CN101875561A - 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 PDFInfo
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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 macroscopic structure 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
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
In the past 20 in the period of, the refractory technology main development tendency 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 bigger with developed country's gap aspect kind and structure and new varieties.Therefore, need exert to carry out the unsetting refractory castable of energy-saving high-performance, high quality high-performance acidity 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 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, the problem that has general character is to be matrix phase (the finely divided property material phase) problem of representative with the wedding agent system.This problem is the key problem in technology problem of unsetting quality product of decision and use.When this problem of research, the most noticeable nano ceramics wedding 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 ceramics wedding agent material is selected, analyze final phase composite of refractory castable and organizational structure thereof, the microstructure of microcosmic particularly, under concrete working 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 coadaptation mutually, for each disperse phase, all has the dispersed medium of oneself the best, it can be best to the full extent satisfies and the 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 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 elevated temperature heat construction equipment.The present invention nanometer SiO
2, CaO composite ceramics bonded silica fire resistant castable preparation with use successfully, to improving the ratio that the unsetting refractory castable of China accounts for the refractory materials ultimate production, to increase refractory castable new variety, and wedding agent systematic research of new generation and exploitation, all significant.Adopt nanometer SiO
2, CaO composite ceramics bonded silica fire resistant castable, it is acid refractory material typical case representative, occupies critical role in refractory materials principal item.Its preparation with uses successfully, to unshape refractory expansion kind, the increase overall productivity improves the quality, and impels the industrial development of China's refractory materials, and catches up with and surpasses 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 special outstanding high temperature resistance, refractoriness and load softening point, high temperature creep-resisting, anti-bursting property and aggressiveness and high durability
2, CaO composite ceramics combining silica refractory castable, to satisfy and to adapt to the growth requirement that modern iron-smelting blast furnace accessory high-blast-temperature hot-blast stove, glass melter superstructure, pit kiln etc. use; Silica fire resistant castable is typical case's representative of acid refractory on the other hand, increases the particularly acid or alkaline refractory castable of refractory castable principal item and enlarges the mould material use range, 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 the nano ceramics wedding 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 made up 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 is formed:
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 batching are formed:
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 made up 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 ceramics wedding 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 to be starting raw material with the ultra-fine quartz of≤4 μ m, silica, silicon ash or water glass, adopts high energy mechanical chemical method, the precipitator method, sol-gel method several different methods to make.In the high energy mechanical chemical 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, lattice distorts, also make a large amount of mechanical energy of powder internal reservoir and chemical energy simultaneously, therefore this course of processing in essence, can reduce mechanical force and chemical action, the mechanical activation method can influence mineral substance under the effect of mechanical force, carry out the variation of dynamics state, physical structure and chemical property when levigate, thus utilize mechanical energy participate in directly with initiating chamical reaction be a kind of new concept.Therefore, the high energy mechanical chemical 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 factory step by step, 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 promptly 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 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 made up of the colloidal particle of different dispersity and extent of hydration, under various factors influence, setting and harden takes place 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 to be starting raw material with superfine CaO powder, 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, mixes mutually 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 this mould material ideal mineralizer, 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 is when adopting inorganic phosphate as dispersion medium, and the phosphoric acid that add this moment still is a kind of fine aftereffect toughener, and the solation process is 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 the nano ceramics wedding 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 ceramics wedding agent is to realize it and condense and hardened owing to polymerization reaction take place with regard to its essence.With nanometer SiO
2Ceramic bond is an 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 grain composition such as silica use in a kind of 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 the needs of ensuring the quality of products, also be the demand that reduces cost and develop a circular economy.Adopt calcined silica or useless silica brick to give birth to the fine particle that silica is made 0.1-1mm in this batching as macrobead and middle particle, the employing of batching, to strengthen the caking power of mould material, can not the choose reasonable of siliceous mould material variable grain also simultaneously because of quartz transition works the mischief.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 important guaranteed conditions, 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 given birth to ground silica (≤10 μ m) and calcined silica powder (≤44 μ m) by superfine) etc. form.In addition, also add multiple effective admixture.Ceramic nanocomposites, it is meant that heterogeneous phase nanoparticle is evenly dispersed in formed matrix material in the matrix of ceramic oxide, it is meant 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.Be to adopt nanometer SiO aspect the nanometer material
