CN115159966A - High-strength refractory castable and preparation method thereof - Google Patents
High-strength refractory castable and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength refractory castable and a preparation method thereof, wherein the refractory castable comprises, by weight, 50-70 parts of refractory aggregate, 20-40 parts of powder and 1-10 parts of binding agent; the refractory castable also comprises a water reducing agent, and the addition amount of the water reducing agent is 0.1-0.5wt% of the total weight of the refractory aggregate, the powder and the binding agent. According to the high-strength refractory castable and the preparation method thereof, provided by the invention, the polyvinyl alcohol modified polyurethane is introduced as the water reducing agent, so that the refractory castable with good fluidity and high strength is obtained.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a high-strength refractory castable and a preparation method thereof.
Background
The refractory material plays an indispensable role in national construction and national development due to the characteristics of ultrahigh refractoriness, namely higher than 1580 ℃, and stable physicochemical properties in the sintering process. With the increasing application fields of refractory materials, most refractory materials are applied in the high temperature field due to good physicochemical properties of the refractory materials. There are many types of refractory materials available, which can be generally divided into shaped and unshaped forms. As a novel refractory material, the refractory castable can be directly used without high-temperature heat treatment and is widely applied. Meanwhile, the refractory castable also has various performance advantages: the lining material has the advantages of long service life, more mechanized construction, very high construction efficiency and high construction kiln airtightness, and ensures that gas in the kiln is more sufficient, so the lining material is widely applied to the lining material of the thermotechnical kiln with a complex structure. So far, new varieties of refractory castable are continuously updated, and materials and production processes are continuously improved, so that the refractory castable is more and more effectively used, and the application field is more and more extensive.
At present, the refractory castable is composed of refractory aggregate, refractory powder, a bonding agent, an additive, water or other liquid materials, has high fluidity, can be molded by methods such as pouring, vibration, tamping and the like, can also be directly made into prefabricated parts, and can be hardened without heating. After the refractory castable is stirred by adding water, a water molecular layer can be formed on the surfaces of castable particles due to hydration, and in addition, association is generated among the particles due to anisotropic charges on the surfaces of the particles, so that a flocculation structure is formed in the castable. Therefore, a portion of the mixing water is entrapped in the particles and cannot participate in free flow and lubrication, thereby affecting the flowability of the casting material.
The water reducing agent is an anionic surfactant, and is added into the refractory castable, and is adsorbed on the surfaces of castable particles, so that the castable particles are charged with the same kind of charges to form an electrostatic repulsion effect, the castable particles are mutually dispersed, the flowability of the castable particles is improved, the unit water consumption is reduced, and the construction is facilitated. In addition, the structure of the water reducing agent has hydrophilic branched chains, and the hydrophilic branched chains extend in an aqueous solution, so that a hydrophilic three-dimensional adsorption layer with a certain thickness can be formed on the surfaces of the adsorbed castable particles. When the castable particles approach, the adsorption layers begin to overlap, steric hindrance effect is generated among the particles, the more the overlapping is, the larger the steric hindrance repulsive force is, the larger the obstruction to the condensation effect among the castable particles is, and the slump of the castable is kept good.
The existing common water reducing agents comprise polycarboxylic acids, phosphates, polyacrylates and the like, but the water reducing agents are sensitive to raw materials of the refractory castable and are easy to inactivate, so that the dispersing effect of the refractory castable is influenced. How to improve the activity of the water reducing agent so as to improve the dispersion and anticoagulation effects of the refractory castable and further improve the strength and other properties of the obtained refractory castable is a significant research subject in the field of refractory materials at present.
Disclosure of Invention
Based on the technical problems, the invention provides a high-strength refractory castable and a preparation method thereof, and finally obtains the refractory castable with good fluidity and high strength by introducing polyvinyl alcohol modified polyurethane as a water reducing agent.
The invention provides a high-strength refractory castable, which comprises, by weight, 50-70 parts of refractory aggregate, 20-40 parts of powder and 1-10 parts of a bonding agent;
wherein the refractory castable also comprises a water reducing agent, and the addition amount of the water reducing agent is 0.1-0.5wt% of the total weight of the refractory aggregate, the powder and the bonding agent.
Preferably, the water reducing agent is polyvinyl alcohol modified polyurethane, and is specifically obtained by performing condensation polymerization on a hydroxyl monomer comprising dimethylolbutyric acid and polyethylene glycol ether and an isocyanate monomer to obtain a polyurethane prepolymer, and then performing a crosslinking reaction on the polyurethane prepolymer and polyvinyl alcohol.
Preferably, the isocyanate monomer is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate;
preferably, the dimethylolbutyric acid is added in an amount of 5 to 15wt% of the polyethylene glycol ether;
preferably, the polyvinyl alcohol is added in an amount of 20-40wt% of the polyethylene glycol ether.
