CN101875561B - Nano-SiO2 and nano-CaO composite ceramic bond siliceous refractory castable and preparation method thereof - Google Patents

Nano-SiO2 and nano-CaO composite ceramic bond siliceous refractory castable and preparation method thereof Download PDF

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CN101875561B
CN101875561B CN 201010165554 CN201010165554A CN101875561B CN 101875561 B CN101875561 B CN 101875561B CN 201010165554 CN201010165554 CN 201010165554 CN 201010165554 A CN201010165554 A CN 201010165554A CN 101875561 B CN101875561 B CN 101875561B
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silica
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高树森
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Abstract

The invention relates to a nano-SiO2 and nano-CaO composite ceramic bond siliceous refractory castable and a preparation method thereof. The castable uses nano-SiO2 and nano-CaO composite sol-suspension as nanometer ceramic bonding agent. The preparation method uses quartz, silica, silica fume or water glass as the starting material and adopts the high-energy mechanochemical method, the precipitation method and the sol-gel method; and the prepared sol-suspension is directly added in the mixture under wet mixing to form a nano-structural matrix using SiO2 as the main component through the solation process and prepare the nano-SiO2 refractory castable of the invention. The castable of the invention utilizes the nanometer technology and the nanometer material so as to improve the macroscopicstructure and the microcosmic structure and obviously increase the durability; and the siliceous refractory castable with special high-temperature resistance and crack resistance can be prepared and successfully applied in high-wind-temperature hot stoves, glass smelting kilns, coke ovens and the like.

Description

Nanometer SiO 2, CaO composite ceramics combining silica refractory castable and preparation method thereof
Technical field
The invention belongs to technical field of refractory materials, relate in particular to a kind of employing nanometer SiO 2, CaO composite ceramics combining silica refractory castable and preparation method thereof.
Background technology
Between in the past 20 years, the main trend of refractory technology development is constantly to increase integral material or unshape refractory, particularly its output in many national mould material of the use of refractory castable is over half above ultimate production, particularly the use of mould material has reached 70% in Japan steel industry, the U.S. accounts for 53% of refractory materials total amount, the high-quality and efficient unshape refractory of European countries accounts for about 50%, and China's unshape refractory only accounts for 30%, and is particularly larger with developed country's gap aspect kind and structure and new varieties.Therefore, need exert to carry out energy-saving high-performance Unshaped Casting Refractories, high quality high-performance acidic or alkaline refractory castable and wedding agent systematic research of new generation and exploitation.Compare with shaping refractory product, unshape refractory in production, labour productivity, operating efficiency, materials consumption, improve the advantage of the aspects such as execution conditions, save energy, environment protection, make it all obtain fast development at home and abroad.In recent years, because the appearance of high-quality high-performance raw material, the employing of various new and high technologies, the application of the constructional method that mechanize is new, make refractory castable at aspects such as material, kind, construction and uses, obtained further great development, even under some extreme severe condition, also can adapt to fully and satisfy service requirements, so adopt the monolithic lining of new and effective refractory castable to become the important directions of refractory materials development.With regard to unshape refractory, be matrix phase (finely divided property material phase) problem take the wedding agent system as representative with the problem of general character.This problem is the key problem in technology problem that determines unsetting quality product and use.When this problem of research, the most noticeable nano-grade ceramic binding agent of new generation---the high-dispersion nano ceramic sol suspension wedding agent that the most meaningfully adopts in other words, it is a kind of ceramic bond of artificial preparation, the characteristics of this type of wedding agent maximum utilize most of refractory oxides, composite oxides, oxide compound and non-oxidized substance or fire-resistant natural matter prepares, and can form the refractory castable of nano-structured matrix.It is the analysis that starts from phase equilibrium diagram that a new generation's nano-grade ceramic binding agent material is selected, analyze the final phase composite of refractory castable and organizational structure thereof, the microstructure of microcosmic particularly, under concrete application conditions, this phase composite and weave construction should guarantee that it has higher anti-damage; To select another principle of wedding agent be dispersed medium with disperse phase between must the phase coadaptation, for each disperse phase, all has the dispersed medium of oneself the best, its is can be to the full extent best satisfies and user demand of adaptation refractory castable.Therefore, there is not the what is called " omnipotent wedding agent " that is adapted to all kinds mould material.But, for every kind of concrete mould material, then existing the best combination agent, it can guarantee mould material in use, has the highest anti-damage.