2With CaO compound oxidate ceramic wedding agent, its matrix batching major technique characteristics are: the one, and the mould material that adopts the nanocomposite oxide ceramic wedding agent to make; The 2nd, the matrix powder 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 big, the chemical reactivity height, 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 is taken place, thermal structure react and the formation of nano-structured matrix provides important assurance; The 3rd, its structure, particularly microtexture are improved at all, every performance index are 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 guaranteed conditions of nano composite oxide combining silica mould material of the present invention, also is one of silica fire resistant castable major technique 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, mixing stirring, 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, mixes each later operation of stirring and 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 dried mixing 1-2 minute in the forced mixer, will be the SiO of 53-58% through the concentration of making after dispersion and the dilution then
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, rewetting mixed 5 minutes, 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 curing 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 is checked 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 of the nano composite ceramic of the excellent and uniform microstructure of obtained performance.This technology 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 homodisperse 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 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 refractory castable 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 has confirmed that the functional performance that nanotechnology and nano material had 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 nano composite ceramic bonded silica fire resistant castable is in the following areas: the one, and every performance index significantly improve comprehensively and improve, and after 120 ℃ of oven dry, withstand voltage and folding strength reaches 40MPa respectively and more than the 8MPa; After 1450 ℃ of calcinings, withstand voltage and folding strength reaches 60MPa respectively 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 afterwards the line velocity of variation is little, 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-resisting (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 high temperature creep-resisting the bests, and 1550 ℃ of insulations 50 hours, its high temperature creep-resisting was at 2Kg/cm
2Under the loading, creep rate≤0.05% is compared with the pure corundum of mullite, pure corundum products, demonstrates excellent more high temperature creep-resisting; 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 take place, so these characteristics are laid a good foundation for its successful use in the hot industry stove.
Adopt the monolithic lining of novel refractory castable 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 unsetting refractory castable, 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 the 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 matter ball and high alumina matter ball to demonstrate better result of use, be mainly reflected in high temperature creep-resisting, corundum ball and the high temperature deformation of high alumina stone ball are bigger, 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 positions such as big 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 outstanding result of use similarly.
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 hot industry kiln, it is the inexorable trend of elevated temperature heat construction equipment development, serialization and mechanize in construction process, have been realized, compared with building by laying bricks or stones with refractory brick 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, reduce the effective measures of environmental pollution.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, CaO complex sol suspension bonded silica fire resistant castable prescription, compound joined to do in the forced mixer mixed 1-2 minute, then will through dispersion and dilute 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, rewetting mixed 5 minutes, in the wet mixing process, according to the actual water that needs the regimen condition to add 0-1% of wet mixing, makes 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-resisting 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 that ironmaking high-blast-temperature hot-blast stove high-temperature zone uses.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, CaO complex sol suspension bonded silica fire resistant castable prescription, compound joined to do in the forced mixer mixed 1-2 minute, then will through dispersion and dilute 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, rewetting mixed 5 minutes, in the wet mixing process, according to the actual water that needs the regimen condition to add 0-1% of wet mixing, makes 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 that adopting the vibration casting construction, can also adopt additive method to construct, and is applicable in glass melter superstructure and the coke oven and uses.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 (6)
1. relate to a kind of nanometer SiO that uses
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, it is characterized in that mass percent that refractory castable batching forms is made up of the aggregate of 63-70% and 30-37% matrix powder and wedding agent system, aggregate batching consists of siliceous grog of calcining or useless silica brick: 51-70%, and 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 batching are formed: 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 2.0～3.0; Thinner and dispersion agent: be made up 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%.
