CN105837236B - A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof - Google Patents
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof Download PDFInfo
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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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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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
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- B22D41/32—Manufacturing or repairing thereof characterised by the materials used therefor
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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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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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
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- 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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- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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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
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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
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Abstract
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof.Its technical solution is:First by the plate diamond spar of 70 ~ 89wt%, the α Al of 5 ~ 10wt%2O3The antioxidant mixing of powder, the ZrC modified graphites of 1 ~ 5wt%, the thermosetting phenolic resin of 4 ~ 10wt% and 1 ~ 5wt%, compression moulding keep the temperature 3 ~ 7h under the conditions of 1400 ~ 1600 DEG C, and furnace cooling obtains addition ZrC modified graphite aluminum-carbon sliding materials.The preparation method of ZrC modified graphites:By zirconium powder: crystalline flake graphite: sodium chloride: the mass ratio of sodium fluoride is 1: (0.1 ~ 0.5): (1.4 ~ 3): (0.07 ~ 0.3) dispensing obtains mixture after mixing;Corundum crucible equipped with mixture is put into vacuum atmosphere heating furnace, 1 ~ 7h is kept the temperature under the conditions of argon gas atmosphere and 900 ~ 1200 DEG C, furnace cooling is dissolved and filtered after coming out of the stove, dry to get ZrC modified graphites.Present invention process is simply and at low cost, and made product has good antioxygenic property, resistance to slag corrosion and mechanical behavior under high temperature.
Description
Technical field
The invention belongs to aluminum-carbon sliding field of material technology.More particularly to a kind of addition ZrC modified graphite aluminum-carbon sliding materials
Material and preparation method thereof.
Background technology
Since the 1970s, refractory material worker by thermal conductivity factor height, good toughness, to the wetability of slag difference
Graphite is introduced into refractory material, develop mechanical property, thermal shock resistance and resistance to slag corrosion it is excellent oxide-carbon it is compound
Refractory material, this oxide-carbon composite refractory are widely used in the furnace lining materials such as converter, electric furnace, ladle and continuous casting system
System.As the development of iron and steel smelting technology proposes refractory material new requirement, for example, the damage of molten steel recarburization, material corrosion and
Greenhouse effects etc..Therefore for the angle of Clean Steel Smelting, energy-saving and emission-reduction and resources effective utilization, carbon composite refractory
It is inevitable to develop to low-carbon, even Ultra-low carbon direction while realizing that long service life satisfaction safety in production requires.In carbon composite fire
During the use of material, it is maximum the problem of be the oxidation of carbon, the carbon composite refractory after being aoxidized can shape inside it
Into apparent decarburized layer, so as to destroy the institutional framework of material internal, the performance of carbon composite refractory is reduced.Aluminium carbon is slided
For plate as common continuous casting slide board material, the research in terms of improving performance and reducing carbon content is subject to more technology people
The concern of member.
Document " Al2O3-C-ZrO2The development and production of matter composite slide-plate "(The triumphant .Al of Li Zhu2O3-C-ZrO2Matter composite slide-plate
Development and production Sichuan it is metallurgical, 2003,25 (2):10-12)One kind is described by being directly added into zirconium mullite, fused alumina zirconia
Or zirconium oxide prepares Al2O3-C-ZrO2The method of matter composite slide-plate.This method need to add in substantial amounts of zirconium-containing material and prepared
Composite slide-plate contains substantial amounts of carbon, therefore and unresolved carbon content it is high the problem of.
Document " influence of the species of carbon to aluminum-zirconium-carbon slide performance " (slide aluminium zirconium carbon from the species into carbon by Ma Lihong, gold
The influence refractory materials of plate performance, 2007,41 (2):153-154)Crystalline flake graphite, carbon black and pitch is described to slide aluminium zirconium carbon
The influence of plate performance, the experimental results showed that when adding in crystalline flake graphite, required resin is minimum.Although at this point, slide plate have compared with
Good antioxygenic property and good apparent porosity and bulk density, but other physical properties of material do not carry significantly
It is high.
Document " development and use of Nitride firing aluminum-zirconium-carbon slide "(Wei Zhongxian, Li Jingjing, Liu Xinhong Nitride firing aluminium
The development of zirconium-carbon slide and use refractory materials, 2011,45 (1):33-36)One kind is described by high temperature in a nitrogen atmosphere
Form SiC and Si2N2O is come performance indicator that aluminum-zirconium-carbon slide is made to reach higher, but its preparation flow is complicated.