Preferably, the refractory aggregate is at least one of corundum, alumina or quartz;
preferably, the particle size of the refractory aggregate is 0.088-10mm.
Preferably, the powder material is at least one of corundum powder, alumina powder, silicon micropowder, chromium oxide powder or zirconium oxide powder.
Preferably, the binding agent is aluminate cement;
preferably, the alumina content of the aluminate cement is 50-80wt%.
Preferably, the refractory castable also comprises fibers, and the addition amount of the fibers is 0.1-2wt% of the total weight of the refractory aggregate, the powder and the binder.
Preferably, the fibers are organic fibers and/or inorganic fibers;
preferably, the organic fiber is at least one of polypropylene explosion-proof fiber, carbon fiber or graphite fiber, and the inorganic fiber is at least one of stainless steel fiber, aluminum silicate fiber, glass fiber or asbestos fiber.
The invention also provides a preparation method of the high-strength refractory castable, which comprises the following steps: and dry-mixing the refractory aggregate, the powder and the binding agent in a stirrer according to the formula amount, adding a water reducing agent and water for wet mixing, pouring the obtained mixture into a mold, vibrating, demolding and maintaining to obtain the high-strength refractory castable.
Compared with the prior art, the invention provides a high-strength refractory castable, which is characterized in that polyvinyl alcohol modified polyurethane is selected as a water reducing agent, dimethylolbutyric acid, hydroxyl monomers of polyglycol ether and isocyanate monomers are subjected to polycondensation to form long-chain polyurethane, and the long-chain polyurethane has carboxylic acid groups and can be subsequently crosslinked with polyvinyl alcohol, so that the obtained polyvinyl alcohol modified polyurethane has rich polar groups and can be effectively adsorbed on the surface of castable particles, the dispersibility of the castable particles in water is greatly enhanced, the structure is stable, the flocculation tendency of the water reducing agent is reduced, the obtained refractory castable has good flowing property, and the mechanical property and the fire resistance of the obtained refractory castable under a high-temperature condition are more excellent.
Detailed Description
The present invention will be described in detail with reference to specific examples, but these examples should be explicitly mentioned for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A high-strength refractory castable comprises the following components in parts by weight: 45 parts of 1-6mm tabular corundum, 15 parts of 0.088-1mm fused white corundum, 15 parts of fused white corundum powder less than 0.088mm, 12 parts of alumina powder, 3 parts of silicon micropowder, 4 parts of aluminate cement, 1 part of stainless steel fiber, 1 part of aluminum silicate fiber, 0.2 part of water reducing agent and 3 parts of water;
the water reducing agent is polyvinyl alcohol modified polyurethane and is prepared by the following method: adding polyglycol ether (molecular weight is 350) and toluene diisocyanate into a reaction kettle according to the proportion of NCO/OH =1.5, uniformly mixing, adding dimethylol butyric acid (8 wt% of the mass of polyglycol ether), heating to 60 ℃, adding dibutyltin dilaurate (the addition amount is 2wt% of the mass of polyglycol ether), heating to 85 ℃, and stirring for reacting for 3 hours to obtain a polyurethane prepolymer; and (2) cooling to 40 ℃, adding acetone to dilute the obtained polyurethane prepolymer, adding a polyvinyl alcohol aqueous solution (PVA 1799, wherein the addition amount of the polyvinyl alcohol is 30wt% of the mass of the polyethylene glycol ether, and the content of the aqueous solution is 15 wt%), heating to 90 ℃, and then continuously stirring for reaction for 2 hours to obtain polyvinyl alcohol modified polyurethane, namely the water reducing agent.
The preparation method of the high-strength refractory castable specifically comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fiber are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould for uniform vibration, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the mixture is dried for 24 hours at 110 ℃, and the sample to be tested is obtained after heat preservation and heat treatment for 3 hours at 1100 ℃ under the air condition.
Example 2
A high-strength refractory castable comprises the following components in parts by weight: 40 parts of 1-6mm tabular corundum, 10 parts of 0.088-1mm fused white corundum, 20 parts of fused white corundum powder less than 0.088mm, 10 parts of alumina powder, 4 parts of silica powder, 6 parts of zirconia powder, 4 parts of aluminate cement, 1 part of stainless steel fiber, 0.2 part of water reducing agent and 3 parts of water;
the water reducing agent is polyvinyl alcohol modified polyurethane and is prepared by the following method: adding polyglycol ether (molecular weight is 350) and toluene diisocyanate into a reaction kettle according to the proportion of NCO/OH =1.5, uniformly mixing, adding dimethylol butyric acid (8 wt% of the mass of polyglycol ether), heating to 60 ℃, adding dibutyltin dilaurate (the addition amount is 2wt% of the mass of polyglycol ether), heating to 85 ℃, and stirring for reacting for 3 hours to obtain a polyurethane prepolymer; and (2) cooling to 40 ℃, adding acetone to dilute the obtained polyurethane prepolymer, adding a polyvinyl alcohol aqueous solution (PVA 1799, wherein the addition amount of the polyvinyl alcohol is 30wt% of the mass of the polyethylene glycol ether, and the content of the aqueous solution is 15 wt%), heating to 90 ℃, and then continuously stirring for reaction for 2 hours to obtain polyvinyl alcohol modified polyurethane, namely the water reducing agent.