2. use nanometer SiO for one kind
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, the preparation technology who it is characterized in that refractory castable is that the mould material that will prepare joins dried mixing 1-2 minute in the forced mixer, then will be through making the SiO that concentration is 53-58% after dispersion and the dilution
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, rewetting mixed 5 minutes, 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, again through vibrations, maintenance, baking, makes SiO of the present invention
2, CaO composite ceramics combining silica refractory castable; This employing wet processing is with SiO
2, Ca (OH)
2Complex sol suspension is as SiO
2, CaO composite ceramics wedding agent processing method, nanoparticle is fully disperseed in mould material, produce the nanometer refractory castable that nanoparticle is uniformly dispersed, reunites few, simultaneously, it has also solved the dust pollution question of nano material in preparation and production process; On the other hand, this SiO
2, Ca (OH)
2Complex sol suspension wedding agent has been realized in maintenance and drying course by the conversion process of colloidal sol to gel process, has also realized condensing and sclerosis of mould material simultaneously, so the SiO that this employing sol-gel method is produced
2, Ca (OH)
2The production technique that complex sol suspension wedding agent can make the nanometer mould material more rationally, more effective, the above, all being the important guaranteed conditions of nano composite ceramic combining silica refractory castable of the present invention, also is one of silica fire resistant castable major technique content of the present invention simultaneously.
3. according to claim 1,2 described nanometer SiO
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, it is characterized in that with ultra-fine quartz, silica, silicon ash or water glass be starting raw material, adopt several different methods such as high energy mechanical chemical method, the precipitator method, sol-gel method to make, with SiO
2, the CaO composite oxides are that the high density collosol suspension liquid of presoma is as SiO
2CaO composite ceramics wedding agent, and directly join in the compound, pass through in-situ synthesized reaction, the matrix powder is added and contains in the complex sol suspension of the precursor that can generate the nanophase component, in oven dry and heat-processed, finished by the conversion process of colloidal sol to gel, also realized simultaneously condensing and sclerosis of mould material, the characteristics of this synthetic method are to guarantee the homodisperse 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 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 silicon refractory casting material of this synthesis of nano structural matrix; Relevant raw-material selection, machining process, preparation method and working conditions etc. all are the important guaranteed conditions of nano composite ceramic combining silica refractory castable of the present invention, also are one of silica fire resistant castable major technique contents of the present invention simultaneously.
4. according to claim 1,2 described, nanometer SiO
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, it is characterized in that refractory aggregate accounts for 70% of total stuff amount in the refractory castable batching is formed, its material is selected and grain composition, structure, performance and use to mould material produce material impact and effect, select for use have different sorts, different qualities, the compound use in of the multiple aggregate of different grades with a kind of mould material, with the contradiction between balance kind, quality and the production cost; This system of aggregate is made of many kinds matrix material in the mould material, mould material of the present invention selects for use the siliceous grog of calcining or different types of aggregate such as useless silica brick, living silica material to constitute respectively, wherein adopt calcined silica or useless silica brick macrobead and middle particle as batching, adopt living silica to make the following fine particle of 0.1-1mm, to strengthen the caking power of mould material, can not the choose reasonable of siliceous mould material variable grain also simultaneously because of quartz transition works the mischief; Aspect the particles of aggregates grating, critical granularity is 15mm, macrobead content is many, the gradation scope is wide, be divided into five kinds of variable grains and batching in varing proportions, provide important guaranteed conditions, the material selection of relevant aggregate and grain composition etc. for producing high-compactness, low pore, high strength silica fire resistant castable, all being the important guaranteed conditions of nano composite ceramic combining silica refractory castable of the present invention, also is one of silica fire resistant castable major technique content of the present invention simultaneously.
5. according to claim 1,2,3 described, nanometer SiO
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, it is characterized in that with matrix powder, wedding agent and admixture being that the matrix phase of representative is formed and design, it is Ben Nami SiO
2, CaO composite ceramics combining silica refractory castable the technological core content, 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 this mould material; The wedding agent system adopts SiO
2, Ca (OH)
2Complex sol suspension is the composite ceramics wedding agent; Matrix powder system adopts superfine to give birth to ground silica (≤10 μ m), calcined silica powder or useless silica brick compositions such as (≤44 μ m), its matrix batching major technique characteristics are: the one, and the mould material that adopts the nanocomposite oxide ceramic wedding agent to make, phosphoric acid is the important component during this batching is formed, it is not only dispersion medium, still be the compound aftereffect enhanced of a kind of high-quality wedding agent, and the solation process is also had promoter action; The 2nd, the matrix powder is wide in variety, grade thin (≤44 μ m), some component is to adopt ultra-fine matrix powder, its grade is≤4 μ m, the nanometer grade powder that contains nano junction mixture system, therefore the particle of material is little, specific surface area is big, the chemical reactivity height, 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 is taken place, thermal structure react and the formation of nano-structured matrix provides important assurance; The 3rd, its structure, particularly microtexture are improved at all, every performance index are 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 guaranteed conditions of nano composite ceramic combining silica refractory castable of the present invention, also is one of silica fire resistant castable major technique content of the present invention simultaneously.
