CN113372063B - Heat-resistant concrete and preparation method thereof - Google Patents
Heat-resistant concrete and preparation method thereof Download PDFInfo
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- CN113372063B CN113372063B CN202110699919.4A CN202110699919A CN113372063B CN 113372063 B CN113372063 B CN 113372063B CN 202110699919 A CN202110699919 A CN 202110699919A CN 113372063 B CN113372063 B CN 113372063B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/46—Rock wool ; Ceramic or silicate fibres
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/12—Multiple coating or impregnating
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application relates to the field of building materials, and particularly discloses heat-resistant concrete and a preparation method thereof. The heat-resistant concrete comprises the following components in parts by weight: 220 parts of Portland cement, 520 parts of basalt broken stone, 370 parts of sand, 70-90 parts of admixture, 30-40 parts of filler, 15-20 parts of modified copper-plated ceramic fiber, 6-8 parts of water reducer and 80-100 parts of water; the modified copper-plated ceramic fiber is obtained by respectively carrying out chemical copper plating and silicon dioxide layer coating on ceramic fiber; the filler is formed by mixing montmorillonite powder, expandable graphite and sepiolite porous ceramic in a weight ratio of 1-3:1-3: 5. The heat-resistant concrete can be used for buildings which are in high-temperature conditions for a long time, and has the advantages of high compressive strength and good heat resistance.
Description
Technical Field
The application relates to the field of building materials, in particular to heat-resistant concrete and a preparation method thereof.
Background
The common concrete is artificial stone which is prepared by taking cement as a main cementing material, taking sand and stone as aggregates, adding a chemical additive and a mineral admixture if necessary, mixing the materials according to a proper proportion, adding water, uniformly stirring, densely molding, curing and hardening. The common concrete generally has a requirement only for pressure resistance, and when a building is in a high-temperature environment (for example, a blast furnace and a coke oven which are cast by concrete can generate a temperature of 200-. The main reasons for the common concrete not resisting high temperature are: calcium hydroxide and limestone coarse aggregate in concrete are decomposed at high temperature, quartz sand is subjected to crystal form transformation at high temperature and undergoes volume expansion, and moreover, the cement stone and the aggregate have different thermal expansion coefficients, so that the problems of increased cracks and reduced strength of common concrete at high temperature are caused, and the service life of a building is seriously influenced.
At present, the heat-resistant concrete is usually prepared by taking aluminate cement as a cementing material, taking high-alumina bricks, crushed magnesia bricks and the like as aggregates and adding a chemical additive and a mineral admixture; the concrete has good heat resistance, but due to the large hydration heat of aluminate cement, the tendency of reducing the long-term strength and other properties, and the low strength of high-alumina bricks and broken magnesia bricks, the compressive strength of the heat-resistant concrete is only C20-C40 generally, so that the concrete cannot be applied to structures bearing for a long time and projects in high-temperature and high-humidity environments, and the application range of the concrete is limited. Therefore, there is a need for a heat-resistant concrete having a higher strength.
Disclosure of Invention
In order to improve the heat resistance and the compressive strength of concrete, the application provides heat-resistant concrete.
In a first aspect, the present application provides a heat-resistant concrete, which adopts the following technical scheme:
the heat-resistant concrete comprises the following components in parts by weight:
220 parts of Portland cement, 520 parts of basalt broken stone, 370 parts of sand, 70-90 parts of admixture, 30-40 parts of filler, 15-20 parts of modified copper-plated ceramic fiber, 6-8 parts of water reducer and 80-100 parts of water;
the modified copper-plated ceramic fiber is obtained by respectively carrying out chemical copper plating and silicon dioxide layer coating on ceramic fiber;
the filler is formed by mixing montmorillonite powder, expandable graphite and sepiolite porous ceramic in a weight ratio of 1-3:1-3: 5.
By adopting the technical scheme, the ceramic fiber is a fibrous light refractory material, has the advantages of light weight, high temperature resistance, high thermal stability and low thermal conductivity, can resist the temperature of more than 1000 ℃, and has better heat resistance compared with other heat-resistant fibers (such as polymer fibers, glass fibers and basalt fibers). A copper plating layer with higher density can be formed on the ceramic fiber by an electroless copper plating method, so that on one hand, the strength and heat resistance of the ceramic fiber can be increased, and the strength and heat resistance of concrete can be increased; on the other hand, the density of the ceramic fiber can be properly increased, so that the ceramic fiber can be uniformly dispersed in the concrete mixture, the segregation phenomenon caused by the descending of coarse aggregate and the ascending of light ceramic fiber in the concrete mixture is reduced, and the stability of the hardened concrete structure is favorably improved.
After chemical copper plating, a metal copper plating layer can be formed on the ceramic fiber, and after the metal copper plating layer is coated with a silicon dioxide layer, on one hand, the bonding force between the copper plating layer and the ceramic fiber can be improved, and on the other hand, the formed silicon dioxide layer can improve the interface bonding strength between the modified copper-plated ceramic fiber and a cement matrix.
