CN101417884A - Nano Al2O3 film encapsulated carbon-aluminum spinelle refractory castable and preparation method thereof - Google Patents
Nano Al2O3 film encapsulated carbon-aluminum spinelle refractory castable and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon-aluminum spinel refractory castable material wrapped up by a nano AL2O3 film and a preparation method thereof. The preparation method of the carbon containing castable material firstly puts the mixture of hydrated alumina, carbon powders and water in a high speed impact mixing-stirring mill for coating processing treatment, the materials impact and collide with each other after high-speed impact treatment, thus forming a composite sol suspension liquid of carbon and aluminum hydroxide and causing the aluminum hydroxide to be strongly absorbed on the surface of the carbon, therefore, the manufacture technology for coating carbon powders by using aluminum hydroxide is realized, then the composite sol suspension liquid is directly added to the mixed materials for preparing alumina gel coatings by controlling the conversion process from the aluminum hydroxide to the gel, and hence the whole-covered, crack-free and high-strength compact alumina wrapping layer is formed; and during the mixing and stirring process of the castable material, magnesium hydroxide sols are generated by the hydration reaction of magnesia powders and mixed water in matrix powders, then the nanostructure matrix of carbon-aluminum-spinel is generated by the in-situ synthesized reaction of the magnesium hydroxide sol and aluminum hydroxide sol suspension liquid, and finally the carbon-aluminum refractory castable material is prepared.
Description
[technical field]
The invention belongs to technical field of refractory materials, relate in particular to a kind of whole ladle carbon-aluminum spinelle refractory castable of nano aluminium oxide film wrapped and preparation method thereof of secondary refining of making steel.
[background technology]
Along with the increase of Clean Steel output, the secondary refining The Application of Technology is also more and more general, and in order to catch up with the Clean Steel developing steps, the secondary refining technology has obtained fast development.LF external refining method is to adopt more a kind of method of refining at present both at home and abroad, and it is the comparatively general a kind of form of present refining ladle that its inner lining material adopts magnesia carbon brick or Al2O3MgOC Bricks to build ladle by laying bricks or stones.The magnesia carbon brick that adopts phosphorous flake graphite is a kind of refractory materials of excellent property, is used widely in ladle.But use recent years magnesia carbon brick some problems to occur in steelmaking process: the thermal conductivity that the phosphorus flake graphite is high causes that effect of heat insulation descends, thereby causes heat loss rate to increase, and causes ladle shell deformation and work-ing life to be reduced; Carbon in the magnesia carbon brick can enter and cause molten steel recarburization in the molten steel, especially behind steel secondary refining, has a strong impact on steel quality, therefore, the steel industry strong request reduces the carbon content in the magnesia carbon brick, and for this reason, the researchist just is being less than 5% novel magnesia carbon brick in the focus development carbon content.By using nano-scale carbon particle and mixed carbon black, traditional structure matrix can be changed into nano-structured matrix, successfully developed the magnesia carbon brick of MgO parcel with high-heat resistance shock resistant, high erosion resistance and better heat-proof quality.[exploitation of Shigeyuki Takanaga. nanotechnology refractory materials-IIIMgO parcel magnesia carbon brick, the 9th associating international refractory materials academic conference (UNTECR ' 05) paper translated " latest developments of external refractory materials science and technology " P27-31 selectively].On the researchdevelopment basis of magnesia carbon brick and aluminum-carbon brick, researched and developed Al2O3MgOC Bricks and aluminate carbon brick, and in refining ladle, obtained widespread usage.But Al2O3MgOC Bricks uses in the secondary refining stove, and its work-ing life is generally not high, exists problem on the low side in work-ing life.The original design bag wall of Taiyuan Iron and Steel Co. the 4th steelworks 180t refining ladle uses magnesia-alumina-carbon brick, bag end aluminate carbon brick, and be about 75 heats its mean life; The slag line magnesia carbon brick, be about 45 heats disposable mean life, this in work-ing life level, using in the LF refining ladle at home is very representational level.On the other hand, adopt Al2O3MgOC Bricks and magnesia carbon brick to build ladle by laying bricks or stones, also exist engineering time length, labour intensity to cause problems such as molten steel pollution greatly, easily.So, incompatible with the secondary refining technical development, can not satisfy the secondary refining Technical Development Requirement.Compare with the typing refractory product, unsetting refractory castable in production, labour productivity, operating efficiency, materials consumption, improve the advantage of aspects such as execution conditions, save energy, at home and abroad all obtained developing rapidly.In recent years, because the appearance of high-quality high-performance raw material, the quoting of various new and high technologies, the application of the constructional method that mechanize is new makes refractory castable obtain developing rapidly at aspects such as material, kind, construction and application.Replace refractory product with refractory castable, also can be competent fully even under some extreme conditions, use, therefore more and more higher to refractory castable performance and service requirements, so adopt the whole refining ladle of high material, the cast of high quality refractory castable to become the main developing direction of secondary refining ladle with refractory materials.
