CN108147826A - A kind of high-purity CM2A8Material and preparation method thereof - Google Patents
A kind of high-purity CM2A8Material and preparation method thereof Download PDFInfo
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- CN108147826A CN108147826A CN201711387949.1A CN201711387949A CN108147826A CN 108147826 A CN108147826 A CN 108147826A CN 201711387949 A CN201711387949 A CN 201711387949A CN 108147826 A CN108147826 A CN 108147826A
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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
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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
- C04B35/01—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
- C04B35/44—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 aluminates
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention provides a kind of high-purity CM2A8Material and preparation method thereof, synthesis material principal crystalline phase are CaMg2Al16O27, for purity more than 98%, bulk density is 2.8 ~ 3.5g/cm3, chemical composition：Al2O385.6 86.9%, MgO 7.2 8.5%, CaO 5.8 5.9%, by the way that Al will be contained2O3Raw material, the raw material containing CaO and the raw material containing MgO according to Al2O385.6~86.9%, MgO 7.2~8.5%, CaO 5.8~5.9% is matched, and is ground altogether using ball mill 2~10 hours, the bonding agent of additional 1~6wt% of said mixture.After mixing, by high-pressure molding of the raw material through 10MPa~200MPa, 1650~1750 DEG C are warming up to after dry under air, keeps the temperature 120~720 minutes sintering synthesis CM2A8Material.
Description
Technical field
The invention belongs to technical field of refractory materials, and in particular to a kind of high-purity CM2A8Material and preparation method thereof.
Background technology
Using ladle, tundish refractory material come cleaning molten steel, it is refractory material institute's phase for many years to remove the field trash in molten steel
The critical function of prestige, the MgO-CaO-C bricks released as last century the nineties, MgO-CaO bricks and the filtering of tundish CaO matter
The CaO materials such as device, with certain purification function.However, due to the aquation problem of CaO itself, the CaO being had great expectations
Material fails to realize the extensive use in molten steel purifying field.
Calcium hexaluminate（CaAl12O19, CA6）It is CaO-Al2O3Al in system2O3The highest aluminic acid calcium phase of content, its theoretical density
For 3.79g/cm3, fusing point is higher than 1875°C, coefficient of thermal expansion is close with corundum, has in reducing atmosphere（CO）In alkaline environment
Chemical stability is good, to molten metal and slag（Steel and non-ferrous metal）Wetability is low to wait key properties.Though the series raw material
So contain CaO, but without hydrability, there is certain cleaning molten steel.It is practised however, as the unique crystallization of calcium hexaluminate
Property, it is difficult to it is fine and close, ladle or tundish lining material can not be applied independently in.
And spinelle（MgAl2O4, MA）It is MgO-Al2O3Compound uniquely stable, fusing point are up to 2135 in system°C, tool
There is the features such as coefficient of thermal expansion is low, intensity is high, thermal conductivity is good, chemical stability is good.As patent CN104072170A " one kind six
Calcium aluminate-magnesium aluminate spinel composite diphase material and preparation method thereof ", a kind of CN102030545A " MgAl2O4-CaAl12O19Complex phase
Heat-resisting material and preparation method thereof " etc., by the compound of calcium hexaluminate and spinelle, can prepare suitable for ladle or
Between ladle-lining, there is the CA of certain purification of molten steel ability6/ MA multiple phase refractory materials.
Relative to CA6/ MA two-phase composite materials, single-phase CaOxMgOyAl2O3Ternary layered material has some spies
Different property.G bbels et al. are in research Al2O3CaMg is found that in-CaO-MgO ternary systems2Al16O27（CM2A8）With
Ca2Mg2Al28O46（C2M2A14）Material is the CA of magnetoplumbite type6Occur to be dissolved at high temperature with the MA of cubic structure and be formed.
In its C axis direction, magneto-plumbite type matrix M and spinelle matrix S stack to form CM in a manner of (MS) n2A8Ternary compound.