The content of the invention
It is contemplated that prior art defect is overcome, and it is an object of the present invention to provide addition ZrC a kind of simple for process and at low cost
The preparation method of modified graphite aluminum-carbon sliding material, with this method prepare addition ZrC modified graphite aluminum-carbon slidings material not only
With good antioxygenic property, resistance to slag corrosion and mechanical behavior under high temperature, moreover it is possible to effectively reduce the carbon content in molten steel.
To achieve the above object, the technical solution adopted by the present invention is:First by the plate diamond spar of 70 ~ 89wt%, 5 ~ 10wt%
α-Al2O3The antioxidant mixing of powder, the ZrC modified graphites of 1 ~ 5wt%, the thermosetting phenolic resin of 4 ~ 10wt% and 1 ~ 5wt%,
The compression moulding under conditions of 150 ~ 200MPa, then keeps the temperature 3 ~ 7h under the conditions of 1400 ~ 1600 DEG C, and furnace cooling is added
Add ZrC modified graphite aluminum-carbon sliding materials.
The purity of the plate diamond spar is more than 96wt%;The grain composition of the plate diamond spar is:Granularity is 3 ~ 1mm, granularity
Less than 1mm and be less than 0.5mm more than or equal to 0.5mm, granularity and be less than 0.043mm more than or equal to 0.043mm, granularity and be more than etc.
In 0.02mm and granularity be less than 0.02mm account for successively the 37.5 ~ 52wt%, 21.5 ~ 25wt%, 21.5 ~ 25wt% and 5 of plate diamond spar ~
12.5wt%。
α-the Al2O3Granularity be less than 0.002mm;Purity is more than 99.9wt%.
The antioxidant is one or more of Al powder and Si powder;The granularity of the Al powder is less than 0.088mm, described
Si Powder Particle Sizes are less than 0.043mm.
The preparation method of the ZrC modified graphites is as follows:
(1)First press zirconium powder: crystalline flake graphite: sodium chloride: the mass ratio of sodium fluoride is 1: (0.1 ~ 0.5): (1.4 ~ 3): (0.07
~ 0.3) dispensing is carried out, is subsequently placed in batch mixer and mixes 1 ~ 1.5h to get mixture;
(2)The mixture is placed in corundum crucible, then crucible is put into vacuum atmosphere heating furnace;In argon gas atmosphere item
Under part, 900 ~ 1200 DEG C are warming up to the rate of 5 DEG C/min, keeps the temperature 1 ~ 7h;Furnace cooling obtains pre-synthesis ZrC modified graphites;
(3)The pre-synthesis ZrC modified graphites are dissolved and filtered with distilled water, the number of dissolving and filtering is 3 ~ 4 times,
Dry 12 under the conditions of 80 ~ 110 DEG C ~ for 24 hours to get ZrC modified graphites.
Due to the adoption of the above technical scheme, the present invention has following good effect compared with prior art:
The present invention by adding modified graphite, make prepared addition ZrC modified graphite aluminum-carbon sliding materials inoxidizability,
High-temperature mechanics, resistance to slag corrosion are greatly improved, while effectively reduce the carbon content in aluminum-carbon sliding material.
ZrC modified graphites go out what ZrC particles obtained by the zirconium powder in fused-salt medium in common flake graphite's surface growth in situ, ZrC
With aluminum-carbon sliding aggregate Ceramic bond occurs for grain under the high temperature conditions, effectively increases the high-temperature mechanics of aluminum-carbon sliding material
Energy.
Oxidation forms what is easily undergone phase transition to ZrC modified graphites prepared by the present invention first in high temperature oxidative atmosphere or air
ZrO2, ZrO2Protective film can not only prevent material from further aoxidizing, moreover it is possible to effectively reduce material under 1000 ~ 1500 DEG C of high temperature
Coefficient of thermal expansion so that the thermal shock resistance of aluminum-carbon sliding significantly improves, do not allow in heat fluctuation particularly at high temperature
Crackle is also easy to produce, therefore the addition of ZrC modified graphites improves the inoxidizability of aluminum-carbon sliding.When aluminum-carbon sliding is contacted with slag,
The ZrC of graphite surface is preferentially contacted with slag, is effectively increased the resistance to slag corrosion of aluminum-carbon sliding material, while can be reduced in material
Carbon content.
Therefore, it is good anti-to have the characteristics that aluminum-carbon sliding simple for process and at low cost, prepared not only has by the present invention
Oxidation susceptibility, resistance to slag corrosion and mechanical behavior under high temperature, moreover it is possible to effectively reduce the carbon content in molten steel.
Specific embodiment
With reference to specific implementation real mode, the invention will be further described, not to the limitation of its protection domain.