At present at home and abroad, particularly in Japan, generally adopt the whole ladle technology of refractory castable, be extensive use of alumina-magnesia castable and alumina-spinelle mould material aspect the integral lining use material, consider from mould material material aspect, Japan's steel ladle casting material has adapted to the whole ladle service requirements of secondary refining basically.But, increase along with the refining steel grade, the application of secondary refining steel is also more and more general, and widely used such mould material is damaged because of chemical erosion and the structure spalling that the slag poor permeability causes such as the Bao Biyong alumina-magnesia castable from also there are some shortcomings on performance at present; The bag end, use the alumina-spinelle mould material because of heat-shock resistance, particularly slag penetration resistance is incompatible requires the crackle that causes and peels off damage, all be to have a strong impact on the refining ladle major cause in work-ing life, so still demonstrate ladle work-ing life and the incompatible situation of refining techniques demand for development from the material aspect.[latest developments of Mitsuo Sugawara Japan mould material technology, the 9th associating international refractory materials academic conference (UNTECR ' 05) paper translated " latest developments of external refractory materials science and technology " P303-309 selectively].
Carbon have be difficult for by molten steel and slag moistening, low thermal expansivity, high thermal conductivity and at high temperature life-time service can not soften, so carbon is joined in the refractory castable based on oxide compound, structure and performance are improved at all.Therefore, the research and development of carbon containing mould material have at present become the hot subject of a ten minutes concern in the domestic and international refractories industry.Yet, in the production and application of carbon containing mould material, still there is an a series of difficult problem, such as: the wettability of carbon and the problem of bad dispersibility; The selection problem of carbon source and efficient oxidation inhibitor; Problem of oxidation under the high temperature; Be unsettled on thermodynamics between oxide compound and the carbon, produce redox reaction and cause weave construction deterioration problem; Problems such as the wetting ability of carbon, rheological, water consumption, these problems have all become the great difficult problem that restriction carbon containing mould material further develops and uses.Therefore, do not carry out industrialized production yet and in secondary refining, obtain practical application,, develop nanometer AL so how to address these problems up to present carbon containing mould material
2O
3The carbon-aluminum spinelle refractory castable of film wrapped is the key issue of steel-making secondary refining technical development.
[summary of the invention]
The object of the invention provides a kind of have excellent anti-molten steel and slag corrosion, slag penetration resistance, heat-shock resistance, high volume stability, high temperature creep-resisting and heat-proof quality preferably, and it is with nanometer AL
2O
3Carbon-aluminum spinelle refractory castable of parcel and preparation method thereof.In secondary refining LF, use, solve the various difficult problems that present carbon containing mould material exists in producing and using, to satisfy the secondary refining Technical Development Requirement, for Iron And Steel Industry provides optimal service.
For achieving the above object, technical scheme that the present invention takes mainly comprises two major technique contents: the selection of first coating material and coating processes preparation method thereof.Be to adopt nanometer AL in the scheme
2O
3As coating material, it is to be starting raw material with the hydrated aluminum oxide, adopt colloidal sol-gel process, make aluminum hydroxide sol suspension by the hydration reaction of hydrated aluminum oxide, this collosol suspension liquid is put into high speed impact stirrer (1500～2000 rev/mins) with carbon dust and is carried out the coating processes processing treatment, through high speed impact and collision, causing forming aluminum hydroxide sol is adsorbed on the carbon dust surface consumingly, realized applying the manufacture craft of carbon dust with aluminum hydroxide sol, directly join this complex sol liquid in the compound then, prepare the alumina gel coating by the control aluminum hydroxide sol to the conversion process of gel, thereby formed all standing, flawless, the aluminum oxide integument of high-strength compact.It two is forming processes of carbon-aluminum spinelle nano-structured matrix, it is in mould material mixing and whipping process, magnesia powder in the matrix powder and mixing water generation hydration reaction, generate magnesium hydroxide colloidal sol, it and aluminum hydroxide sol suspension pass through in-situ synthesized reaction, form the nano-structured matrix of carbon-aluminum-spinel, made carbon-aluminum spinelle refractory castable of the present invention.
Nanometer AL of the present invention
2O
3The carbon-aluminum spinelle mould material of film wrapped is to adopt following batching preparation.
