-Al composite sliding plate and preparation method thereof - Google Patents

Al containing ZrO2O3-ZrO2-Al composite sliding plate and preparation method thereof Download PDF

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CN111842870A
CN111842870A CN202010566806.2A CN202010566806A CN111842870A CN 111842870 A CN111842870 A CN 111842870A CN 202010566806 A CN202010566806 A CN 202010566806A CN 111842870 A CN111842870 A CN 111842870A
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zro
sliding plate
corundum
temperature
raw materials
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李勇
郑清瑶
李宏宇
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • 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
    • B22D41/14—Closures
    • B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
    • B22D41/28—Plates therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing 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
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • 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
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    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

The invention relates to Al containing ZrO2O3‑ZrO2-Al composite sliding plate andthe preparation method belongs to the field of refractory materials. The sliding plate comprises 65-90 wt% of corundum and 3-20 wt% of ZrO24-15% of metal aluminum powder and phenolic resin accounting for 2-6% of the total amount of the raw materials are added as a binding agent. During production, the raw materials are weighed according to the proportion, evenly mixed, mixed to obtain pug, then pressed and formed, dried for 10-30h at the temperature of 120-500 ℃, and then sintered at the high temperature of 1000-1600 ℃. The product has an oxide-non-oxide composite structure and has excellent physical performance indexes: apparent porosity of 6-14%, volume density of 2.9-3.6g/cm3And the normal temperature compressive strength is 70-250 MPa. The product can replace the traditional aluminum-zirconium-carbon sliding plate, avoids carbon pollution to molten steel, contains ZrO phase and has better oxidation resistance.