The inventor is exactly according to this theory, use on aluminium-spinelle refractory castable basis at the whole ladle of depth study of second refining, quote nanotechnology and nano material is used in aluminium-spinel pouring material, made nanocomposite oxide ceramic combining alumina-spinelle refractory castable [contriver: Gao Shusen; Denomination of invention: nanocomposite oxide ceramic combining alumina-spinel refractory mould material and preparation method thereof; Patent of invention publication number CN.101397212A].In addition, also invent a kind of nanometer Al 2O 3Aluminium-the spinelle refractory castable of film wrapped carbon [contriver: Gao Shusen; Denomination of invention: nanometer Al 2O 3Refractory castable of the carbon-aluminate of film wrapped and preparation method thereof; Patent of invention publication number 101417884A].Two nanometer refractory castable patent of invention achievements to the progress and development of China's nanotechnology and nano material, have played important pushing effect, for enforcement and the development of satisfying the hot industry growth requirements such as iron and steel and new technology provides optimal service.The siliceous mould material of domestic production is compared with siliceous silica brick at present, and performance is generally on the low side, so silica fire resistant castable seldom is applied in the high temperature Thermal Equipment.The present invention nanometer SiO 2, the combination of CaO composite ceramics silica fire resistant castable preparation with use successfully, account for the ratio of refractory materials ultimate production to improving China's Unshaped Casting Refractories, to increase refractory castable new variety, and wedding agent systematic research of new generation and exploitation, all significant.Adopt nanometer SiO 2, the combination of CaO composite ceramics silica fire resistant castable, it is acid refractory material Typical Representative, occupies critical role in refractory materials principal item.Its preparation with uses successfully, unshape refractory is enlarged kind, the increase overall productivity, the raising quality is impelled the industrial development of China's refractory materials, and caught up with and surpassed the world's advanced levels, and is all significant.
Summary of the invention
The present invention seeks to adopt nanotechnology and nano material, start a kind of nanometer SiO with resistance to elevated temperatures, refractoriness and load softening point, high temperature creep resistance, anti-bursting property and aggressiveness and high durability of special excellence 2, CaO composite ceramics combining silica refractory castable, to satisfy and to adapt to the growth requirement that the attached high-blast-temperature hot-blast stove of modern iron-smelting blast furnace, glass melter superstructure, pit kiln etc. use; Silica fire resistant castable is the Typical Representative of acid refractory on the other hand, increases particularly acid or alkaline refractory castable expansion mould material use range of refractory castable principal item, increases overall unshape refractory output.
Nano-silicon refractory casting material of the present invention is to adopt SiO 2, CaO complex sol suspension is as nano-grade ceramic binding agent, the gordian technique of this mould material is nanometer SiO 2, CaO composite ceramics wedding agent preparation and application in siliceous mould material, employing with the polycomponent compounding ingredient of kinetic characteristic and new production process method correspondingly, this mould material batching is comprised of refractory aggregate, matrix powder, wedding agent and admixture system etc.Wherein the refractory aggregate consumption is 63-70%, and matrix powder and wedding agent system consumption are 30-37%.
Aggregate batching forms:
Calcine siliceous grog or useless silica brick: 51-70%, wherein 10-15mm macrobead material is 25-35%; The 5-10mm particulate material is 7-15%; The 3-5mm particulate material is 5-12%; The 1-3mm particulate material is 5-12%; 0.1-1mm the fine particle material is 0-12%;
Give birth to silica material fine particle material: 0.1-1mm, 0-12%;
Matrix powder and wedding agent system composition:
Nanometer SiO 2Collosol suspension liquid is in dry measure 3~5%;
Nanometer Ca (OH) 2Collosol suspension liquid is in CaO amount 1~3%;
Give birth to the silica ultrafine powder :≤10 μ m, 15~25%;
Calcined silica powder or useless silica brick powder :≤44 μ m, 5~15%;
Silicon ash: 1.5~3%;
White clay: 0~3%;
Mineral acid (hydrochloric acid or phosphoric acid) is as peptizing agent and dispersion medium, and it adds quantity and is as the criterion with control pH value 2.5~3;
Thinner and dispersion agent: be comprised of Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, tartrate, ethylene glycol, butanols class, its add-on is 0.2~0.5%;
Add water: 0~1%.