The weight percentage of each component is in the batching: the aggregate add-on is 67-73%, and matrix powder add-on is 27-33%.Aggregate batching is formed:
High grade bauxite grog: 33-50%, wherein the 10-25mm macrobead is 25-35%, the 5-10mm particulate material is 7-14%;
Sub-white corundum or brown corundum: 3-5mm, 5-12%; Aluminum-spinel: 1-3mm, 0-8%; 0.1-1mm, 6-10%;
Fused white corundum or plate diamond spar: 1-3mm, 0-10%; 0.1-1mm, 5-12%;
The matrix powder is formed:
Pure calcium aluminate cement: 2-4%; Silicon ash: 0.5-2%; White fused alumina or plate diamond spar :≤44 μ m are 5-14%;
Magnesia :≤44 μ m, 0-5%; Electrosmelted magnesite clinker: 0-5%; Aluminum-spinel :≤44 μ m, 0-12%;
Calcine industrial α-AL
2O
3Ultrafine powder :≤4 μ m are 0-5%; The activated alumina ultrafine powder :≤2 μ m are 1-5%;
Carbon dust: D
50=2.6 μ m, 3-5%; Silicon carbide: 2-4%; Metallic aluminium powder: 0-0.5%; Metallic silicon power: 0.5-2.5%;
Aluminum hydroxide sol liquid is in siccative amount: 2-4%; Thinner and dispersion agent (adding): 0.1-0.4%; Sodium hexametaphosphate 99,
Tripoly phosphate sodium STPP adds: 0-0.35%; Organic ethylene glycol, butanols class dispersion agent add: 0-0.35%, water (adding): 0-1%.
Carbon dust described in the batching is that to adopt coke powder be carbon source, granularity 2 μ m, and its maximum characteristics are to have solved that to use flake graphite be a difficult problem more than the existing dilution of carbon source, wettability, dispersiveness, mobile difference and the water consumption.Carbon dust and aluminum hydroxide sol suspension are by chemisorption and colloidal sol keying action, realized fine and close combination, and the viscosity of carbon containing mould material is reduced greatly, flowability improves greatly, water consumption is reduced to minimum, reach and the similar degree of alumina-spinelle mould material that does not add carbon, the mould material water consumption under the condition about 5%, prepare high-compactness, high strength ,≤5% low-carbon (LC)-aluminate mould material; Carbon dust is compared with the phosphorus flake graphite, and at high temperature oxidation-resistance is relatively poor relatively, and this can be by adding oxidation inhibitor and solving with nano-oxide film wrapped carbon dust technology.Another subject matter of carbon containing mould material is oxidation-resistance difference and low intensity, in the carbon containing mould material, has higher void content owing to comparing with corresponding refractory product, thereby makes problem more outstanding.So in the wettability of improving carbon, dispersiveness, above-mentioned coating method has also improved oxidation-resistance.However, still need oxygen-proof property and the physical strength of oxidation inhibitor further to improve the carbon containing mould material efficiently.All add at silicon carbide, metallic aluminium powder and metallic silicon power described in the batching and adding quantity thereof, to the at high temperature anti-oxidation vital role that played of carbon containing mould material of the present invention as efficient oxidation inhibitor.In addition, this class oxidation inhibitor is except the oxygenizement of anti-blocking, two vital role of also influential mould material character, promptly improve the formation of hot strength and secondary carbon, the particularly important is the effect in its secondary carbon formation and the deposition process, the secondary carbon laydown that generates is on the surface of mould material matrix pore, and it is to improving the slag resistance of carbon containing mould material, and particularly slag penetration resistance has been brought into play vital role.
Wedding agent described in the batching is to be main wedding agent with aluminum hydroxide sol suspension, it is to be starting raw material with the hydrated aluminum oxide, adopt sol gel process to make, and add the composite binder that a spot of pure calcium aluminate cement is formed through hydration reaction and solation processing.Described thinner and dispersion agent are meant Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, ethylene glycol, butanols etc.
Aggregate described in the batching partly is to be used in a kind of mould material by high grade bauxite grog, brown corundum, sub-white corundum, fused white corundum or multiple different varieties such as plate diamond spar, spinel, characteristic and grain composition, with the contradiction between balance kind, quality and the production cost.This many kinds aggregate mixes use, it is one of novel refractory castable key character, particularly the above macrobead of 5mm adopts the high grade bauxite grog, its materials amount reaches total batching more than 40%, the production cost of its this novel high-grade mould material is significantly reduced, for good feasible condition has been created in its widespread use.Yet＜5mm fine particle aggregate, select for use high-grade white fused alumina, plate diamond spar, brown corundum or synthetic aluminum-spinel to improving the mould material quality and particularly improve high-temperature behavior and the resistance to slag corrosion aspect having played vital role, also is significantly improved work-ing life simultaneously.Aspect grading of aggregate, outstanding feature is that critical granularity is big, be 25mm, macrobead content is many, and the 10-25mm macrobead reaches 35%, and the gradation scope is wide, be divided into five kinds of particle grades of size, and being formulated as the production high-compactness in varing proportions, high-strength fireproof pour material provides important assurance, also is one of refractory castable important technology content of the present invention simultaneously.