It is first that the technical parameter of the related material involved by present embodiment or preparation method is unified to avoid repeating
It is described as follows, is repeated no more in embodiment:
The purity of the plate diamond spar is more than 96wt%;The grain composition of the plate diamond spar is:Granularity is 3 ~ 1mm, granularity
Less than 1mm and be less than 0.5mm more than or equal to 0.5mm, granularity and be less than 0.043mm more than or equal to 0.043mm, granularity and be more than etc.
In 0.02mm and granularity be less than 0.02mm account for successively the 37.5 ~ 52wt%, 21.5 ~ 25wt%, 21.5 ~ 25wt% and 5 of plate diamond spar ~
12.5wt%。
α-the Al2O3Granularity be less than 0.002mm;Purity is more than 99.9wt%.
The antioxidant is one or more of Al powder and Si powder;The granularity of the Al powder is less than 0.088mm, described
Si Powder Particle Sizes are less than 0.043mm.
The preparation method of the ZrC modified graphites is as follows:
(1)First press zirconium powder: crystalline flake graphite: sodium chloride: the mass ratio of sodium fluoride is 1: (0.1 ~ 0.5): (1.4 ~ 3): (0.07
~ 0.3) dispensing is carried out, is subsequently placed in batch mixer and mixes 1 ~ 1.5h to get mixture;
(2)The mixture is placed in corundum crucible, then crucible is put into vacuum atmosphere heating furnace;In argon gas atmosphere item
Under part, 900 ~ 1200 DEG C are warming up to the rate of 5 DEG C/min, keeps the temperature 1 ~ 7h;Furnace cooling obtains pre-synthesis ZrC modified graphites;
(3)The pre-synthesis ZrC modified graphites are dissolved and filtered with distilled water, the number of dissolving and filtering is 3 ~ 4 times,
Dry 12 under the conditions of 80 ~ 110 DEG C ~ for 24 hours to get ZrC modified graphites.
Embodiment 1
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof.First by the plate diamond spar of 70 ~ 75wt%, 8 ~
α-the Al of 10wt%2O3Powder, the ZrC modified graphites of 4 ~ 5wt%, the thermosetting phenolic resin of 8 ~ 10wt%, the Al powder of 1 ~ 2wt% and 2 ~
Then the Si powder mixing of 3wt%, the compression moulding under conditions of 150 ~ 200MPa keep the temperature 5 ~ 7h under the conditions of 1400 ~ 1500 DEG C,
Furnace cooling obtains addition ZrC modified graphite aluminum-carbon sliding materials.
Embodiment 2
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof.First by the plate diamond spar of 75 ~ 80wt%, 7 ~
α-the Al of 9wt%2O3The Si powder mixing of powder, the ZrC modified graphites of 3 ~ 4wt%, the thermosetting phenolic resin of 7 ~ 9wt% and 3 ~ 4wt%,
The compression moulding under conditions of 150 ~ 200MPa, then keeps the temperature 4 ~ 6h under the conditions of 1440 ~ 1540 DEG C, and furnace cooling is added
Add ZrC modified graphite aluminum-carbon sliding materials.
Embodiment 3
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof.First by the plate diamond spar of 80 ~ 85wt%, 6 ~
α-the Al of 8wt%2O3The Al powder mixing of powder, the ZrC modified graphites of 2 ~ 3wt%, the thermosetting phenolic resin of 6 ~ 8wt% and 1 ~ 2wt%,
The compression moulding under conditions of 150 ~ 200MPa, then keeps the temperature 3 ~ 5h under the conditions of 1470 ~ 1570 DEG C, and furnace cooling is added
Add ZrC modified graphite aluminum-carbon sliding materials.
Embodiment 4
A kind of addition ZrC modified graphite aluminum-carbon sliding materials and preparation method thereof.First by the plate diamond spar of 84 ~ 89wt%, 5 ~
α-the Al of 7wt%2O3The Si powder mixing of powder, the ZrC modified graphites of 1 ~ 2wt%, the thermosetting phenolic resin of 4 ~ 7wt% and 1 ~ 2wt%,
The compression moulding under conditions of 150 ~ 200MPa, then keeps the temperature 3 ~ 5h under the conditions of 1500 ~ 1600 DEG C, and furnace cooling is added
Add ZrC modified graphite aluminum-carbon sliding materials.