CM2A8Ternary material is released by the disintegration of self structure with potential purification steel when with slag haptoreaction
The CA of outlet capacity2/CA（It continues gradually be changed into C with slag reaction12A7）, while formd at reaction interface based on CA2/
The transition resistant to corrosion layer of CA and MA not only prevents slag from continuing internally to permeate, but also by the last decomposition of self structure, can
Constantly play the effect of its cleaning molten steel.Therefore, CM2A8It is a kind of with the effect of continuing purge molten steel and erosion resistant excellent resistance to
Fiery raw material, has broad application prospects.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of high-purity CM2A8The preparation method of material, the method pass through by
Raw material containing CaO, the raw material containing MgO and containing Al2O3Raw material carry out common mill mixing, the knot of additional 1~6 wt% of said mixture
Mixture mixes aftershaping, is warming up to 1650~1850 DEG C after dry in air atmosphere, keeps the temperature 120~720 minutes, naturally cold
But, high-purity CM is made2A8Material；
Further, the method includes：
S1：Al will be contained2O3Raw material, the raw material containing CaO and the raw material containing MgO match according to following chemical composition and mass percent
Than Al2O385.6~86.9%, MgO 7.2~8.5%, CaO 5.8~5.9% is ground 2~10 hours altogether；
S2：Add in the bonding agent of 1~6wt% of mixture in S1；
S3：S2 is added in high-pressure molding of the mixture through 10MPa~200MPa of bonding agent；
S4：It is dry after keeping the temperature 120~720 minutes under 1650~1850 DEG C of air atmospheres；
S5：Sintering synthesis CM2A8Material；
Further, the raw material containing CaO is dolomite, lime stone, lime, calcium hydroxide, calcium carbonate or calcium oxide etc.,
Granularity is less than 180 mesh；
Further, the raw material containing MgO is rich calcium dolomite, rich conite, fused magnesite, magnesite clinker, seawater
Magnesia or magnesia, granularity are less than 180 mesh；
Further, it is described to contain Al2O3Raw material be diaspore, aluminium hydroxide, commercial alumina, Reactive alumina or
Aluminium oxide, granularity are less than 180 mesh；
Further, the bonding agent be starch, dextrin, Aluminum sol, spent pulping liquor, calcium lignosulfonate, polyvinyl alcohol or
Methylcellulose；
Further, a kind of high-purity CM2A8Material, the CM2A8Material is with CaMg2Al16O27For main object phase, mass fraction
More than 98%, bulk density is 2.8 ~ 3.5g/cm；
Beneficial effects of the present invention are as follows：
1）：CM of the present invention2A8When with slag haptoreaction, released by the disintegration of self structure has ternary material
The CA of potential purification molten steel ability2/ CA continues gradually be changed into C with slag reaction12A7；
2）：It is formd at reaction interface based on CA2The transition resistant to corrosion layer of/CA and MA not only prevents slag from continuing internally
Infiltration, and by the last decomposition of self structure, can constantly play the effect of its cleaning molten steel；
3）CM2A8It is a kind of with the effect of continuing purge molten steel and erosion resistant excellent refractory raw material, with before wide application
Scape.
Description of the drawings
Fig. 1 is CM of the present invention2A8Phasor.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.On the contrary, the present invention cover it is any be defined by the claims the present invention spirit and scope on do
Replacement, modification, equivalent method and scheme.Further, in order to which the public is made to have a better understanding the present invention, below to this
It is detailed to describe some specific detail sections in the datail description of invention.It is thin without these for a person skilled in the art
The description of section part can also understand the present invention completely.
The invention will be further described in the following with reference to the drawings and specific embodiments, but not as a limitation of the invention.
Below most preferred embodiment is enumerated for the present invention：
As shown in Figure 1, the present invention is has the function of that the ladle of purification of molten steel and tundish lining provide suitable raw material, this hair
A kind of bright high-purity CM of synthesis2A8Refractory raw material.It is an object of the present invention to synthesize principal crystalline phase for CaMg2Al16O27, purity
Refractory material new raw material more than 98%.Bulk density is 2.8 ~ 3.5g/cm3, chemical composition is（Mass percent）：Al2O3
85.6-86.9%, MgO 7.2-8.5%, CaO 5.8-5.9%.
By phasor, as shown in Figure 1, to illustrate CM2A8Ingredient.It is replaced due to the ion in its structure and is substituted with vacancy,
CM2A8There are a certain range of solid solution regions.According to 1 bend region of attached drawing（CM2A8It is dissolved region）Carry out dispensing, after synthesis
Object is mutually pure CM2A8Solid solution refractory raw material.
Its preparation method is：Al will be contained2O3Raw material, the raw material containing CaO and the raw material containing MgO according to following chemical composition
It is matched with mass percent, Al2O385.6~86.9%, MgO 7.2~8.5%, CaO 5.8~5.9% grinds 2 altogether using ball mill
~10 hours, the bonding agent of additional 1~6wt% of said mixture.After mixing, by height of the raw material through 10MPa~200MPa
It is molded, 1650~1850 DEG C of heat preservations, 120~720 minutes sintering synthesis CM are warming up to after dry in air atmosphere2A8Material.