Matrix powder described in the batching partly is by the nano-oxide ceramic powder, micron and the various matrix powders of submicron grade, composition such as carbon dust and admixture, it is characterized in that the matrix powder is wide in variety, grade is thin, usually≤44 μ m, some component is to adopt superfine powder, its grade is≤4 μ m, also has nanometer grade powder, therefore materials chemistry reactive behavior height, the in-situ synthesized reaction that this just descends to be taken place for the combining case between the matrix powder of the nanoparticle of high dispersive and micron and submicron grade and thermal structure reacts and the formation of nano-structured matrix provides assurance.Aspect matrix powder material, adopt the polycomponent compounding ingredient, principal item has: comprise calcining α-AL in alumina series
2O
3, reactive behavior AL
2O
3, fused white corundum, plate diamond spar etc., they all have different separately characteristics, for example: calcining α-AL
2O
3Can be used as refractoriness, intensity and resistance to fouling that wedding agent improves mould material; Reactive active A L
2O
3Have very high reactive behavior and low water requirement, with the matrix of strengthening mould material to improve its effect; The plate diamond spar micro-structural feature is to have a large amount of sealed porositys and open pore seldom, and the mould material that contains plate diamond spar at high temperature has higher intensity, good thermal fatigue resistance and erosion-resisting characteristics; Fused white corundum is the monocrystalline product, is applied in the mould material, mainly is to improve high temperature creep and anti-slag corrosion.In the magnesium oxide component, adopt electrically molten magnesia and sintered magnesia respectively, with the reaction process of control spinel.Therefore, during above-described matrix phase was formed, the different varieties of employing, adding quantity and granularity requirements all were one of important technology contents of carbon containing refractory castable of the present invention, also are the important guaranteed conditions of carbon containing refractory castable of the present invention.
The construction technology condition of whole refining ladle is: make through mixing operations such as stirring, model installation, casting and constructing, vibrating forming, the demoulding and maintenance, baking.
Require at first the dry type compound for preparing to be joined dried mixing 1-2 minute in the forced mixer according to batching of the present invention, will through disperse and dilution after the concentration that make be 58-61% carbon-aluminium hydroxide complex sol liquid directly joins in the compound, rewetting mixed 5 minutes, in mixing process, need the regimen condition to add the water of 0.1-1.0% according to compound, wet mixed mould material joins in the ladle model by distributor, the moulding of material is to adopt the shock club vibrating forming, move in the Ladle-casting apparatus after maintenance in 24 hours and toast, the whole ladle of the cast after the baking can come into operation.
Nanometer AL of the present invention
2O
3In the production technique of the carbon-aluminum spinelle mould material of film wrapped, adopt liquid phase dispersed encapsulated method to carry out, its concrete implementation step, at first be with hydrated aluminum oxide as raw material, add quantitative water, adopt the high speed impact stirring technique, through solation and dispersion treatment, and add under the situation of dispersion agent, making concentration is the aluminum hydroxide sol suspension of 45-47%, to reach abundant dispersion and to destroy the purpose of original reunion; Next is that the specified quantity carbon dust is added wherein, proceed high speed impact and stirring, by adjusting synthesis technologic parameter, making concentration is carbon-aluminium hydroxide complex sol suspension of 58-61%, not having crystallization, reunion, sedimentation etc. to cause under the situation of the uneven factor existence of dispersion, make system precipitation, gel, polymerization; The 3rd, under the oven dry heating condition, realized the conversion process of colloidal sol to gel, obtained nanometer AL
2O
3The integument of film wrapped carbon dust.Particularly this process using high speed rotating mixes Technology, the homogeneity and the dispersiveness of composite granule are guaranteed, but also making carbon powder particle further obtain refinement, the particle shape spheroidization is for the flowability that improves tap density and slurry has been created favourable condition; Simultaneously the surface energy of composite granule and surfactivity are improved greatly, therefore, the alumine hydroxide colloid particle is adsorbed on the surface of carbon securely, forms flawless, all standing, high fine and close coating integument.It is successfully used the quality that guarantees paint-on technique and paint-on technique and has played vital role.Nano-structured matrix is incorporated in the carbon-aluminum spinelle mould material structure,, makes aluminate form AL by improving processing method
2O
3The integument of film wrapped carbon dust is successfully developed and is used nanometer AL
2O
3The carbon-aluminum spinelle mould material of film wrapped.This carbon containing refractory castable had both had favorable tissue structure and mechanical performance index, had excellent slag resistance, slag penetration resistance energy, heat-shock resistance, high volume stability, high temperature creep-resisting and suitable heat conductivility again.In addition, when at high temperature using, a series of thermal structure reactions will take place.The combining case thermal structure down that is mainly reflected in nano-ceramic powder and submicron and micron grade matrix powder reacts, this is the substance of research and development nanometer refractory materials, also being formation and its successfully use in refining ladle that causes nano-structured matrix, all is very crucial.