Nano-silicon refractory casting material of the present invention is with nanometer SiO 2, Ca (OH) 2Complex sol suspension is as the nano-grade ceramic binding agent of siliceous mould material, so this high density SiO 2The preparation of collosol suspension liquid and the application in siliceous mould material just become core technology of the present invention, also are the gordian techniquies of nano-silicon refractory casting material win or lose.
Highly concentrated nano SiO described in the batching 2The preparation of collosol suspension liquid is take the ultra-fine quartz of≤4 μ m, silica, silicon ash or water glass as starting raw material, adopts high-energy mechanochemistry method, the precipitator method, sol-gel method several different methods to make.In high-energy mechanochemistry method, ultra-fine siliceous raw material, water and various admixture joined when pulverizing in the high energy ball mill make.Research and development along with powder machinery, material is processed through high energy mechanical, particle is attenuated, specific surface area increases, the lattice distorted, also make simultaneously a large amount of mechanical energy of powder internal reservoir and chemical energy, therefore this course of processing in essence, can be summarized as mechanical force and chemical action, the mechanical activation method can affect mineral substance under the effect of mechanical force, carrying out the variation of dynamics state, physical structure and chemical property when levigate, is a kind of new concept so utilize mechanical energy to participate in directly with initiating chamical reaction.Therefore, high-energy mechanochemistry method is a kind of important method of preparation nano-powder material, also is important development trend in the nanometer field of new.Along with nanotechnology and nano material further investigation and development, liquid phase synthesizing method reaches its maturity with perfect in the chemical method, and entered step by step factory, we have used the precipitator method in chemical method, sol-gel method has been made single-phase or complex phase nano-ceramic powder material, and have carried out successfully using in the nanometer refractory materials.Chemical precipitation method is to utilize the precipitation principle that solute is separated from solution, throw out after through processes such as filtration, washing, drying and pyrolytic decompositions, the nano-powder material of formation.Sol-gel technique is the gelation process of colloidal sol, and namely the elementary cell particle in the liquid medium develops into the three-dimensional net structure of gel.The dispersed powder of superelevation is as disperse phase, with mineral acid and water as dispersion medium, add under the dispersion agent such as Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, tartrate, ethylene glycol and the thinner condition, in the wet processing course of processing, because liquid phase and solid phase interact, make and formed a large amount of silicic acid sols in its suspension, it is comprised of the colloidal particle of different dispersity and extent of hydration, under various factors impact, setting and harden occurs very easily, thereby it is very strong and have a gel of solid property to become bonding force.
Ca (OH) in the complex sol suspension described in the batching 2The preparation of collosol suspension liquid is take ultra-fine CaO powder as starting raw material, and CaO is that the form with dry powder joins in the compound, and add-on is 1-3%.The CaO powder of high dispersive is to carry out hydration reaction with the water that adds compound in stirrer, generates the calcium hydroxide sol solutions, mutually mixes with suspension mesosilicic acid colloidal sol again, makes complex sol suspension wedding agent of the present invention.Ca (OH) 2Sol solutions makes mould material produce very high low temperature bond intensity in drying course; Under the high temperature, Ca (OH) 2Decomposing generation CaO, is again the desirable mineralizer of this mould material, and it is produced the silica fire resistant castable that does not contain remaining quartz and have very vital role promoting that quartz transition is cristobalite, tridymite.This mould material when adopting inorganic phosphate as dispersion medium, the phosphoric acid that add this moment or a kind of aftereffect toughener of high-quality, and the solation process also had promoter action.
The nanometer SiO of a new generation 2Ceramic bond has the bond structure of organic polymer, but its basic structure is silicon-oxy tetrahedron, and nano-grade ceramic binding agent must have water as mass transfer and reaction media in formation and reaction process, behind the setting and harden, the part free water is present in the reactant as water of constitution.The bonding mechanism of nano-grade ceramic binding agent is to realize it and condense and harden owing to polymerization reaction take place with regard to its essence.With nanometer SiO 2Ceramic bond is example, at colloid SiO 2The surface will have silanol group (Si-OH) to form, and it will be decomposed into Si-O in water --H +, and produce the hydrogen combination, and in oven dry and heat-processed, dehydration forms the mesh skeleton structure of siloxanes (≡ Si-O-Si ≡), thus polymerization reaction take place, and its reaction formula is:
≡Si-OH+HO-Si≡→≡Si-O-Si≡+H 2O
So its setting and harden mechanism is realized its setting and harden by polymerization reaction take place, thereby produce high binding ability, and produce high strength.