The filler consists of sepiolite porous ceramic, montmorillonite powder and expandable graphite, the sepiolite porous ceramic and the montmorillonite powder have good adsorbability, and the expandable graphite has the function of heat absorption and expansion; the filler is added to play two roles: when the concrete is in a high-temperature condition, the filler can absorb heat and expand properly, and can fill cracks when the concrete cracks, so that the compactness of the concrete is improved, and the reduction of the strength of the concrete under the high-temperature condition is reduced; when the modified copper-plated ceramic fiber is matched with the filler, the modified copper-plated ceramic fiber is distributed in a three-dimensional disorderly manner to form a three-dimensional network structure, and when the filler absorbs heat to expand, the modified copper-plated ceramic fiber can limit the excessive expansion of the filler and prevent the concrete from generating cracks due to the excessive expansion of the filler; secondly, when modified copper facing ceramic fiber and filler cooperate, utilize the adsorptivity and the mobility of filler, at the in-process of mixing with the concrete mixture, the filler can drive its and other raw materials misce bene in the concrete mixture to improve the homogeneity of modified copper facing ceramic fiber dispersion in the concrete mixture, increase the workability of concrete mixture, improve the cohesion of modified copper facing ceramic fiber and concrete mixture raw materials, reduce the stress concentration point of concrete, thereby improve the compressive strength of concrete.
The Portland cement has high strength and the basalt broken stone has good heat resistance, and the concrete formed by hardening and molding the concrete mixture prepared from the Portland cement, the basalt broken stone, the sand, the admixture, the filler, the modified metal-based ceramic fiber, the additive and a certain amount of water has high compressive strength and heat resistance.
Preferably, the modified copper-plated ceramic fiber is prepared by the following method:
firstly, cleaning and drying ceramic fibers to obtain cleaned ceramic fibers;
soaking the cleaned ceramic fiber in concentrated nitric acid, and standing at 50-60 ℃ for 30-40min to obtain pretreated ceramic fiber; cleaning the pretreated ceramic to be neutral, and drying to obtain acid-treated ceramic fiber;
thirdly, soaking the acid-treated ceramic fiber in chemical copper plating solution, performing ultrasonic dispersion, and then keeping the temperature and standing for 3-5 hours at the temperature of 50-60 ℃ to obtain pre-plated copper ceramic fiber;
cleaning the pre-plated copper ceramic fiber to be neutral, and sintering at the temperature of 700-800 ℃ for 10-12h to obtain the copper-plated ceramic fiber;
soaking the copper-plated ceramic fiber in a silicon dioxide modification solution, stirring for 1-2h at the temperature of 50-60 ℃, then adding an alkaline agent to adjust the pH to 8-9, standing for reaction for 2-4h at the temperature of 80-90 ℃, and aging, washing and drying to obtain the modified copper-plated ceramic fiber;
the silicon dioxide modified solution is prepared by mixing an ethanol solution of a silane coupling agent, an aqueous solution of a surfactant and tetraethoxysilane in a weight ratio of 8-10:4-6: 1.
By adopting the technical scheme, the ceramic fiber is subjected to surface etching treatment by using concentrated nitric acid, so that the surface roughness of the ceramic fiber can be improved, and the interface bonding force of the copper-plated layer and the ceramic fiber is improved through a mechanical interlocking structure formed between the copper-plated layer and the ceramic fiber; however, the transverse tensile strength of the interface formed by the physical bonding method is not very high, so the application further coats the silicon dioxide layer on the copper-plated ceramic fiber to improve the interface bonding force between the copper-plated layer and the ceramic fiber.
Preferably, the ethanol solution of the silane coupling agent is formed by mixing 1:50 parts by weight of octadecyl trimethoxy silane and 50% by volume of ethanol aqueous solution;
the aqueous solution of the surfactant is prepared by mixing cetyl trimethyl ammonium bromide and water in a weight ratio of 1: 100.
By adopting the technical scheme, the formation of the silicon dioxide layer can be promoted by adopting the octadecyl trimethoxy silane and the hexadecyl trimethyl ammonium bromide, and the binding force between the silicon dioxide layer and the copper plating layer is improved.
Preferably, the sepiolite porous ceramic is prepared by the following method: uniformly mixing 30-40 parts of sepiolite fibers, 0.15-0.2 part of isobutylene maleic anhydride copolymer, 0.06-0.1 part of polyvinylpyrrolidone and 100 parts of water in parts by weight to obtain mixed slurry; pressing and molding the mixed slurry to obtain a ceramic blank; and drying the ceramic blank, heating to the temperature of 700-800 ℃, then carrying out heat preservation sintering for 2-3h, and cooling to the room temperature to obtain the sepiolite porous ceramic.
By adopting the technical scheme, the sepiolite porous ceramic has good heat resistance and porous adsorption, and the sepiolite porous ceramic is matched with montmorillonite powder and expandable graphite, so that the filler has the advantages of good heat resistance, strong adsorption and good fluidity.
Preferably, the pressure of the mixed slurry for press molding is 250-270MPa, and the molding time is 4-5 min.
By adopting the technical scheme, the pressing forming is carried out at normal temperature under the pressure of 250-270MPa, the forming process is simple, and the preparation is easy.
Preferably, the admixture is formed by mixing fly ash and mineral powder in a weight ratio of 2: 1.