The refining ladle integration is refining techniques development objective requirement, it also is the inexorable trend of refining ladle development, its major advantage can make the ladle construction process realize serialization and mechanize, make whole construction course realize streamline operration, with build ladle by laying bricks or stones with refractory brick and compare, labour intensity is little, engineering time is short, quality can be guaranteed, and to have the ladle of building by laying bricks or stones of a large amount of brickwork joints usually be the major cause that causes badly bleeding and bleed-out, from steel-making refining techniques angle, adopt the secondary refining technology to produce ultra clean steel, minimizing is mingled with, and the quality that improves steel is to realize the basic goal of integrated poured ladle.On the other hand, the maximum characteristics of the whole ladle of this cast are can realize the spray repair operation and overlap the huge potential ability of repairing continuously, promptly realize the purpose of so-called " permanent liner ".For whole ladle, this measure is to reduce materials consumption and production cost most effectual way, also is simultaneously to improve resource utilization, reduces environmental pollution effective measure the most, is the important directions of secondary refining technical development.
Nanometer AL of the present invention
2O
3The carbon-aluminum spinelle mould material of film wrapped, according to the actual difference of using position, working conditions and damage mechanism in refining ladle, also inequality to the characteristic requirement of carbon containing mould material.Therefore, batching is formed and manufacturing condition has successfully been developed two types nanometer carbon-aluminum spinelle mould material with different qualities by changing, i.e. synthetic carbon-aluminum spinelle mould material of reaction and pre-synthetic carbon-aluminum spinelle mould material.Because batching is formed and production technique different, so two kinds of functions that mould material had and characteristic are also inequality.The former carbon containing mould material since the building-up reactions of spinel produce and use in carry out, in the spinel forming process, produce bigger volumetric expansion, thereby the space of mould material and pore are effectively filled, make it have very high mechanical property and resistance to slag corrosion and slag penetration resistance, therefore be more suitable for using in positions such as refining ladle side wall, impact zones; Quoting of latter's spinel is based on synthetic spinel in advance, and the reaction synthetic spinel is auxilliary, so it is little to have thermal expansivity, and excellent structural stability, be difficult for cracking and peeling off damage in actual use.Therefore, it is more suitable for using in furnace bottom, is also usually used at the impact zone position sometimes.The research and development success of two kinds of carbon-aluminum spinelle mould material with different qualities and in refining ladle, successfully use development and the application that has effectively promoted the secondary refining technology.
Nanometer AL of the present invention
2O
3Function and characteristic that the preparation of the carbon-aluminum spinelle mould material of film wrapped and the success of use confirm nanotechnology and nano material fully and had are fully confirmed in nanometer carbon containing mould material, this just uses in carbon containing mould material field for nanotechnology and becomes a reality and possibility, has also indicated direction for secondary refining with the development of carbon containing mould material simultaneously.Its outstanding feature is the weave construction densification, microstructure is obviously improved, nano-structured matrix is formed, show through SEM and XRD microstructure assay, at 1100 ℃, after 1550 ℃ of burnings, and in the sample after using, the existence and the formation of carbon-aluminum spinelle nano-structured matrix have all been found, and this nano-structured matrix has been controlled nanocrystal effectively and has further been grown up, the function and the characteristics of nanometer refractory materials have been given full play to, made the present invention's nano spinel bonded carbon-aluminum spinelle refractory castable, its every performance index significantly improve comprehensively and improve, 110 ℃ of oven dry posterior spiracle rates are 14%, and withstand voltage and folding strength reaches 100MPa respectively and more than the 10MPa; After 1550 ℃ of calcinings, volume density reaches 3.03g/cm
3, void content is 14%, withstand voltage and folding strength reaches 100MPa respectively and more than the 28MPa.On the other hand, also demonstrate excellent performance at aspects such as anti-molten steel, slag corrosion, slag penetration resistance, heat-shock resistance, high volume stability, high temperature creeps, these characteristics are successfully used in steel-making secondary refining stove for it and are had laid a good foundation.The large scale prefabricated member that adopts carbon-aluminum spinelle mould material of the present invention to make, use at the harshest impact zone position of 195t refining ladle and to reach 120 heats disposable mean life, reach 180 heats the highest work-ing life, former employing Al2O3MgOC Bricks is built ladle by laying bricks or stones, be about the 70-75 heat disposable mean life, and is significantly improved its work-ing life.At the bottom of the whole refining furnace with carbon-aluminum spinelle mould material of the present invention cast, side wall also all obtained outstanding result of use.And the present invention nanometer AL
2The carbon-aluminum spinelle mould material of O parcel, material is selected, complete processing is rationally advanced; Production cost is relatively low, and economical adaptation is strong; No dust pollution, compliance with environmental protection requirements is real green product; Adapt to the recycling economy development requirement.Therefore, in secondary refining, use the development prospect that wide expansion is arranged.