Raw material containing CaO is one kind or several in dolomite, lime stone, lime, calcium hydroxide, calcium carbonate or calcium oxide etc.
Kind, granularity is less than 180 mesh；
Raw material containing MgO is in rich calcium dolomite, rich conite, fused magnesite, magnesite clinker, seawater magnesia and magnesia etc.
One or more, granularity be less than 180 mesh；
Containing Al2O3Raw material be in diaspore, aluminium hydroxide, commercial alumina, Reactive alumina or aluminium oxide etc. one
Kind is several, and granularity is less than 180 mesh；
Bonding agent is in starch, dextrin, Aluminum sol, spent pulping liquor, calcium lignosulfonate, polyvinyl alcohol, methylcellulose etc.
It is one or more of.
Embodiment 1
With lime, fused magnesite and commercial alumina are raw material, are matched according to chemical composition after synthesis and mass percent,
Al2O385.6%, MgO 8.5%, CaO 5.9% is ground 6 hours altogether, and the dextrin of additional said mixture 3wt% is as bonding agent.It is mixed
After conjunction, by high-pressure molding of the raw material through 150MPa, 1750 DEG C of heat preservations are warming up to after dry in air atmosphere and are burnt within 480 minutes
It is combined into CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/cm3。
Embodiment 2
With lime stone, magnesite clinker and Reactive alumina are raw material, are matched according to chemical composition after synthesis and mass percent
Than Al2O385.6%, MgO 8.5%, CaO 5.9% is ground 6 hours altogether, and the dextrin of additional said mixture 3wt% is as combination
Agent.After mixing, by high-pressure molding of the raw material through 150MPa, 1750 DEG C of heat preservations 480 are warming up to after dry in air atmosphere
Minute sintering synthesis CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/
cm3。
Embodiment 3
With calcium hydroxide, rich conite and diaspore are raw material, are matched according to chemical composition after synthesis and mass percent,
Al2O385.6%, MgO 8.5%, CaO 5.9% is ground 6 hours altogether, and the dextrin of additional said mixture 3wt% is as bonding agent.It is mixed
After conjunction, by high-pressure molding of the raw material through 150MPa, 1750 DEG C of heat preservations are warming up to after dry in air atmosphere and are burnt within 480 minutes
It is combined into CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/cm3。
Embodiment 4
With dolomite, seawater magnesia and aluminium oxide are raw material, are matched according to chemical composition after synthesis and mass percent, Al2O3
85.6%, MgO 8.5%, CaO 5.9% is ground 6 hours altogether, and the dextrin of additional said mixture 3wt% is as bonding agent.After mixing,
By high-pressure molding of the raw material through 150MPa, 1750 DEG C of heat preservations sintering in 480 minutes is warming up to after dry in air atmosphere and is closed
Into CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/cm3。
Embodiment 5
With lime, fused magnesite and commercial alumina are raw material, are matched according to chemical composition after synthesis and mass percent,
Al2O386.9%, MgO 7.3%, CaO 5.8% is ground 6 hours altogether, and the methylcellulose of additional said mixture 2wt% is as knot
Mixture.After mixing, by high-pressure molding of the raw material through 150MPa, it is warming up to 1750 DEG C of heat preservations in air atmosphere after dry
480 minutes sintering synthesis CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/
cm3。
Embodiment 6
With lime stone, magnesite clinker and Reactive alumina are raw material, are matched according to chemical composition after synthesis and mass percent
Than Al2O386.9%, MgO 7.3%, CaO 5.8% is ground 6 hours, the methylcellulose conduct of additional said mixture 2wt% altogether
Bonding agent.After mixing, by high-pressure molding of the raw material through 150MPa, it is warming up to 1750 DEG C of heat preservations in air atmosphere after dry
360 minutes sintering synthesis CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/
cm3。
Embodiment 7
With calcium hydroxide, rich conite and diaspore are raw material, are matched according to chemical composition after synthesis and mass percent,
Al2O386.9%, MgO 7.3%, CaO 5.8% is ground 6 hours, the calcium lignosulfonate conduct of additional said mixture 2wt% altogether
Bonding agent.After mixing, by high-pressure molding of the raw material through 150MPa, it is warming up to 1750 DEG C of heat preservations in air atmosphere after dry
480 minutes sintering synthesis CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/
cm3。
Embodiment 8
With dolomite, seawater magnesia and aluminium oxide are raw material, are matched according to chemical composition after synthesis and mass percent, Al2O3
86.9%, MgO 7.3%, CaO 5.8% is ground 6 hours altogether, and the calcium lignosulfonate of additional said mixture 2wt% is as combination
Agent.After mixing, by high-pressure molding of the raw material through 150MPa, 1750 DEG C of heat preservations 360 are warming up to after dry in air atmosphere
Minute sintering synthesis CaMg2Al16O27（CM2A8）Material.Its principal crystalline phase is CaMg2Al16O27, bulk density is 2.8 ~ 3.5g/
cm3。
One kind of embodiment described above, only more preferably specific embodiment of the invention, those skilled in the art
The usual variations and alternatives that member carries out in the range of technical solution of the present invention should all include within the scope of the present invention.