The preparation method of the high-strength refractory castable specifically comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fiber are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould for uniform vibration, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the mixture is dried for 24 hours at 110 ℃, and the sample to be tested is obtained after heat preservation and heat treatment for 3 hours at 1100 ℃ under the air condition.
Example 3
A high-strength refractory castable comprises the following components in parts by weight: 45 parts of 1-6mm tabular corundum, 25 parts of 0.088-1mm fused white corundum, 10 parts of fused white corundum powder less than 0.088mm, 8 parts of alumina powder, 2 parts of silicon micropowder, 3 parts of aluminate cement, 1 part of stainless steel fiber, 2 parts of aluminum silicate fiber, 0.2 part of water reducing agent and 3 parts of water;
the water reducing agent is polyvinyl alcohol modified polyurethane and is prepared by the following method: adding polyglycol ether (molecular weight is 350) and toluene diisocyanate into a reaction kettle according to the proportion of NCO/OH =1.5, uniformly mixing, adding dimethylol butyric acid (8 wt% of the mass of polyglycol ether), heating to 60 ℃, adding dibutyltin dilaurate (the addition amount is 2wt% of the mass of polyglycol ether), heating to 85 ℃, and stirring for reacting for 3 hours to obtain a polyurethane prepolymer; cooling to 40 ℃, adding acetone to dilute the polyurethane prepolymer, adding a polyvinyl alcohol aqueous solution (PVA 1799, the addition amount of the polyvinyl alcohol is 30wt% of the mass of the polyethylene glycol ether, and the content of the aqueous solution is 15 wt%), heating to 90 ℃, and then continuously stirring for reaction for 2 hours to obtain polyvinyl alcohol modified polyurethane, namely the water reducer.
The preparation method of the high-strength refractory castable comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fiber are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould for uniform vibration, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the mixture is dried for 24 hours at 110 ℃, and the sample to be tested is obtained after heat preservation and heat treatment for 3 hours at 1100 ℃ under the air condition.
Example 4
A high-strength refractory castable comprises the following components in parts by weight: 45 parts of 1-6mm tabular corundum, 15 parts of 0.088-1mm fused white corundum, 15 parts of fused white corundum powder less than 0.088mm, 12 parts of alumina powder, 3 parts of silicon micropowder, 4 parts of aluminate cement, 1 part of stainless steel fiber, 1 part of aluminum silicate fiber, 0.2 part of water reducing agent and 3 parts of water;
the water reducing agent is polyvinyl alcohol modified polyurethane and is prepared by the following method: adding polyglycol ether (molecular weight is 350) and isophorone diisocyanate into a reaction kettle according to the proportion of NCO/OH =1.5, uniformly mixing, adding dimethylolbutyric acid (5 wt% of the mass of the polyglycol ether), heating to 60 ℃, adding dibutyltin dilaurate (the addition is 2wt% of the mass of the polyglycol ether), heating to 85 ℃, and stirring for reacting for 3 hours to obtain a polyurethane prepolymer; and (2) cooling to 40 ℃, adding acetone to dilute the obtained polyurethane prepolymer, adding a polyvinyl alcohol aqueous solution (PVA 1799, wherein the addition amount of the polyvinyl alcohol is 20wt% of the mass of the polyethylene glycol ether, and the content of the aqueous solution is 15 wt%), heating to 90 ℃, and then continuously stirring for reaction for 2 hours to obtain polyvinyl alcohol modified polyurethane, namely the water reducing agent.
The preparation method of the high-strength refractory castable comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fiber are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould for uniform vibration, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the mixture is dried for 24 hours at 110 ℃, and the sample to be tested is obtained after heat preservation and heat treatment for 3 hours at 1100 ℃ under the air condition.
Comparative example 1
A high-strength refractory castable comprises the following components in parts by weight: 45 parts of 1-6mm tabular corundum, 15 parts of 0.088-1mm fused white corundum, 15 parts of fused white corundum powder less than 0.088mm, 12 parts of alumina powder, 3 parts of silica micropowder, 4 parts of aluminate cement, 1 part of stainless steel fiber, 1 part of aluminum silicate fiber, 0.2 part of water reducing agent and 3 parts of water; wherein the water reducing agent is sodium tripolyphosphate.