Embodiment:
Embodiment 1:
List in the reaction synthesis of nano AL of table 1 embodiment 1 according to the present invention
2O
3The carbon-aluminum spinelle casting material formula of film wrapped, compound was joined in the forced mixer dry blending 1-2 minute, to stir then that to carry out solation and dispersion treatment concentration be that nano-sized carbon-aluminium hydroxide complex sol suspension of 58-61% directly joins in this compound through high speed impact, rewetting mixed 5 minutes, in mixing process, according to the actual water that needs the regimen condition to add 0-1% of compound, make reaction synthesis of nano AL of the present invention
2O
3The carbon-aluminum spinelle mould material of film wrapped.The basic mechanical design feature index of present embodiment mould material is listed in table 2, its maximum characteristics are: the weave construction densification, and void content is low, withstand voltage and folding strength height, and excellent resistance to slag corrosion and slag penetration resistance, be suitable for positions such as secondary refining LF furnace side wall, impact zone and use.
Embodiment 2
List in the embodiment 2 pre-synthetic carbon-aluminum spinelle casting material formulas of table 1 according to the present invention, compound is added in the forced stirrer dry blending 1-2 minute, then will through high speed impact stir carry out solation and dispersion treatment concentration 58-61% carbon-aluminium hydroxide complex sol suspension directly joins in the compound, rewetting mixed 5 minutes, add the water of 0-1% in the mixing process according to the actual moisture situation of compound, make pre-synthesis of nano AL of the present invention
2O
3Carbon-the aluminum spinelle refractory castable of film wrapped.The basic mechanical design feature index of present embodiment mould material is listed in table 2, and its maximum characteristics are heat-shock resistance and thermal structure excellent in stability, is difficult in actual use crackle taking place and peeling off damage, is suitable for position, LF refining furnace bottom and uses.
Embodiment 3
List in the embodiment 3 nanometer AL of table 1 according to the present invention
2O
3The carbon-aluminum spinelle casting material formula of film wrapped, mix stirring through stirrer, adopt bumper or shock club vibrating forming, make and be of a size of 1120/1200 * 670 * 460 centimetres, the large scale prefabricated member of substance 1100kg, air care 24 hours is toasted in the electrically heated stoving oven, storing temperature: 280 ℃, storing time: 120 hours.Then large scale prefabricated member is seated in refining ladle impact zone position, integrated poured to carrying out at the bottom of the refining ladle bag again.It is that anti-molten steel impact property is very strong that the maximum characteristics of prefabricated large-scale component are adopted at this impact zone position, significantly improve work-ing life, it adopts on-the-spot integrated poured structure to compare with impact zone, can improve its work-ing life more than the 50-80%, it also provides favourable condition for the whole refining ladle difficult generation crackle in bake process that adopts mould material preparation of the present invention bursts in addition.The basic mechanical design feature index of the large scale prefabricated member of present embodiment is listed in table 2.