Claims (7)
1. a kind of high-purity CM2A8The preparation method of material, which is characterized in that the method by the way that the raw material of CaO will be contained, containing MgO's
Raw material and containing Al2O3Raw material carry out common mill mixing, the bonding agent of additional 1~6 wt% of said mixture mixes aftershaping, does
1650~1850 DEG C are warming up to after dry in air atmosphere, keeps the temperature 120~720 minutes, high-purity CM is made in natural cooling2A8Material
Material.
2. according to the method described in claim 1, it is characterized in that, the method includes：
S1：Al will be contained2O3Raw material, the raw material containing CaO and the raw material containing MgO match according to following chemical composition and mass percent
Than Al2O385.6~86.9%, MgO 7.2~8.5%, CaO 5.8~5.9% is ground 2~10 hours altogether；
S2：Add in the bonding agent of 1~6wt% of mixture in S1；
S3：S2 is added in high-pressure molding of the mixture through 10MPa~200MPa of bonding agent；
S4：It is dry after keeping the temperature 120~720 minutes under 1650~1850 DEG C of air atmospheres；
S5：Sintering synthesis CM2A8Material.
3. according to the method described in claim 2, it is characterized in that, the raw material containing CaO is dolomite, lime stone, stone
Ash, calcium hydroxide, calcium carbonate or calcium oxide etc., granularity are less than 180 mesh.
4. according to the method described in claim 2, it is characterized in that, the raw material containing MgO is that rich calcium dolomite, rich magnesium are white
Marble, fused magnesite, magnesite clinker, seawater magnesia or magnesia, granularity are less than 180 mesh.
5. according to the method described in claim 2, it is characterized in that, described contains Al2O3Raw material be diaspore, aluminium hydroxide,
Commercial alumina, Reactive alumina or aluminium oxide etc., granularity are less than 180 mesh.
6. according to the method described in claim 2, it is characterized in that, the bonding agent is starch, dextrin, Aluminum sol, paper pulp
Waste liquid, calcium lignosulfonate, polyvinyl alcohol or methylcellulose.
7. a kind of high-purity CM2A8Material, based on the method described in one of the claims 1-6, which is characterized in that the CM2A8
Material is with CaMg2Al16O27For main object phase, mass fraction is more than 98%, and bulk density is 2.8 ~ 3.5g/cm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113523262A (en) * | 2020-04-17 | 2021-10-22 | 宝山钢铁股份有限公司 | Anti-blocking submerged nozzle |
| CN114560687A (en) * | 2021-12-30 | 2022-05-31 | 北京科技大学 | Industrial preparation method of CMA material based on MgO controlled raw material crystal morphology |
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| CN102030545A (en) * | 2010-10-28 | 2011-04-27 | 中国地质大学（北京） | MgAl2O4-CaAl12O19 composite-phase high-temperature resistant material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113523262A (en) * | 2020-04-17 | 2021-10-22 | 宝山钢铁股份有限公司 | Anti-blocking submerged nozzle |
| CN113523262B (en) * | 2020-04-17 | 2022-10-21 | 宝山钢铁股份有限公司 | Anti-blocking immersion water gap |
| CN114560687A (en) * | 2021-12-30 | 2022-05-31 | 北京科技大学 | Industrial preparation method of CMA material based on MgO controlled raw material crystal morphology |
| CN114560687B (en) * | 2021-12-30 | 2023-09-29 | 北京科技大学 | Industrial preparation method of CMA material based on MgO regulation and control of raw material crystal morphology |
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