6. according to claim 1,2,3,5 described, nanometer SiO
2, CaO composite ceramics combining silica refractory castable and preparation method thereof, the use that it is characterized in that various admixtures is nanometer SiO of the present invention
2, CaO composite ceramics combining silica refractory castable important technology content, particularly nano-oxide pottery fire resistant pouring material does not have the use of various effective admixtures to make, and the admixture of nanometer refractory castable of the present invention is meant thinner, dispersion agent, peptizing agent and mineralizer etc.; Principal item has Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, tartrate, ethylene glycol, hydrochloric acid, industrial phosphoric acid etc. for thinner, dispersion agent, peptizing agent, it adds kind and adds wherein a kind of sometimes, sometimes be two or more composite additive, add-on is 0.2-0.5%, or add various acid or alkali reaches 2.0-3.0 with the pH value of regulating this sol system, make SiO of the present invention
2, Ca (OH)
2Complex sol suspension wedding agent; Mainly contain CaO for mineralizer, it is produced the silica fire resistant castable that does not contain remaining quartz and has vital role promoting that quartz transition is cristobalite, tridymite; Therefore the employing kind of various admixtures, adding quantity and working conditions all are the important guaranteed conditions of nano composite ceramic combining silica refractory castable of the present invention, also are one of silica fire resistant castable major technique contents of the present invention simultaneously.
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| CN103880439A (en) * | 2014-02-17 | 2014-06-25 | 武汉科技大学 | Preparation method of light-weight silica brick |
| CN104860656A (en) * | 2015-05-04 | 2015-08-26 | 安徽省亚欧陶瓷有限责任公司 | High fire resistance ceramic tile and production method thereof |
| CN105565850A (en) * | 2015-12-11 | 2016-05-11 | 河南工业大学 | Micropore light weight silica brick and preparation method thereof |
| CN107352988A (en) * | 2017-06-27 | 2017-11-17 | 苏州楚博生物技术有限公司 | A kind of superhigh intensity ceramic powder |
| CN110914216A (en) * | 2017-05-30 | 2020-03-24 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Method for preparing insulation material and insulation product for fire-resistant industry, corresponding insulation material and product and use |
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| CN102351547A (en) * | 2011-07-06 | 2012-02-15 | 马鞍山市泰来冶金炉料有限责任公司 | High strength high temperature resistance semi-lightweight high alumina castable and its preparation method |
| CN103588488A (en) * | 2013-07-24 | 2014-02-19 | 安徽铜冠有色金属（池州）有限责任公司九华冶炼厂 | Method for preventing through washing of lead chute by use of poured coating |
| CN103588488B (en) * | 2013-07-24 | 2016-05-25 | 安徽铜冠有色金属（池州）有限责任公司九华冶炼厂 | The anti-plumbous chute of cast coating is washed circulation method |
| CN103880439A (en) * | 2014-02-17 | 2014-06-25 | 武汉科技大学 | Preparation method of light-weight silica brick |
| CN104860656A (en) * | 2015-05-04 | 2015-08-26 | 安徽省亚欧陶瓷有限责任公司 | High fire resistance ceramic tile and production method thereof |
| CN105565850A (en) * | 2015-12-11 | 2016-05-11 | 河南工业大学 | Micropore light weight silica brick and preparation method thereof |
| CN110914216A (en) * | 2017-05-30 | 2020-03-24 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Method for preparing insulation material and insulation product for fire-resistant industry, corresponding insulation material and product and use |
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| CN107352988A (en) * | 2017-06-27 | 2017-11-17 | 苏州楚博生物技术有限公司 | A kind of superhigh intensity ceramic powder |
| CN112624568A (en) * | 2020-12-31 | 2021-04-09 | 凤阳常隆科技材料有限公司 | Glass kiln burdening production method |
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