Table 1, the prescription of the embodiment of the invention 1, embodiment 2 embodiment 3 refractory castablies
Table 2 embodiment of the invention 1, embodiment 2, embodiment 3 nanometers carbon containing-aluminate mould material salient features
Claims (7)
1, a kind of nanometer AL
2O
3Carbon-aluminum spinelle mould material of film wrapped and preparation method thereof, it is characterized in that mass percent that carbon containing mould material batching forms is made up of 67-73% aggregate and 27-33% matrix powder, wherein aggregate batching is: high grade bauxite grog: 33-50%, wherein the 10-25mm macrobead is 25-35%, and the 5-10mm particulate material is 7-14%; Sub-white corundum or brown corundum 3-5mm particulate material are 5-12%; Fused white corundum or plate diamond spar: 6-16%, wherein the 1-3mm particulate material is 0-10%, the 0.1-1mm particulate material is 5-12%; Aluminum-spinel: 6-14%, wherein the 1-3mm particulate material is 0-8%, the 0.1-1mm particulate material is 6-10%; The matrix powder is: the aluminum-spinel powder :≤44 μ m are 0-12%; White fused alumina or plate diamond spar :≤44 μ m are 5-14%; Calcining α-AL
2O
3Ultrafine powder≤4 μ m are 0-5%: active A L
2O
3Ultrafine powder :≤2 μ m are 1-5%; Calcining MgO≤44 μ m are 0-5%; Electric smelting MgO, 0-5%; Carbon dust D
50=2.6 μ m, 3-5%; Carborundum powder: 2-4%; Metallic silicon power: 0.5-2.5%; Metallic aluminium powder: 0-0.5%; Pure calcium aluminate cement: 2-4%; Silicon ash: 0.5-2%; The nano-aluminum hydroxide collosol suspension liquid is in siccative amount: 2-4%; Sodium hexametaphosphate 99, tripoly phosphate sodium STPP add: 0-0.35%; Organic ethylene glycol, butanols class dispersion agent add: 0-0.35%, water adds: 0-1%.
2, a kind of nanometer AL
2O
3Carbon aluminate mould material of film wrapped and preparation method thereof, the preparation technology who it is characterized in that the mould material of carbon-aluminum spinelle does the dry mix of preparation to mix 1-2 minute in forced mixer, then the 58-61% nano-aluminum hydroxide complex sol suspension of making directly being joined in the compound rewetting mixes and stirred 5 minutes, in mixing process, add the water of 0-1% according to slip dehydration situation, through wet mixing stirring, cast, vibrating forming, maintenance, baking, make the refractory castable of carbon-aluminum spinelle of the present invention again; According to the actual position of using in refining ladle, the difference of working conditions and damage mechanism, characteristic to the carbon-aluminum spinelle mould material requires also inequality, batching is formed and processing method has successfully been developed two types carbon-aluminum spinelle mould material with different qualities by changing, synthetic carbon-aluminum spinelle mould material of i.e. reaction and pre-synthetic carbon-aluminum spinelle mould material, they use at refining ladle different sites and different condition, its ladle life is significantly improved, for the secondary refining technology provides suitable more carbon-aluminum spinelle mould material new variety, advantageously promoted the development of secondary refining technology.
3, according to claim 1,2 described nanometer AL
2O
3Carbon-aluminum spinelle mould material of film wrapped and preparation method thereof, it is characterized in that with aluminum hydroxide sol suspension as the nano ceramics wedding agent of this carbon containing mould material and the coating material of coating carbon dust, its preparation technology adopts the sol-gel technology method, be to be starting raw material with the hydrated aluminum oxide fine powder, add quantitative water, the impact mixing and blending machine of putting into high speed rotating disperses to handle with solation, make hydrated aluminum oxide generation hydration reaction, after dilution and dispersion treatment, form aluminum hydroxide sol suspension; Secondly in this production technique, adopt liquid phase dispersed encapsulated method to carry out, its concrete implementation step is carbon dust to be joined high speed rotating impact in the stirrer, carrying out high speed impact handled 1-4 hour, carbon and aluminium hydroxide complex sol suspension have been produced, thisly mix Technology through high speed impact, the homogeneity and the dispersiveness of composite granule are guaranteed, but also make carbon powder particle further obtain refinement, the particle shape spheroidization, created favourable condition for improving slurry density and flowability, simultaneously the surface energy of composite granule and surfactivity are improved greatly, therefore make of the Chemical bond and the adsorption of aluminum hydroxide sol suspension by colloidal sol, the nanoparticle of colloidal sol is adsorbed on the surface of carbon dust securely, form flawless, all standing, the coating integument of high density carbon, it has played vital role to guaranteeing paint-on technique quality and paint-on technique successful Application.