Aggregate described in the batching partly be by calcined silica grog, useless silica brick, to give birth to that multiple different varieties, characteristic and the grain composition such as silica use in the same mould material be one of novel siliceous mould material key character, also is one of important measures of ensuring the quality of products, making rational use of resources and reducing production costs.A large amount of calcined silicas or useless silica bricks of using in silica fire resistant castable, comprise the waste product in the production and use after waste product (wanting removal of contamination), be not only needs of ensuring the quality of products, also be reduction cost and the demand of developing a circular economy.Adopt calcined silica or useless silica brick to give birth to the fine particle that silica is made 0.1-1mm as macrobead and middle particle, the employing of batching in this batching, to strengthen the caking power of mould material, can because quartz transition works the mischief, not the choose reasonable of siliceous mould material variable grain also simultaneously.Aspect the particles of aggregates grating, critical granularity is 15mm, macrobead content is many, the gradation scope is wide, being divided into five kinds of variable grains also prepares burden in varing proportions, for production high-compactness, low pore, high strength silica fire resistant castable provide the important guarantee condition, adapt to better and the user demand of satisfying silica fire resistant castable.
Matrix powder described in the batching and wedding agent, admixture system are the SiO by different qualities 2Matter matrix powder, SiO 2With compositions such as CaO compound oxidate ceramic, composite binder and admixtures.The matrix powder is by ultra-fine living ground silica (≤10 μ m) and calcined silica powder (≤44 μ m)) etc. form.In addition, also add multiple effective admixture.Ceramic nanocomposites, it refers to that heterogeneous phase nanoparticle is evenly dispersed in formed matrix material in the matrix of ceramic oxide, it refers to heterogeneous phase nano composition, be primarily characterized in that: from the granularity angle of matrix complex phase powder, it is by the nano-oxide ceramic powder, micron and the various matrix powders of submicron grade, divide by matrix and disperse phase material footpath size, nano heterogeneous ceramic comprises the compound of the matrix powder of micron, submicron grade crystal grain formation and nanoparticle level disperse phase.To adopt nanometer SiO aspect the nanometer material 2With CaO compound oxidate ceramic wedding agent, its matrix batching technical characteristics is: the one, and the mould material that adopts the nanocomposite oxide ceramic wedding agent to make; The 2nd, the matrix powder material is wide in variety, grade is thin, is≤44 μ m, and some component is to adopt ultra-fine matrix powder, and its grade is≤4 μ m, contains the nanometer grade powder of nano junction mixture system.Therefore the particle of material is little, specific surface area is large, chemical reactivity is high, this just be high dispersive nanoparticle with micron and the matrix powder of submicron grade between under the combining case, the in-situ synthesized reaction that occurs, thermal structure react and the formation of nano-structured matrix provides important guarantee; The 3rd, its structure, particularly microtexture are improved at all, property indices is significantly improved, and the security of wearing quality and use is able to remarkable improvement.Therefore, in the composition of above-described matrix phase, the employing of nanotechnology and different varieties, adding quantity, adding mode and different grain size requirement, all being the important guarantee condition of nano composite oxide combining silica mould material of the present invention, also is one of silica fire resistant castable main technical content of the present invention simultaneously.
The construction technology of nanocomposite oxide ceramic combining silica mould material is to make through operations such as batching, mix and blend, model installation, casting and constructing, vibrating forming, the demoulding and maintenance, bakings.Each operation is carried out in refractory materials factory before the mould material batching, and each later operation of mix and blend is using the working-yard to carry out.