By adopting the technical scheme, the fly ash can improve the fluidity, cohesiveness and water-retaining property of the concrete mixture; the mineral powder has good chemical activity, and after being mixed with water, the mineral powder generates secondary hydration reaction, reduces communication holes of concrete and improves the compactness of the concrete; the strength of the concrete can be improved by adding the fly ash and the mineral powder.
Preferably, the fly ash is class F II fly ash, and the mineral powder is class S95 mineral powder.
By adopting the technical scheme, the class F II fly ash and the class S95 mineral powder have better performance and are beneficial to improving the strength of concrete.
Preferably, the particle size of the basalt broken stone is 5-20mm continuous gradation, the mud content is less than 0.5%, and the content of needle-shaped particles is less than or equal to 5%.
By adopting the technical scheme, the crushed stones with 5-20mm continuous gradation are used as coarse aggregates, and the crushed stones with different particle sizes can be stacked to form a densely filled lap joint framework, so that the porosity can be reduced, and the strength of the concrete is improved.
Preferably, the sand is the sand in the area II, the particle diameter is 0.5-0.25mm, and the mud content is less than 1.0%.
Through adopting above-mentioned technical scheme, the gradation of II district middlings is better, and its granule is more mellow and smooth, particle shape is good, and II district middlings can be filled in the gap between cement and the coarse aggregate, reduces the space of concrete to improve the concrete strength.
In a second aspect, the present application provides a method for preparing heat-resistant concrete, which adopts the following technical scheme:
a preparation method of heat-resistant concrete comprises the following steps: according to the proportion, firstly, uniformly mixing the modified copper-plated ceramic fiber and the filler to obtain a premix; then adding portland cement, basalt broken stone, sand, an admixture, a water reducing agent and water into the premix, and uniformly mixing according to a proportion.
By adopting the technical scheme, the modified copper-plated ceramic fiber is mixed with the filler, so that the adsorption efficiency of the filler on the modified copper-plated ceramic fiber can be increased, and the matching effect of the filler and the modified copper-plated ceramic fiber can be improved.
In summary, the present application has the following beneficial effects:
1. because the application adopts the matching of the filler and the modified copper-plated ceramic fiber, the effect of obviously improving the compressive strength and the heat resistance of the concrete is obtained. The modified copper-plated ceramic fiber has the advantages of good heat resistance and high strength, and the filler has the advantages of good heat resistance, strong adsorbability and good fluidity.
2. According to the method, the filler and the modified copper-plated ceramic fiber are mixed in advance, so that the effect of improving the adsorption efficiency of the filler on the modified copper-plated ceramic fiber is achieved.
Detailed Description
In order to solve the problem that the compressive strength and the heat resistance of the heat-resistant concrete in the prior art cannot be considered at the same time, the applicant adds the raw materials such as the filler, the modified copper-plated ceramic fiber and the like into the formula, so that the obtained heat-resistant concrete has the strength of more than 50Mpa after being burnt at the temperature of 700 ℃, and has good performance stability. The applicant finds that the ceramic fiber has good heat resistance and light weight density, and can improve the heat resistance of concrete when being added into the concrete, but because the raw materials of the concrete generally have heavier weight, and the light weight of the common ceramic fiber can cause the poor dispersibility of the common ceramic fiber in concrete mixtures, the applicant improves the strength and the heat resistance of the concrete and improves the workability of the concrete mixtures by modifying the common ceramic fiber and adding the raw materials such as fillers.
The present application will be described in further detail with reference to examples.
Preparation example of electroless copper plating solution
The starting materials in the preparation examples are all commercially available.
The chemical copper plating solution is prepared by the following method: 20kg of copper sulfate pentahydrate, 45kg of disodium ethylene diamine tetraacetate, 12kg of potassium sodium tartrate, 12kg of formaldehyde and 13kg of 2, 2' -bipyridyl are mixed and added with ammonia water, and the pH value is adjusted to 12, so as to obtain the chemical copper plating solution.
Preparation example of silica-modified liquid
The raw materials in the following preparation examples are commercially available, wherein the tetraethoxysilane is selected from industrial-grade tetraethoxysilane with a silicon dioxide content of 40% provided by Shandong Shuo chemical Co., Ltd.
Preparation example 1 of silica-modified liquid
The silicon dioxide modified solution is prepared by the following method: mixing octadecyl trimethoxy silane and 50% ethanol water solution according to the weight ratio of 1:50 to prepare ethanol solution of silane coupling agent;
mixing cetyl trimethyl ammonium bromide and water according to the proportion of 1:100 to prepare an aqueous solution of a surfactant;
and uniformly mixing 8kg of ethanol solution of silane coupling agent, 4kg of aqueous solution of surfactant and 1kg of ethyl orthosilicate to obtain the silicon dioxide modified solution.
Preparation example 2 of silica-modified solution
This production example differs from production example 1 of the silica-modified liquid in that the amount of the ethanol solution of the silane coupling agent was 9kg and the amount of the aqueous solution of the surfactant was 5 kg.
Preparation example 3 of silica-modified solution
This production example differs from production example 1 of the silica-modified liquid in that the amount of the ethanol solution of the silane coupling agent was 10kg and the amount of the aqueous solution of the surfactant was 6 kg.