4, according to claim 1,2,3 described nanometer AL
2O
3Carbon-aluminum spinelle mould material of parcel and preparation method thereof, it is characterized in that making carbon-aluminium hydroxide complex sol suspension directly joins in the compound, this wet method preparation process through high speed impact and stir process, the reunion and the dispersive difficult problem of nano-powder have not only been solved, and solved the wettability of carbon, the difficult problem of bad dispersibility, nano-powder is fully disperseed in the matrix of compound, prepared not have and reunited, the carbon aluminate mould material of high dispersive, meanwhile also solved of the pollution problem of nanometer dust to environment, in addition, produce the alumina gel coating by the control aluminum hydroxide sol to the conversion process of gel, thereby formed all standing, flawless, the nano aluminium oxide integument of high-strength compact, in production technique of the present invention, the formation of carbon-aluminum spinelle nano-structured matrix is in mould material mixing and whipping process, sintered magnesia powder in the matrix powder and mixing water generation aquation generate magnesium hydroxide colloidal sol, it and aluminum hydroxide sol suspension pass through in-situ synthesized reaction, form the carbon-aluminum spinelle nano-structured matrix, made carbon-aluminum spinelle refractory castable of the present invention.
5, according to claim 1,2 described nanometer AL
2O
3Carbon aluminate mould material of parcel and preparation method thereof, the different varieties that it is characterized in that aggregate, select and grain composition, it is to the mould material structure, performance and use produce material impact, aspect the selection of aggregate material, select for use and have different sorts, different qualities, the compound use in of the multiple aggregate of different grades with a kind of mould material, with the balance kind, contradiction between quality and the production cost, mould material aggregate of the present invention is selected for use respectively: the high grade bauxite grog, palm fibre corundum or sub-white corundum, plate diamond spar or white fused alumina, the aggregate of five kinds of different qualities such as aluminum-spinel constitutes, wherein all adopt the high grade bauxite grog, its AL greater than 5mm macrobead aggregate
2O
3〉=88%, volume density 〉=3.25g/cm
3, its amount reaches more than 40% of total stuff amount, and this compares with all adopting high-grade high-purity artificial-synthetic material at present both at home and abroad usually, and production cost is significantly reduced.
6, according to claim 1,2,3,4 described, use nanometer AL
2O
3Carbon containing-aluminate mould material of parcel carbon dust and preparation method thereof, it is characterized in that with nano composite oxide and carbon being the matrix phase composition and the design thereof of representative, it is the technological core content of this carbon containing mould material, comprise wedding agent system and matrix powder system, it has critical material impact to the formation of structure, performance, use and the nano-structured matrix of carbon containing mould material, and the wedding agent system is the composite binder that adopts aluminum hydroxide sol suspension and magnesium hydroxide colloidal sol, pure calcium aluminate cement to form; Matrix powder system adopts fused white corundum or plate diamond spar, sintering α-AL
2O
3, composition such as reactive activated alumina, electrically molten magnesia, magnesia calcined, aluminum-spinel; It is wide in variety that the matrix phase batching is formed materials, grade is thin, adopt the polycomponent compounding ingredient to greatest extent, make it give full play to various characteristics, be to form one of nano-structured matrix carbon containing mould material most important characteristics, the matrix powder is generally very thin, usually≤44 μ m, some component is to adopt superfine powder, its grade is 2-4 μ m, also have nanometer grade powder, so the chemical reactivity height of material, this just lays a good foundation for the compound and reaction between the nanoparticle of high dispersive and micron and the sub-micrometer grain grade matrix powder, their effect is the control rheology, thereby is convenient to construction and cast; Building-up reactions under the low temperature and structural response under the high temperature have been promoted greatly, and can generate useful fire-resistant synthetic phase, the different varieties that therefore above-described matrix phase adopts in forming, adding quantity and grade requirement, all being one of important technology content of carbon containing mould material of the present invention, also is the important guaranteed conditions of carbon containing mould material of the present invention.
7, according to claim 1,2,3,4,6 described, nanometer AL
2O
3Carbon-aluminum spinelle mould material of parcel and preparation method thereof, the use that it is characterized in that various efficient additives is a carbon-aluminum spinelle mould material important techniques condition of the present invention, this is one of nanometer carbon containing mould material most important characteristics, the admixture of nanometer carbon-aluminum spinelle mould material of the present invention, be meant the oxidation inhibitor of anti-blocking oxidation at high temperature, silicon carbide in the matrix powder, metallic silicon power, metallic aluminium powder and adding quantity thereof, be exactly the oxidation inhibitor that carbon containing mould material of the present invention adopts, its use has been played vital role at high temperature preventing oxidation of coal; Sodium hexametaphosphate 99 in the matrix powder, tripoly phosphate sodium STPP, ethylene glycol, butanols etc. are the thinner and the dispersion agent of mould material of the present invention, it adds kind and adds wherein a kind of sometimes, sometimes be two or more composite additive, add-on is 0.1-0.4%; Concerning peptizing agent, be that various acid of adding or alkali reach 2.5-3.0 with the pH value of regulating this sol system, making concentration of the present invention is 58-61% highly concentrated nano hydroxide colloid suspension wedding agent and coating material.
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