According to batching requirement of the present invention, at first be that the mould material that will prepare joins and is dry mixed 1-2 minute in the forced mixer, then will through dispersion and dilution after the concentration made be the SiO of 53-58% 2The matter collosol suspension liquid directly joins in the mixing and blending machine, and the CaO in the compound and the mixing water of adding carry out hydration reaction, generates Ca (OH) 2Sol solutions, mix formation complex sol wedding agent with silicic acid sol suspension, mixed 5 minutes of rewetting, in the wet mixing process, add the water of 0-1% according to wet mixing and need regimen condition, mould material after the wet mixing joins in the model of construction body through automatic feeding device, behind the electromagnetic shaker vibrating forming, through air natural maintenance 24-48 hour, remove model, can carry out baker according to the baker system, oven drying temperature is controlled at 800-1000 ℃, be incubated after 1-2 days, the monolithic lining of the cast after the blowing out cooling checks can put into production use.
The preparation of nano combined collosol suspension liquid and use are important steps in this production technique, this is because the key of preparation ceramic base composite nano-powder is that nanoparticle is evenly dispersed in the matrix ceramic structure, produce and mix, few composite granule of reuniting is the prerequisite that obtains the nano composite ceramic of excellent performance and uniform microstructure.This technique is to adopt in-situ synthesis, and the matrix powder in the complex sol suspension that contains the precursor that can generate the nanophase component, has been finished by the conversion process of colloidal sol to gel in oven dry and heat-processed, has also realized condensing and sclerosis of mould material simultaneously.The characteristics of this synthetic method are to guarantee the Uniform Dispersion problem of nano heterogeneous ceramic, and, the nano composite oxide gel particle that in oven dry and heat-processed, generates, do not exist nanoparticle to disperse the problems such as uneven and reunion, this highly active nanoparticle can be under lower temperature condition, form nano-structured matrix by in-situ synthesized reaction, made the Novel fire-resistant mould material of this synthesis of nano structural matrix.
The making of nanocomposite oxide ceramic combining silica refractory castable of the present invention with use successfully, another functional performance that has confirmed that nanotechnology and nano material have can fully show in the siliceous mould material of nanometer, this just is applied in fire resisting material field for reality and possibility for nanotechnology, has also indicated direction for the refractory industry development simultaneously.The maximum outstanding characteristics performance of the silica fire resistant castable of nano composite ceramic combination is in the following areas: the one, and property indices significantly improves comprehensively and improves, and after 120 ℃ of oven dry, withstand voltage and folding strength reaches respectively 40MPa and more than the 8MPa; After 1450 ℃ of calcinings, withstand voltage and folding strength reaches respectively 60MPa and more than the 7MPa, line velocity of variation≤+ 0.25 after 1500 ℃ of burnings, and true specific gravity<2.33 illustrates that mould material burns that the line velocity of variation is little afterwards, do not have remaining quartz, all are converted into phosphorus quartz and cristobalite; Produce the silica fire resistant castable of fine and close, high-strength, low pore; The 2nd, the high-temperature behavior of the siliceous mould material of nanometer is significantly improved, and refractoriness reaches 1750-1770 ℃; Loading softening starting point (T 0.6) 1730 ℃, high temperature creep resistance (0.2MPa * 1550 ℃ * 50h)≤0.05%.The refractoriness of high-quality silica brick is 1690 ℃-1710 ℃, and the loading softening starting point is 1670 ℃-1690 ℃, compares with high-quality silica brick, and refractoriness, load softening point improve respectively more than 50 ℃, and this is the historical breakthrough that domestic and international siliceous refractory [material research obtains.The maximum characteristics of the siliceous mould material of nanometer are that high temperature creep resistance is best, and 1550 ℃ of insulations 50 hours, its high temperature creep resistance was at 2Kg/cm 2Under the loading, creep rate≤0.05% is compared with the pure corundum of mullite, pure corundum products, demonstrates more excellent high temperature creep resistance; The 3rd, high volume stability, heat-shock resistance, antistripping, anti-bursting property are very good, the most outstanding shortcoming of siliceous refractory [material is above-mentioned poor performance, in high temperature action, even in the baker process, be easy to occur severe crack, burst apart, burst etc. and damage phenomenon, even yet the siliceous mould material of nanometer is under high temperature more than 1450 ℃, directly use various damage problems also never occur, so these characteristics are laid a good foundation for its successful use in the hot industry stove.