Examples of production of modified copper-plated ceramic fiber
The electroless copper plating solution in the following preparation examples was obtained from the preparation examples of electroless copper plating solutions; the length of the ceramic fiber is 1-1.2mm, and the fineness is 2.8-3D.
Preparation example 1 of modified copper-plated ceramic fiber
The modified copper-plated ceramic fiber is prepared by the following method: firstly, cleaning ceramic fibers with deionized water, and drying at the temperature of 80 ℃ for 1h to obtain the cleaned ceramic fibers;
soaking the cleaned ceramic fiber in concentrated nitric acid with the mass fraction of 68 wt% which is 10 times of the weight of the ceramic fiber, and standing for 40min at the temperature of 50 ℃ to obtain pretreated ceramic fiber; cleaning the pretreated ceramic with deionized water to neutrality, and drying at 80 ℃ for 1h to obtain acid-treated ceramic fiber;
thirdly, soaking the acid-treated ceramic fiber in chemical copper plating solution which is 5 times of the weight of the acid-treated ceramic fiber, performing ultrasonic dispersion for 10min under the condition that the ultrasonic frequency is 60KHz, and standing for 5h at the temperature of 50 ℃ to obtain pre-plated copper ceramic fiber;
fourthly, cleaning the pre-plated copper ceramic fiber with deionized water to be neutral, and then sintering the pre-plated copper ceramic fiber at the temperature of 700 ℃ for 12 hours to obtain the copper-plated ceramic fiber;
soaking the copper-plated ceramic fiber in a silicon dioxide modification solution (selected from preparation example 1 of the silicon dioxide modification solution) with the weight 5 times of the copper-plated ceramic fiber, keeping the temperature and stirring for 2 hours at the temperature of 50 ℃, then adding ammonia water to adjust the pH to 8, keeping the temperature and standing for reaction for 4 hours at the temperature of 80 ℃, aging for 24 hours, taking out, cleaning with absolute ethyl alcohol, and drying for 1 hour at the temperature of 105 ℃ to obtain the modified copper-plated ceramic fiber.
Preparation example 2 of modified copper-plated ceramic fiber
The modified copper-plated ceramic fiber is prepared by the following method: firstly, cleaning ceramic fibers with deionized water, and drying at the temperature of 80 ℃ for 1h to obtain the cleaned ceramic fibers;
soaking the cleaned ceramic fiber in concentrated nitric acid with the mass fraction of 68 wt% which is 10 times of the weight of the ceramic fiber, and standing for 35min at the temperature of 55 ℃ to obtain pretreated ceramic fiber; cleaning the pretreated ceramic with deionized water to neutrality, and drying at 80 ℃ for 1h to obtain acid-treated ceramic fiber;
thirdly, soaking the acid-treated ceramic fiber in chemical copper plating solution which is 5 times of the weight of the acid-treated ceramic fiber, performing ultrasonic dispersion for 10min under the condition that the ultrasonic frequency is 60KHz, and standing for 4h at the temperature of 55 ℃ to obtain pre-plated copper ceramic fiber;
fourthly, cleaning the pre-plated copper ceramic fiber with deionized water to be neutral, and then sintering at the temperature of 750 ℃ for 11 hours to obtain the copper-plated ceramic fiber;
soaking the copper-plated ceramic fiber in a silicon dioxide modification solution (selected from preparation example 2 of the silicon dioxide modification solution) with the weight 5 times of the copper-plated ceramic fiber, preserving heat and stirring for 1.5 hours at the temperature of 55 ℃, then adding ammonia water to adjust the pH to 8, preserving heat and standing for reaction for 3 hours at the temperature of 85 ℃, aging for 24 hours, taking out, washing with absolute ethyl alcohol, and drying for 1 hour at the temperature of 105 ℃ to obtain the modified copper-plated ceramic fiber.
Preparation example 3 of modified copper-plated ceramic fiber
The modified copper-plated ceramic fiber is prepared by the following method: firstly, cleaning ceramic fibers with deionized water, and drying at the temperature of 80 ℃ for 1h to obtain the cleaned ceramic fibers;
soaking the cleaned ceramic fiber in concentrated nitric acid with the mass fraction of 68 wt% which is 10 times of the weight of the ceramic fiber, and standing for 30min at the temperature of 60 ℃ to obtain pretreated ceramic fiber; cleaning the pretreated ceramic with deionized water to neutrality, and drying at 80 ℃ for 1h to obtain acid-treated ceramic fiber;
thirdly, soaking the acid-treated ceramic fiber in chemical copper plating solution which is 5 times of the weight of the acid-treated ceramic fiber, performing ultrasonic dispersion for 10min under the condition that the ultrasonic frequency is 60KHz, and standing for 3h at the temperature of 60 ℃ to obtain pre-plated copper ceramic fiber;
fourthly, cleaning the pre-plated copper ceramic fiber with deionized water to be neutral, and then sintering the pre-plated copper ceramic fiber at the temperature of 800 ℃ for 10 hours to obtain the copper-plated ceramic fiber;
soaking the copper-plated ceramic fiber in a silicon dioxide modification solution (selected from preparation example 3 of the silicon dioxide modification solution) with the weight 5 times of the copper-plated ceramic fiber, preserving heat and stirring for 1h at the temperature of 60 ℃, then adding ammonia water to adjust the pH to 8, preserving heat and standing for reaction for 2h at the temperature of 90 ℃, aging for 24h, taking out, washing with absolute ethyl alcohol, and drying for 1h at the temperature of 105 ℃ to obtain the modified copper-plated ceramic fiber.