Description

Al containing ZrO2O3-ZrO2-Al composite sliding plate and preparation method thereof
Technical Field
The invention relates to preparation of a sliding plate for steelmaking continuous casting, in particular to Al containing ZrO2O3-ZrO2an-Al composite sliding plate and a preparation method thereof belong to the field of refractory materials.
Background
The slide plate is a key part of the sliding gate nozzle and is used for controlling the flow and the flow rate of molten steel. The used refractory material is required to have better erosion resistance and scouring resistance; excellent thermal shock resistance and high wear resistance; excellent oxidation resistance. At present, the large and medium-sized steel ladle mainly takes aluminum carbon and aluminum zirconium carbon as main materials. An Al-Zr-C refractory material for continuous casting is prepared from Al-Zr-C refractory material and Al-Zr-C refractory material through proportional mixing, and features high strength, high strength and low thermal shock resistance. ZrO (ZrO) 2Has the phase change toughening characteristic and can improve the thermal shock resistance of the material. Meanwhile, the aluminum-zirconium-carbon refractory material has better erosion resistance to calcium-treated steel. However, with the progress of steel-making technology and the change of market demand, the traditional high-carbon material sliding plate is difficult to meet the production process of high-quality steel.
Replacement of Al by metallic aluminium2O3-ZrO2Carbon in-C materials, i.e. fired Al2O3-ZrO2-Al composite skateboard. Can effectively solve the problems of carbon pollution and oxidation resistance. The excellent performance of the carbon-containing refractory material is mainly reflected in high melting point, better slag corrosion resistance, low thermal expansion coefficient and high thermal conductivity. Metallic aluminum and Al2O3Or ZrO2The non-oxide obtained after the reaction also has the advantages. Meanwhile, the metal is added to play a role of a metal transition plastic phase, namely, a certain amount of metal is added into the rigid inorganic material, the metal is used as plastic to promote forming at the beginning, liquefaction or softening is carried out in the sintering process to promote sintering, and a high-strength non-oxide reinforcing phase is obtained after sintering.
In the conventional Zr-O equilibrium system, there is no ZrO phase, and the system is in a narrow oxygen partial pressure intervalOne of the non-equilibrium phases. ZrO is generally considered to be synthesized under an atmosphere of low oxygen partial pressure. It is a transition metal Zr and ZrO 2Meta-stable phase between which it oxidizes to form ZrO in a high temperature oxidizing environment2It will be reduced to Zr (requiring extremely low oxygen partial pressure) under high temperature reduction conditions. ZrO itself has high strength and refractoriness as a non-oxide phase. The use of ZrO-containing refractory materials under oxidizing conditions can enhance the oxidation resistance of the material.
In order to solve the problem that the aluminum-zirconium-carbon sliding plate has high carbon content and cannot adapt to the production of clean steel, the invention uses metal aluminum to replace carbon to prepare Al2O3-ZrO2The Al composite sliding plate contains non-oxide ZrO, so that the material has excellent oxidation resistance.
Disclosure of Invention
The invention aims to prepare Al containing ZrO2O3-ZrO2The Al-Al composite sliding plate has the advantages that ZrO contained in the product has better oxidation resistance. Meanwhile, the product is used as an oxide-bonded non-oxide refractory material, has the characteristics of high strength, good thermal shock stability, good erosion resistance and the like, can replace the traditional aluminum-zirconium-carbon sliding plate, and avoids carbon pollution to molten steel.
The technical scheme of the invention is as follows:
al containing ZrO2O3-ZrO2-Al composite skateboard, characterized in that: the sliding plate comprises 65-90 wt% of corundum and 3-20 wt% of ZrO24-15% of metal aluminum powder and phenolic resin accounting for 2-6% of the total amount of the raw materials are added as a binding agent.
The corundum has three particle sizes of 1-2mm, 0.5-1mm and 0-0.5mm, the ZrO2 is 0-0.1mm, and the particle size of the metal aluminum powder is 0-0.1 mm. The proportion of the corundum in the coarse grain, fine grain and fine powder is as follows: 10-30% of coarse particles (the particle size is more than or equal to 2 and less than 1mm), 15-30% of medium particles (the particle size is more than or equal to 1 and less than 0.5mm), and 40-70% of fine particles and fine powder (the particle size is more than or equal to 0.5 and less than 0 mm). Under the proportioning condition, a green body with better strength after being dried is obtained.
Al containing ZrO as described above2O3-ZrO2The preparation method of the-Al composite sliding plate is characterized by comprising the following steps: weighing the raw materials according to the proportion, uniformly mixing, mixing to obtain pug, then pressing and forming, drying for 10-30h at the temperature of 120-
The invention has the following positive effects:
1. the product is sintered in a high-temperature nitrogen atmosphere to obtain Al containing ZrO phase2O3-ZrO2Al sliding plate, which has better oxidation resistance.
2. The product of the invention is synthesized at high temperature to obtain a refractory material containing ZrO phase, and the ZrO phase is oxidized to obtain in-situ synthesized ZrO2The material still has high strength.
3. The product of the invention obtains a non-oxide phase through the reaction of the metallic aluminum and the oxide under the high-temperature low-oxygen partial pressure atmosphere, has high-temperature strength and stability, and prolongs the service life of the sliding plate.
4. The product of the invention has excellent physical performance indexes. Apparent porosity of 6-14%, volume density of 2.9-3.6g/cm3And the normal temperature compressive strength is 70-250 MPa.
5. The product of the invention takes phenolic resin as a bonding agent, wherein high-activity residual carbon can participate in the reaction to form non-oxide, and simultaneously, the oxygen partial pressure of the system during high-temperature reaction can be reduced, thereby ensuring that a ZrO phase is obtained.
6. By the reaction of Al in the invention2O3-ZrO2Adding metallic aluminum into the system, and reacting to obtain the oxide-non-oxide combined refractory material. Can replace and exceed the traditional aluminum-zirconium-carbon refractory material, and is beneficial to the cleanness and low carbon of molten steel.
Detailed Description
Example 1: al containing ZrO2O3-ZrO2The preparation method of the-Al composite sliding plate comprises the following raw materials in percentage by weight: 89% of corundum (wherein the grain size is 1-2mm 20%, 0.5-1mm 10%, 0-0.5mm 59%), and 3% of ZrO28 percent of metal aluminum powder and 3 percent of thermosetting phenolic resin.
During production, the raw materials are weighed according to the proportion, evenly mixed, mixed to obtain pug, then pressed and formed by a friction press, dried for 24 hours at the temperature of 120 plus materials and 500 ℃, and then sintered at the temperature of 1300 ℃ in the nitrogen atmosphere.
The powder is ZrO with the granularity of less than 325 meshes 2The aggregate is corundum with the granularity of 1-2mm and 0.1-1 mm; the corundum is plate corundum.
The performance indexes of the obtained product are as follows: apparent porosity of 9.1% and volume density of 3.24g/cm3The normal temperature compressive strength is 228MPa, and the thermal shock resistance, the erosion resistance, the oxidation resistance and the hydration resistance of the material are all better.
Example 2: the production process was the same as in example 1, except that:
the raw materials comprise the following components in percentage by weight: 86% of corundum (wherein the grain size is 1-2mm 20%, 0.5-1mm 10%, 0-0.5mm 56%), 6% of ZrO28 percent of metal aluminum powder and 3 percent of thermosetting phenolic resin. The performance indexes of the obtained product are as follows: apparent porosity of 11.9%, volume density of 3.18g/cm3The normal temperature compressive strength is 75.2MPa, and the thermal shock resistance, the erosion resistance, the oxidation resistance and the hydration resistance of the material are all good.
Example 3: the production process was the same as in example 1, except that:
the raw materials comprise the following components in percentage by weight: 83% of corundum (wherein the grain size is 1-2mm 20%, 0.5-1mm 10%, 0-0.5mm 53%), 9% of ZrO28 percent of metal aluminum powder and 3 percent of thermosetting phenolic resin. The performance indexes of the obtained product are as follows: apparent porosity of 10.6%, volume density of 3.32/cm 3The normal temperature compressive strength is 164MPa, and the thermal shock resistance, the erosion resistance, the oxidation resistance and the hydration resistance of the material are all good.
Example 4: the production process was the same as in example 1, except that:
the raw materials comprise the following components in percentage by weight: 80% of corundum and 12% of ZrO28 percent of metal aluminum powder and 3 percent of thermosetting phenolic resin. The performance indexes of the obtained product are as follows: apparent porosity of 13.5% and volume density of 3.25g/cm3Normal temperature compressive strength of 115MPa, thermal shock resistance,Has good erosion resistance, oxidation resistance and hydration resistance.