Adopt the monolithic lining of Novel fire-resistant mould material to become the important directions that refractory materials develops, novel silicon refractory casting material of the present invention has the characteristics of monolithic lining and Unshaped Casting Refractories, in high-blast-temperature hot-blast stove, glass melter, pit kiln, obtain successful Application, all obtained special result of use.No. 2 medium blast furnaces are examined in the back of the body formula hotblast stove in Taiyuan Iron and Steel Co. company, adopt whole furnace roof and the top high temperature furnace wall of novel siliceous mould material cast, through repairing the use of stove section in one, have obtained successful experience; Also obtained good result of use in certain Steel Plant's outside combustion stove furnace roof use; In the high wind-warm syndrome pebble stove of Nanjing the 3rd Steel Plant, adopting the whole furnace roof big-wall of siliceous mould material cast and diameter that siliceous mould material is made is the siliceous ball of 50mm, make wind pushing temperature reach 1300 ℃, the furnace roof temperature of combustion reaches more than 1500 ℃, working conditions is very harsh, obtain high-blast-temperature hot-blast stove and used successful experience, particularly siliceous ball is than using corundum ball and High-Alumina ball to demonstrate better result of use, be mainly reflected in high temperature creep resistance, corundum ball and the high temperature deformation of high alumina stone ball are larger, the hot blast resistance strengthens, and hotblast stove can not normally be moved.So being the ideal material of ironmaking high-blast-temperature hot-blast stove, novel siliceous mould material selects, it is very big must satisfy and smelted iron the user demand of high wind-warm syndrome development, this siliceous mould material is used in the superstructure of large-scale float glass smelting kiln, domestic glass kiln, comprise the positions such as large arch, regenerator top, little furnace roof, partition wall, arch pin, bocca and top wall same obtained successful use experience.The aspect adopts this mould material to use as hot repair and sealing material at glass melter in addition, has obtained similarly outstanding result of use.
The preparation of nanocomposite oxide ceramic combining silica mould material of the present invention with uses successfully, significant to expansion mould material kind and use range.The integration of high-temperature industrial furnace, it is the inexorable trend of high temperature Thermal Equipment development, serialization and mechanize in construction process, have been realized, with compared with laying fireproof bricks in the past, realized saving time, the saving of labor, laborsaving, improve the rapid construction program of operating environment, from quality and aspect consideration in work-ing life, with have a large amount of brickwork joint lining-ups and compare, seamless integral lining has significant advantage, because a large amount of brickwork joint is the major cause that causes stove race wind gas leakage and too early damage, and the monolithic lining of pouring into a mould can make materials consumption significantly reduce, significantly improve work-ing life, also is simultaneously to improve resource utilization, the effective measures of environmental contamination reduction.This shows that the integral lining of development cast has important society, technology and economic implications, also is the main direction of refractory industry development.
Embodiment
Embodiment 1
List in the embodiment 1 of table 1 according to the present invention, adopt nanometer SiO 2, the combination of CaO complex sol suspension the silica fire resistant castable prescription, compound joined is dry mixed 1-2 minute in the forced mixer, then will through dispersion and dilution after the concentration made be the SiO of 53-58% 2The matter collosol suspension liquid directly joins in the mixing and blending machine, and the CaO in the compound and the mixing water of adding carry out hydration reaction, generates Ca (OH) 2Sol solutions mixes formation complex sol wedding agent with silicic acid sol suspension, mixed 5 minutes of rewetting in the wet mixing process, according to the actual water that needs the regimen condition to add 0-1% of wet mixing, is made SiO of the present invention 2And Ca (OH) 2Complex sol suspension combining silica refractory castable.The maximum characteristics of silica fire resistant castable are that high-temperature behavior, refractoriness and load softening point significantly improve, high temperature creep resistance is splendid, high volume is stable, heat-shock resistance and the anti-excellent property that bursts, and can form the silica fire resistant castable of nano-structured matrix, be applicable to smelt iron the high-blast-temperature hot-blast stove high-temperature zone use.The salient features of present embodiment mould material is listed in table 2.
Embodiment 2
List in the embodiment 2 of table 1 according to the present invention, adopt nanometer SiO 2, the combination of CaO complex sol suspension the silica fire resistant castable prescription, compound joined is dry mixed 1-2 minute in the forced mixer, then will through dispersion and dilution after the concentration made be the SiO of 53-58% 2The matter collosol suspension liquid directly joins in the mixing and blending machine, and the CaO in the compound and the mixing water of adding carry out hydration reaction, generates Ca (OH) 2Sol solutions mixes formation complex sol wedding agent with silicic acid sol suspension, mixed 5 minutes of rewetting in the wet mixing process, according to the actual water that needs the regimen condition to add 0-1% of wet mixing, is made SiO of the present invention 2And Ca (OH) 2Complex sol suspension combining silica refractory castable.The present embodiment silica fire resistant castable has the characteristics similar to embodiment 1, but mould material plasticity is very strong, therefore except adopting the vibration casting construction, can also adopt additive method to construct, and is applicable to use in glass melter superstructure and the coke oven.This enforcement mould material salient features list in table 2.