Preparation example 4 of modified copper-plated ceramic fiber
The present production example is different from production example 1 of modified copper-plated ceramic fiber in that the silica-modified solution is prepared from production example 2 of silica-modified solution.
Preparation example 5 of modified copper-plated ceramic fiber
This production example is different from production example 1 of modified copper-plated ceramic fiber in that the silica-modified liquid is selected from those produced in production example 3 of silica-modified liquid.
Preparation example of sepiolite porous ceramic
The starting materials in the following preparations are all commercially available, wherein the isobutylene maleic anhydride copolymer is selected from the group consisting of ISOBAM available from gory, japan; the polyvinylpyrrolidone is polyvinylpyrrolidone k 90.
Preparation example 1 of sepiolite porous ceramic
The sepiolite porous ceramic is prepared by the following method: mixing 30kg of sepiolite fibers, 0.15kg of isobutylene maleic anhydride copolymer, 0.06kg of polyvinylpyrrolidone and 100kg of water at the speed of 2000r/min for 20min to obtain mixed slurry; keeping the pressure of the mixed slurry at 250MPa for 5min for molding to obtain a ceramic blank; and drying the ceramic blank at 80 ℃ for 2h, heating to 700 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 3h, and cooling to room temperature to obtain the sepiolite porous ceramic.
Preparation example 2 of sepiolite porous ceramic
The sepiolite porous ceramic is prepared by the following method: mixing 35kg of sepiolite fibers, 0.18kg of isobutylene maleic anhydride copolymer, 0.08kg of polyvinylpyrrolidone and 100kg of water at the speed of 2000r/min for 20min to obtain mixed slurry; the mixed slurry is subjected to pressure maintaining molding for 4.5min under the pressure of 260MPa to obtain a ceramic blank; and drying the ceramic blank at 80 ℃ for 2h, heating to 750 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 2.5h, and cooling to room temperature to obtain the sepiolite porous ceramic.
Preparation example 3 of sepiolite porous ceramic
The sepiolite porous ceramic is prepared by the following method: mixing 40kg of sepiolite fibers, 0.2kg of isobutylene maleic anhydride copolymer, 0.1kg of polyvinylpyrrolidone and 100kg of water at the speed of 2000r/min for 20min to obtain mixed slurry; keeping the pressure of the mixed slurry at 270MPa for molding for 4min to obtain a ceramic blank; drying the ceramic blank at 80 ℃ for 2h, heating to 800 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 2h, and cooling to room temperature to obtain the sepiolite porous ceramic.
Examples
The portland cement in the examples is p.o42.5 ordinary portland cement provided by the Union of China; the basalt macadam is a continuous grading with the grain diameter of 5-20mm, and the apparent density of the macadam is 2850kg/m3The loose bulk porosity was 40% and the loose bulk density was 1550kg/m3The mud content is less than 0.5 percent, and the content of the needle-shaped particles is less than or equal to 5 percent; the sand is medium sand in zone II, and the apparent density is 2640kg/m3The diameter of the particles is 0.5-0.25mm, and the mud content is less than 1.0%; the admixture is formed by mixing fly ash and mineral powder in a weight ratio of 2: 1; the fly ash is F class II fly ash, the fineness (45 mu m square hole sieve residue) of the fly ash is less than 15 percent, the water demand ratio is less than 100 percent, the ignition loss is less than 5.5 percent, and the water content is less than 0.5 percent; the mineral powder is S95 grade slag powder with a density of 3.0g/cm3Specific surface area of 415m2Per kg, the 7d activity index is 80 percent, the 28d activity index is 96 percent, the fluidity ratio is 97 percent, and the water content is less than 0.2 percent; the water reducing agent is selected from a polycarboxylic acid water reducing agent with the model number of PM109 provided by Jiangsu Mega building materials science and technology company Limited; the fineness of the montmorillonite powder is 60-80 meshes; the expandable graphite is selected from Shijiazhuanhuidili mineral products, and has a density of 2.8g/cm3The fineness is 60-80 meshes.
The amounts of the raw materials used in the examples are shown in Table 1, and as shown in Table 1, the main difference between examples 1 to 7 is the different ratios of the raw materials. The sepiolite porous ceramic, the montmorillonite powder and the expandable graphite in table 1 were respectively replaced with A, B, C, that is, the weight ratio of a: B: C was 1:1:5, which represents the weight ratio of the montmorillonite powder, the expandable graphite and the sepiolite porous ceramic was 1:1: 5.
The following description will be given by taking example 1 as an example.
The preparation method of the heat-resistant concrete provided in example 1 is as follows:
s1, mixing sepiolite porous ceramic (selected from preparation example 1 of sepiolite porous ceramic), montmorillonite powder and expandable graphite according to a proportion to obtain a filler;
s2, firstly, stirring the modified copper-plated ceramic fiber (selected from preparation example 1 of the modified copper-plated ceramic fiber) and the filler at the speed of 50r/min for 20min to obtain a premix;
and S3, adding portland cement, basalt broken stone, sand, an admixture and a water reducing agent into the premix, uniformly stirring to obtain a concrete mixture, and hardening and forming the concrete mixture to obtain the heat-resistant concrete.