Present embodiment has following good effect compared with prior art:
Present embodiment makes prepared addition ZrC modified graphite aluminum-carbon sliding materials by adding modified graphite
Inoxidizability, high-temperature mechanics, resistance to slag corrosion are greatly improved, while effectively reduce in aluminum-carbon sliding material
Carbon content.ZrC modified graphites go out ZrC particles in common flake graphite's surface growth in situ by the zirconium powder in fused-salt medium and obtain
, with aluminum-carbon sliding aggregate Ceramic bond occurs for ZrC particles under the high temperature conditions, effectively increases the high temperature of aluminum-carbon sliding material
Mechanical property.
Oxidation forms easily hair to ZrC modified graphites prepared by present embodiment first in high temperature oxidative atmosphere or air
The ZrO2 of raw phase transformation, ZrO2 protective films can not only prevent material from further aoxidizing, moreover it is possible to effectively reduce material 1000 ~ 1500
Coefficient of thermal expansion under DEG C high temperature, so that the thermal shock resistance of aluminum-carbon sliding significantly improves, heat wave particularly at high temperature
It is not easy to crack in dynamic, therefore the addition of ZrC modified graphites improves the inoxidizability of aluminum-carbon sliding.When aluminum-carbon sliding and slag
During contact, the ZrC of graphite surface is preferentially contacted with slag, is effectively increased the resistance to slag corrosion of aluminum-carbon sliding material, while can be dropped
Carbon content in low material.
Therefore, present embodiment has the characteristics that aluminum-carbon sliding simple for process and at low cost, prepared not only has
Good antioxygenic property, resistance to slag corrosion and mechanical behavior under high temperature, transducing effectively reduce the carbon content in molten steel.
Claims (4)
1. a kind of preparation method for adding ZrC modified graphite aluminum-carbon sliding materials, it is characterised in that the preparation method is:First will
The plate diamond spar of 70~89wt%, the α-Al of 5~10wt%2O3Powder, the ZrC modified graphites of 1~5wt%, the heat of 4~10wt%
The antioxidant of solidity phenolic resin and 1~5wt% mix, the compression moulding under conditions of 150~200MPa, then 1400
3~7h is kept the temperature under the conditions of~1600 DEG C, furnace cooling obtains addition ZrC modified graphite aluminum-carbon sliding materials;
The preparation method of the ZrC modified graphites is as follows:
(1) zirconium powder: crystalline flake graphite: sodium chloride is first pressed: the mass ratio of sodium fluoride is 1: (0.1~0.5): (1.4~3): (0.07~
0.3) dispensing is carried out, is subsequently placed in batch mixer and mixes 1~1.5h to get mixture;
(2) mixture is placed in corundum crucible, then crucible is put into vacuum atmosphere heating furnace;In argon gas atmosphere condition
Under, 900~1200 DEG C are warming up to the rate of 5 DEG C/min, keeps the temperature 1~7h;Furnace cooling obtains pre-synthesis ZrC modified graphites;
(3) the pre-synthesis ZrC modified graphites being dissolved and filtered with distilled water, the number of dissolving and filtering is 3~4 times,
Dry 12 under the conditions of 80~110 DEG C~for 24 hours to get ZrC modified graphites.
2. the preparation method of ZrC modified graphite aluminum-carbon sliding materials is added according to claim 1, it is characterised in that the α-
Al2O3Granularity be less than 0.002mm;Purity is more than 99.9wt%.
3. the preparation method of ZrC modified graphite aluminum-carbon sliding materials is added according to claim 1, it is characterised in that described anti-
Oxidant is one or more of Al powder and Si powder;The granularity of the Al powder is less than 0.088mm, and the Si Powder Particle Sizes are less than
0.043mm。
A kind of 4. addition ZrC modified graphite aluminum-carbon sliding materials, it is characterised in that the addition ZrC modified graphite aluminum-carbon sliding materials
Material is added according to any one of claims 1 to 3 item prepared by the preparation method of ZrC modified graphite aluminum-carbon sliding materials
Addition ZrC modified graphite aluminum-carbon sliding materials.
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CN101429037A (en) * | 2007-11-07 | 2009-05-13 | 鞍钢集团耐火材料公司 | Aluminum-carbon sliding tile and method of producing the same |
CN102441663A (en) * | 2011-09-02 | 2012-05-09 | 郑州大学 | Metal aluminum-zinc composite low-carbon aluminum carbon sliding plate and preparation method |
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CN101429037A (en) * | 2007-11-07 | 2009-05-13 | 鞍钢集团耐火材料公司 | Aluminum-carbon sliding tile and method of producing the same |
CN102441663A (en) * | 2011-09-02 | 2012-05-09 | 郑州大学 | Metal aluminum-zinc composite low-carbon aluminum carbon sliding plate and preparation method |
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