Table 1 embodiment of the invention 1, embodiment 2 nanometer SiO 2, CaO composite ceramics combining silica casting material formula
Table 2 embodiment of the invention 1, embodiment 2 nanometer SiO 2, CaO composite ceramics combining silica mould material salient features

Claims (3)

1. nanometer SiO 2, CaO composite ceramics combining silica refractory castable, the mass percent that it is characterized in that the refractory castable composition is comprised of the aggregate of 63-70% and 30-37% matrix powder and wedding agent system, with nanometer SiO 2, Ca (OH) 2Complex sol suspension is as nano-grade ceramic binding agent, wherein
Aggregate batching consists of: calcine siliceous grog or useless silica brick: 51-70%, wherein 10-15mm macrobead material is 25-35%; The 5-10mm particulate material is 7-15%; The 3-5mm particulate material is 5-12%; The 1-3mm particulate material is 5-12%; 0.1-1mm the fine particle material is 0-12%; Give birth to silica material fine particle material: 0.1-1mm, 0-12%;
Matrix powder and wedding agent system composition: nanometer SiO 2Collosol suspension liquid is in siccative amount 3~5%; Nanometer Ca (OH) 2Collosol suspension liquid is in the CaO dry measure: 1~3%; ≤ 10 μ m give birth to the silica ultrafine powder: 15~25%; ≤ 44 μ m calcined silica powder or useless silica brick powder: 5~15%; Silicon ash: 1.5~3%; White clay: 0~3%;
Hydrochloric acid or phosphoric acid add as peptizing agent and dispersion medium, and it adds quantity and is as the criterion with control pH value 2.5~3.0; Thinner and dispersion agent: be comprised of Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, tartrate, ethylene glycol, butanols, add, its add-on is 0.2~0.5%; Add water: 0~1%.
2. a kind of nanometer SiO according to claim 1 2, CaO composite ceramics combining silica refractory castable the preparation method, the preparation technology who it is characterized in that refractory castable is that the mould material that will prepare joins and is dry mixed 1-2 minute in the forced mixer, then will through dispersion and dilution after make the nanometer SiO that concentration is 53-58% 2Collosol suspension liquid directly joins in the mixing and blending machine, and the CaO in the compound and the mixing water of adding carry out hydration reaction, generates Ca (OH) 2Sol solutions is with nanometer SiO 2Collosol suspension liquid mixes formation complex sol wedding agent, and mixed 5 minutes of rewetting is in the wet mixing process, add the water of 0-1% according to wet mixing and need regimen condition, mould material after the wet mixing joins in the model of construction body through automatic feeding device, through vibrations, maintenance, baking, makes SiO again 2, CaO composite ceramics combining silica refractory castable.
3. a kind of nanometer SiO according to claim 1 2, CaO composite ceramics combining silica refractory castable the preparation method, it is characterized in that nanometer SiO 2The preparation of collosol suspension liquid is take the ultra-fine quartz of≤4 μ m, silica, silicon ash or water glass as starting raw material, adopts high-energy mechanochemistry method, the precipitator method, sol-gel method to make; Ca (OH) 2The preparation of collosol suspension liquid is as starting raw material take ultra-fine CaO powder, CaO is that the form with dry powder joins in the compound, add-on is 1-3%, and the CaO powder of high dispersive is to carry out hydration reaction with the water that adds compound in stirrer, generates the calcium hydroxide sol solutions; The calcium hydroxide sol solutions again with nanometer SiO 2Collosol suspension liquid mixes mutually, makes SiO 2, Ca (OH) 2Complex sol suspension wedding agent.
CN 201010165554 2010-05-07 2010-05-07 Nano-SiO2 and nano-CaO composite ceramic bond siliceous refractory castable and preparation method thereof Expired - Fee Related CN101875561B (en)

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