Table 1 examples 1-7 raw materials used in raw material usage units of the scale: kg of
Example 8
This example is different from example 1 in that the sepiolite porous ceramic in S1 is selected from the sepiolite porous ceramic prepared in preparation example 2.
Example 9
This example is different from example 1 in that the sepiolite porous ceramic in S1 is selected from the sepiolite porous ceramic prepared in preparation example 3.
Example 10
This example is different from example 1 in that the modified copper-plated ceramic fiber in S2 was selected from those prepared in preparation example 2 of modified copper-plated ceramic fiber.
Example 11
This example is different from example 1 in that the modified copper-plated ceramic fiber in S2 was selected from those prepared in preparation example 3 of modified copper-plated ceramic fiber.
Example 12
This example is different from example 1 in that the modified copper-plated ceramic fiber in S2 was selected from those prepared in preparation example 4 of modified copper-plated ceramic fiber.
Example 13
This example is different from example 1 in that the modified copper-plated ceramic fiber in S2 was selected from those prepared in preparation example 5 of modified copper-plated ceramic fiber.
Comparative example
Comparative example 1
The comparative example differs from example 1 in that the weight ratio of montmorillonite powder, expandable graphite and sepiolite porous ceramic is 1:1: 6.
Comparative example 2
This comparative example differs from example 1 in that the weight ratio of montmorillonite powder, expandable graphite and sepiolite porous ceramic was 4:4: 5.
Comparative example 3
This comparative example differs from example 1 in that the modified copper-plated ceramic fiber was replaced with an equal amount of a common ceramic fiber.
Comparative example 4
The comparative example is different from example 1 in that the modified copper-plated ceramic fiber was replaced with the same amount of copper-plated ceramic fiber, and the copper-plated ceramic fiber was prepared by the method of preparation example 1 of modified copper-plated ceramic fiber, except that the treatment of the steps (r) and (v) was not performed.
Comparative example 5
The comparative example was different from example 1 in that the modified copper-plated ceramic fiber was replaced with an equivalent amount of the coated silica layer ceramic fiber prepared by the modified copper-plated ceramic fiber in preparation example 1, except that the treatment of the third and fourth steps was not performed.
Comparative example 6
This comparative example differs from example 1 in that the filler was only 30kg of montmorillonite powder.
Comparative example 7
This comparative example differs from example 1 in that the filler was only 30kg of expandable graphite.
Comparative example 8
The comparative example differs from example 1 in that the filler was only 30kg of sepiolite porous ceramic.
Comparative example 9
The comparative example differs from example 1 in that the modified copper-plated ceramic fiber was replaced with an equal amount of copper-plated ceramic fiber, and the filler was only 30kg of montmorillonite powder.
Performance test
Detection method
The following performance tests were performed on the concrete provided in examples 1 to 13 and comparative examples 1 to 9 of the present application, and the test data are shown in table 2.
Compressive strength: making a standard test block according to a method in GB/T50081-2016 standard on mechanical property test method of common concrete, and measuring the compressive strength of the standard test block after 3d, 7d and 28d maintenance and the compressive strength at high temperature after standard maintenance for 28 d; the compressive strength under high temperature conditions was tested using the following method:
taking 3 molded test pieces from each group, carrying out standard curing for 28d, drying at 110 ℃ for 24h, placing in a high temperature furnace, respectively burning at 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ and 700 ℃ for 3h, then naturally cooling to room temperature, and testing the compressive strength after high temperature burning.
Isolation rate: segregation of concrete is the phenomenon that cohesion between the constituent materials of the concrete mix is insufficient to resist the sinking of the coarse aggregate, the concrete mix components separate from each other, causing internal compositional and structural non-uniformity, typically manifested as the separation of the coarse aggregate from the mortar, e.g., dense particles deposited at the bottom of the mix, or the coarse aggregate becoming entirely separated from the mix. The concrete segregation rate can represent the uniformity of the mixing of the concrete raw materials, and the smaller the segregation rate is, the better the uniformity of the mixing of the concrete raw materials is. The test is carried out according to the method in the anti-segregation performance test in GB/T50080-2016 standard of common concrete mixture performance test method.
Slump and slump loss: slump is a method and an index for measuring the workability of concrete, and is generally used for measuring the fluidity of a mixture by performing a slump test. The T1 grade is low-plasticity concrete, and the slump is 10-40 mm; the T2 grade is plastic concrete, and the slump is 50-90 mm; the T3 grade is flowable concrete, and the slump is 100-150 mm; t4 is high-fluidity concrete, and the slump is more than or equal to 160 mm. When the slump is tested, the slump loss needs to be tested for 1h, and the larger the slump loss of the concrete mixture is, the faster the water loss is, the poorer the fluidity, the cohesiveness and the like of the concrete are. The test is carried out according to the slump test in GB/T50080-2016 standard for testing the performance of common concrete mixtures and the method in the slump loss test with time.