The preparation method of the high-strength refractory castable comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fiber are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould for uniform vibration, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the mixture is dried for 24 hours at 110 ℃, and the sample to be tested is obtained after heat preservation and heat treatment for 3 hours at 1100 ℃ under the air condition.
Comparative example 2
A high-strength refractory castable comprises the following components in parts by weight: 45 parts of 1-6mm tabular corundum, 15 parts of 0.088-1mm fused white corundum, 15 parts of fused white corundum powder less than 0.088mm, 12 parts of alumina powder, 3 parts of silica micropowder, 4 parts of aluminate cement, 1 part of stainless steel fiber, 1 part of aluminum silicate fiber, 0.2 part of water reducing agent and 3 parts of water;
the water reducing agent is polyurethane and is prepared by the following method: adding polyglycol ether (molecular weight is 350) and toluene diisocyanate into a reaction kettle according to the proportion of NCO/OH =1.5, uniformly mixing, adding dimethylolbutyric acid (8 wt% of the mass of the polyglycol ether), heating to 60 ℃, adding dibutyltin dilaurate (the addition is 2wt% of the mass of the polyglycol ether), heating to 85 ℃, and stirring for reacting for 3 hours to obtain a polyurethane prepolymer, namely the water reducer.
The preparation method of the high-strength refractory castable comprises the following steps: according to the proportion, after the raw materials are weighed, the raw materials corresponding to the refractory aggregate, the powder, the bonding agent and the fibers are added into a stirrer for dry mixing, then the water reducing agent and the water are added for wet mixing, the obtained mixture is poured into a 40mm x 160mm mould and then uniformly vibrated, the mould is removed after natural curing is carried out for 24 hours at room temperature, then the drying is carried out for 24 hours at the temperature of 110 ℃, and the heat preservation and heat treatment are carried out for 3 hours under the air condition of 1100 ℃ to obtain the sample to be tested.
And (3) experimental test:
the samples obtained in the examples and comparative examples were measured for flexural strength according to GB/T3001-2007 standard, and the results are shown in Table 1.
Table 1 effect of performance test of high-strength refractory castable obtained in examples and comparative examples
As can be seen from the above table, in the refractory castable, the water reducer of the invention has better fluidity, flexural strength and compressive strength than other water reducers applied to the system.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. The high-strength refractory castable is characterized by comprising, by weight, 50-70 parts of refractory aggregate, 20-40 parts of powder and 1-10 parts of binding agent;
wherein the refractory castable also comprises a water reducing agent, and the addition amount of the water reducing agent is 0.1-0.5wt% of the total weight of the refractory aggregate, the powder and the bonding agent.
2. The high-strength refractory castable according to claim 1, wherein the water reducing agent is polyvinyl alcohol modified polyurethane, which is obtained by polycondensing hydroxyl monomers including dimethylolbutyric acid and polyglycol ether and isocyanate monomers to obtain polyurethane prepolymer and then performing a cross-linking reaction with polyvinyl alcohol.
3. The high-strength refractory castable according to claim 2, wherein the isocyanate monomer is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate;
preferably, the dimethylolbutyric acid is added in an amount of 5 to 15wt% of the polyethylene glycol ether;
preferably, the polyvinyl alcohol is added in an amount of 20-40wt% of the polyethylene glycol ether.
4. A high strength refractory castable material as claimed in any one of claims 1 to 3, wherein said refractory aggregate is at least one of corundum, alumina or quartz;
preferably, the particle size of the refractory aggregate is 0.088-10mm.
5. The high-strength castable refractory according to any one of claims 1 to 4, wherein the powder material is at least one of corundum powder, alumina powder, silica micropowder, chromium oxide powder or zirconium oxide powder.
6. The high-strength refractory castable material according to any one of claims 1-5, wherein the binder is aluminate cement;
preferably, the alumina content of the aluminate cement is 50-80wt%.
7. A high strength refractory castable material according to any one of claims 1 to 6, further including fibres, the fibres being added in an amount of 0.1 to 2% by weight of the sum of the weight of refractory aggregate, powder and binder.
8. The high strength refractory castable material according to claim 7, wherein the fibres are organic fibres and/or inorganic fibres;
preferably, the organic fiber is at least one of polypropylene explosion-proof fiber, carbon fiber or graphite fiber, and the inorganic fiber is at least one of stainless steel fiber, aluminum silicate fiber, glass fiber or asbestos fiber.
9. The preparation method of the high-strength refractory castable according to any one of claims 1 to 8, characterized in that the refractory aggregate, the powder and the binding agent are dry-mixed in a mixer according to the formula ratio, then the water reducing agent and water are added for wet mixing, the obtained mixture is poured into a mold, and after vibration, demolding and maintenance, the high-strength refractory castable is obtained.
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| JPH09100172A (en) * | 1995-10-02 | 1997-04-15 | Kurosaki Refract Co Ltd | Basic castable refractory |
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