Claims (3)

1. Al containing ZrO2O3-ZrO2-Al composite skateboard, characterized in that: the sliding plate comprises 65-90 wt% of corundum and 3-20 wt% of ZrO24-15% of metal aluminum powder and phenolic resin accounting for 2-6% of the total amount of the raw materials are added as a binding agent.
2. ZrO-containing Al according to claim 12O3-ZrO2-Al composite skateboard, characterized in that: the corundum has three particle sizes of 1-2mm, 0.5-1mm and 0-0.5mm, the ZrO2 is 0-0.1mm, and the particle size of the metal aluminum powder is 0-0.1 mm. The proportion of the corundum in the coarse grain, fine grain and fine powder is as follows: 10-30% of coarse particles (the particle size is more than or equal to 2 and less than 1mm), 15-30% of medium particles (the particle size is more than or equal to 1 and less than 0.5mm), and 40-70% of fine particles and fine powder (the particle size is more than or equal to 0.5 and less than 0 mm); under the proportioning condition, a green body with better strength after being dried is obtained.
3. The method for preparing an unfired ferrosilicon nitride-spinel-corundum composite refractory material according to claim 1 or 2, characterized in that: weighing various raw materials according to the proportion, uniformly mixing, mixing to obtain pug, then pressing and forming, drying for 10-30h at the temperature of 120-1600 ℃, and then sintering at the temperature of 1000-1600 ℃ in a high-temperature nitrogen atmosphere.
CN202010566806.2A 2020-06-19 2020-06-19 Al containing ZrO2O3-ZrO2-Al composite sliding plate and preparation method thereof Pending CN111842870A (en)

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CN103145433A (en) * 2013-03-25 2013-06-12 北京科技大学 Unfired ferrosilicon nitride-spinel-corundum composite refractory material and preparation method thereof
JP2013159514A (en) * 2012-02-03 2013-08-19 Shinagawa Refractories Co Ltd Method for manufacturing alumina-zirconia refractory raw material, alumina-zirconia refractory raw material, and plate refractory
JP2016131987A (en) * 2015-01-16 2016-07-25 新日鐵住金株式会社 SLIDING NOZZLE PLATE FOR Ca TREATED STEEL
CN106470958A (en) * 2014-07-14 2017-03-01 里弗雷克特里知识产权两合公司 Refractory product, the purposes of zirconium dioxide, zirconium dioxide, be used for the method manufacturing refractory product and the refractory product being produced from
CN108349818A (en) * 2015-12-01 2018-07-31 里弗雷克特里知识产权两合公司 For manufacturing the particle of refractory product, the purposes of such particle, refractory product, the method for manufacturing refractory product and the refractory product being produced from it

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101925558A (en) * 2008-01-30 2010-12-22 黑崎播磨株式会社 Raw material for zirconia/mullite refractory and plate brick
JP2013159514A (en) * 2012-02-03 2013-08-19 Shinagawa Refractories Co Ltd Method for manufacturing alumina-zirconia refractory raw material, alumina-zirconia refractory raw material, and plate refractory
CN103145433A (en) * 2013-03-25 2013-06-12 北京科技大学 Unfired ferrosilicon nitride-spinel-corundum composite refractory material and preparation method thereof
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