TABLE 2 tables for testing the properties of the concretes of examples 1 to 13 and comparative examples 1 to 9
As can be seen by combining the examples 1-3 and the table 2, the concrete prepared by the method has the compressive strength of more than 70MPa at normal temperature, the residual strength of more than 50MPa after high-temperature firing, the segregation rate of less than 4 percent, the slump of more than 165mm and the slump loss of less than 20mm after 1 hour; the concrete of the embodiments 1 to 3 of the application has good compressive strength and heat resistance, and the low segregation rate indicates that the raw materials of the concrete are uniformly distributed and have stable structure, thereby being beneficial to improving the strength of the concrete; slump is big and slump loss is little, shows that the concrete mixture of this application has fine mobility and cohesiveness, and the concrete has fine workability at the in-process of preparing, and slump is big, shows that the concrete of this application has pumpability. In summary, the concrete of the present application has the advantages of good pumpability, good heat resistance, high heat-resistant strength, and good workability.
It can be seen from the combination of examples 1, 4-7, comparative examples 1-2 and table 2 that when the weight ratio of the montmorillonite powder, expandable graphite and sepiolite porous ceramic is changed, it has a large effect on the segregation rate, slump and slump loss of the concrete mixture. Comparative example 1 compared to example 1, the slump of the concrete mixture was significantly reduced, the segregation rate and the slump loss were increased, the normal temperature compressive strength of the concrete was increased, and the high temperature compressive strength was decreased, indicating that when the amount of montmorillonite powder and expandable graphite was decreased and the amount of sepiolite porous fiber was increased, the high temperature resistance and workability of the concrete were decreased. Comparative example 2 compared to example 1, slump of the concrete mixture was significantly reduced, segregation rate and slump loss were increased, and normal temperature compressive strength and high temperature compressive strength of the concrete were decreased, indicating that when the amount of montmorillonite powder and expandable graphite was decreased, and the amount of porous sepiolite fibers was decreased, strength, high temperature resistance and workability of the concrete were decreased. Therefore, when the montmorillonite powder, the expandable graphite and the sepiolite porous ceramic are mixed according to the weight ratio of 1-3:1-3:5, the montmorillonite powder, the expandable graphite and the sepiolite porous ceramic have a good synergistic effect, and can be well matched with the modified copper-plated ceramic fiber, so that the compressive strength, the heat resistance and the workability of the concrete are improved.
It can be seen from the combination of comparative example 3, example 1 and table 2 that, compared with the concrete of example 1, the compressive strength at normal temperature and the compressive strength at high temperature are obviously reduced, and the segregation rate is increased in comparative example 4, which shows that when the common ceramic fiber is used, the compressive strength of the concrete can be improved to a certain extent, but because the common ceramic fiber has uneven dispersibility in the concrete and higher segregation rate, the different parts of the concrete are stressed unevenly, and therefore, compared with the concrete added with the modified copper-plated ceramic fiber, the strength and the heat resistance are reduced.
In combination with comparative example 4, example 1 and table 2, it can be seen that the normal temperature compressive strength and the high temperature compressive strength of the concrete of comparative example 4 are significantly reduced and the segregation rate is increased compared to the concrete of example 1; in comparison with comparative example 4 and comparative example 3, it can be seen that the concrete of comparative example 4, the normal temperature compressive strength and the high temperature compressive strength of the ceramic fiber are increased, and the segregation rate is reduced, which shows that after the ceramic fiber is subjected to copper plating modification treatment, the strength and the heat resistance can be obviously improved, but the adsorption force of the filler to the copper-plated ceramic fiber is reduced by only carrying out the copper plating treatment on the ceramic fiber, when the copper-plated ceramic fiber and the filler are mixed in the concrete, the dispersion uniformity of the copper-plated ceramic fiber in the concrete cannot be improved well, after the copper-plated ceramic fiber is coated with the silicon dioxide layer, the adsorbability of the filler to the modified copper-plated ceramic fiber can be improved, and the fluidity of the filler can be utilized to drive the dispersion uniformity of the modified copper-plated ceramic fiber in concrete, so that the stress concentration point of the concrete is reduced, and the strength and the heat resistance of the concrete are improved.
In combination with comparative example 5, example 1 and table 2, it can be seen that the normal temperature compressive strength and the high temperature compressive strength of comparative example 5 are slightly reduced and the segregation rate is increased compared with the concrete of example 1; the analysis of the comparative examples 3 and 4 shows that the dispersion uniformity of the ceramic fiber in the concrete can be improved after the ceramic fiber is respectively subjected to the copper plating treatment or the silicon dioxide coating treatment, but the action effect is not as good as that after the ceramic fiber is subjected to the copper plating treatment and the silicon dioxide coating treatment at the same time, which indicates that when the ceramic fiber is subjected to the copper plating treatment and the silicon dioxide coating treatment at the same time, the two coating layers have a synergistic effect, and when the ceramic fiber is matched with the filler, the dispersion uniformity of the modified copper-plated ceramic fiber in the concrete can be obviously improved, and the compressive strength and the heat resistance of the concrete are improved.
It can be seen from the combination of comparative example 6, comparative example 7, comparative example 8, example 1 and table 2 that when one of the fillers is selected alone, the normal temperature compressive strength, the high temperature compressive strength and the slump of the concrete are reduced to different degrees, and the segregation rate and the slump loss are increased, which shows that when the montmorillonite powder, the expandable graphite and the sepiolite porous ceramic are matched with the fillers, a synergistic effect is achieved, and the strength and the heat resistance of the concrete can be obviously improved.
As can be seen by combining comparative example 9, comparative example 3, comparative example 6, example 1 and table 2, the normal temperature compressive strength, high temperature compressive strength and slump of the concrete of comparative example 9 are significantly reduced and the segregation rate is increased as compared with the concrete of example 1; the modified copper-plated ceramic fiber has a synergistic effect when being matched with the filler, and the compressive strength and the heat resistance of the concrete can be obviously improved after the modified copper-plated ceramic fiber and the filler are added.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The heat-resistant concrete is characterized by comprising the following components in parts by weight:
220 parts of Portland cement, 520 parts of basalt broken stone, 370 parts of sand, 70-90 parts of admixture, 30-40 parts of filler, 15-20 parts of modified copper-plated ceramic fiber, 6-8 parts of water reducer and 80-100 parts of water;
the modified copper-plated ceramic fiber is obtained by respectively carrying out chemical copper plating and silicon dioxide layer coating on ceramic fiber, and is prepared by the following method:
firstly, cleaning and drying ceramic fibers to obtain cleaned ceramic fibers;
soaking the cleaned ceramic fiber in concentrated nitric acid, and standing at 50-60 ℃ for 30-40min to obtain pretreated ceramic fiber; cleaning the pretreated ceramic to be neutral, and drying to obtain acid-treated ceramic fiber;
thirdly, soaking the acid-treated ceramic fiber in chemical copper plating solution, performing ultrasonic dispersion, and then keeping the temperature and standing for 3-5 hours at the temperature of 50-60 ℃ to obtain pre-plated copper ceramic fiber;
fourthly, after the pre-plated copper ceramic fiber is cleaned to be neutral, the pre-plated copper ceramic fiber is sintered for 10 to 12 hours at the temperature of 700 plus materials and 800 ℃ to obtain the copper-plated ceramic fiber;
soaking the copper-plated ceramic fiber in a silicon dioxide modification solution, stirring for 1-2h at the temperature of 50-60 ℃, then adding an alkaline agent to adjust the pH to 8-9, standing for reaction for 2-4h at the temperature of 80-90 ℃, and aging, washing and drying to obtain the modified copper-plated ceramic fiber;
the silicon dioxide modified solution is formed by mixing an ethanol solution of a silane coupling agent, an aqueous solution of a surfactant and tetraethoxysilane in a weight ratio of 8-10:4-6: 1;
the filler is formed by mixing montmorillonite powder, expandable graphite and sepiolite porous ceramic in a weight ratio of 1-3:1-3: 5.
2. The heat-resistant concrete as claimed in claim 1, wherein the ethanol solution of the silane coupling agent is prepared by mixing octadecyl trimethoxy silane and 50% ethanol solution in a weight ratio of 1: 50;
the aqueous solution of the surfactant is prepared by mixing cetyl trimethyl ammonium bromide and water in a weight ratio of 1: 100.
3. The heat-resistant concrete as claimed in claim 1, wherein the sepiolite porous ceramic is prepared by the following method: uniformly mixing 30-40 parts of sepiolite fibers, 0.15-0.2 part of isobutylene maleic anhydride copolymer, 0.06-0.1 part of polyvinylpyrrolidone and 100 parts of water in parts by weight to obtain mixed slurry; pressing and molding the mixed slurry to obtain a ceramic blank; and drying the ceramic blank, heating to the temperature of 700-800 ℃, then carrying out heat preservation sintering for 2-3h, and cooling to the room temperature to obtain the sepiolite porous ceramic.
4. The heat-resistant concrete as claimed in claim 3, wherein the pressure for the press molding of the mixed slurry is 250-270MPa, and the molding time is 4-5 min.
5. The heat-resistant concrete as claimed in claim 1, wherein the admixture is formed by mixing fly ash and mineral powder in a weight ratio of 2: 1.
6. The heat-resistant concrete according to claim 5, wherein the fly ash is class F class II fly ash, and the mineral powder is class S95 mineral powder.
7. The heat-resistant concrete as claimed in claim 1, wherein the basalt broken stone has a continuous grading of 5-20mm in particle size, a mud content of < 0.5%, and a needle-like particle content of < 5%.
8. A heat resistant concrete according to claim 1 wherein the sand is a zone ii sand having a particle diameter of 0.5 to 0.25mm and a mud content of < 1.0%.
9. The method of preparing a heat-resistant concrete of claim 1, comprising the steps of: according to the proportion, firstly, uniformly mixing the modified copper-plated ceramic fiber and the filler to obtain a premix; then adding portland cement, basalt broken stone, sand, an admixture, a water reducing agent and water into the premix, and uniformly mixing according to a proportion.
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| CN105463450A (en) * | 2015-12-01 | 2016-04-06 | 仇颖超 | Method for manufacturing copper-based nano ceramic fiber composite material through laser cladding |
| CN107032695B (en) * | 2017-03-20 | 2020-02-07 | 张家港江苏科技大学产业技术研究院 | Steel fiber self-compacting concrete, preparation method thereof and prefabricated part |
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