CN115417635B - Radiation-proof silicate exterior wall concrete and preparation method thereof - Google Patents
Radiation-proof silicate exterior wall concrete and preparation method thereof Download PDFInfo
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- CN115417635B CN115417635B CN202210962996.9A CN202210962996A CN115417635B CN 115417635 B CN115417635 B CN 115417635B CN 202210962996 A CN202210962996 A CN 202210962996A CN 115417635 B CN115417635 B CN 115417635B
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00258—Electromagnetic wave absorbing or shielding materials
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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
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00293—Materials impermeable to liquids
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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
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
Abstract
The invention discloses radiation-proof silicate exterior wall concrete and a preparation method thereof, and belongs to the technical field of concrete. According to the invention, asphalt cold patch is added into concrete, so that the radiation-proof capability and water penetration resistance of silicate concrete are enhanced, and the radiation-proof silicate exterior wall concrete is beneficial to maintaining excellent long-term performance and durability. The invention also introduces the radiation-proof functional polymer into the silicate concrete system, the radiation-proof functional polymer has good binding capacity with concrete, the hexagonal boron nitride is hybridized and functionalized, the mixability with the polymer is optimized, the morphology is stable, the sectional area for reaction with radiation is maximized, and the radiation-proof performance of the silicate concrete is further increased.
Description
Technical Field
The invention relates to the technical field of concrete, in particular to radiation-proof silicate exterior wall concrete and a preparation method thereof.
Background
There is often a conflict between the radiation shielding properties and other properties of the material. For example, many radiation resistant materials do not meet both shielding function and structural integrity requirements, which greatly limits their use in radiation shielding systems. The concrete is not only a material with shielding function and structural mechanical property, but also has wide application prospect in the field of radiation protection because the concrete is low in cost and is easy to form different sizes and shapes according to structural requirements.
The invention discloses a radiation-proof high-strength concrete and a production process thereof, wherein the invention adopts stainless steel fibers, so that the concrete has excellent radiation-proof capability, meanwhile, the stainless steel fibers, wood fibers and polyvinyl alcohol fibers form mixed fibers, so that excellent bending strength and compressive strength are provided for the concrete, and iron ore is mixed into gravel and broken stone to replace part of the gravel and broken stone, so that the use amount of the gravel and the broken stone is reduced, and meanwhile, the concrete has better radiation-proof performance. The patent adds lead powder into the mixed fiber to fill the gaps in the mixed fiber, thereby playing a role in radiation protection, however, lead element has toxic and side effects on human body, and in actual use, the lead element may form potential harm to human body.
Patent CN110407538A provides an impact-resistant nano boron nitride modified concrete, the raw materials of which include cement, nano boron nitride, silica fume, fly ash, sand, water reducer and water. The nano boron nitride can obviously enhance the dynamic compressive strength, the dynamic peak strain and the impact toughness of the active powder concrete. The interface effect and the dispersion property of the boron nitride and the concrete are not optimized, and the boron nitride and the concrete are difficult to apply to the radiation protection field.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide an anti-radiation silicate exterior wall concrete with excellent radiation shielding capability and component compatibility and a preparation method thereof.
Cement-based mixtures or concretes have a high content of carbon, oxygen, calcium, silicon, aluminium. In order to maintain the overall properties of the concrete, in practical applications, exposure of the above elements to radiation or neutrons should be avoided. According to the invention, the asphalt cold patch is added into the concrete, and as the asphalt cold patch is added, the linear attenuation coefficient of the concrete is increased, the effective atomic coefficient is increased, and the macroscopic radiation protection capability of the concrete is enhanced. In addition, the asphalt cold patch is introduced to increase the water penetration resistance of the concrete, so that the radiation-proof silicate exterior wall concrete is beneficial to maintaining excellent long-term performance and durability.
The preparation method of the radiation-proof silicate exterior wall concrete comprises the following steps of:
s1, mixing 300-480 parts of cement, 30-50 parts of asphalt cold patch, 400-600 parts of sand and 550-800 parts of crushed stone, then adding 180-240 parts of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 10-25 parts of polypropylene anti-cracking fiber, 6-12 parts of water reducer and 25-50 parts of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing and curing the concrete mortar by construction to obtain the radiation-proof silicate exterior wall concrete.
Preferably, the method comprises the steps of, the type of cement in the step S1 is any one of Portland cement P.I 42.5, portland cement P.I 42.5R, portland cement P.I 52.5R, portland cement P.I 62.5R, portland cement P.II 42.5R, portland cement P.II 52.5R, portland cement P.II 62.5R, ordinary Portland cement P.O42.5R, ordinary Portland cement P.O52.5 and ordinary Portland cement P.O 52.5R.
Preferably, the crushed stone in the step S1 is continuous graded crushed stone, and the mass ratio of the crushed stone with the diameter of 5-10 mm to the crushed stone with the diameter of 10-20 mm to the crushed stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
Preferably, the length of the polypropylene anti-cracking fiber in the step S2 is 3-6 mm.
Preferably, the water reducing agent in step S2 is any one of naphthalene-based superplasticizer, aliphatic superplasticizer, amino superplasticizer, and polycarboxylic acid superplasticizer.
The hexagonal boron nitride nano-sheet consists of conjugated nitrogen atoms and boron atoms, has the characteristics of large surface area, light weight, durability and the like and has good radiation shielding capability, and the hexagonal boron nitride nano-sheet is used in the radiation protection field in the prior art. However, hexagonal boron nitride tends to aggregate and re-accumulate after dispersion under the driving of van der waals force, making it difficult to exert an ideal radiation protection effect. In order to avoid the accumulation of hexagonal boron nitride in a concrete system, the invention takes tungstic acid as a raw material and carries out hybridization on the hexagonal boron nitride through oxidation and reduction; tungsten ions are combined with dangling bonds or hydroxyl groups of hexagonal boron nitride, and finally metal tungsten on the surface is combined through tungsten-nitrogen bonds through oxidation and reduction, and the inside of hexagonal boron nitride molecules is fixed through tungsten-oxygen bonds. The metal tungsten is uniformly attached to the hybridized hexagonal boron nitride, so that the morphology of the hexagonal boron nitride is more stable, and the sectional area of the hexagonal boron nitride reacting with radiation is maximized; in addition, the tungsten element has high atomic number and high electron density, has good absorption capacity to gamma rays, and further enhances the radiation protection performance of hexagonal boron nitride.
In order to optimize the interface performance of the hybrid hexagonal boron nitride and the concrete, the hybrid hexagonal boron nitride is combined with the organic polymer, and the organic polymer and the concrete have strong combining capability, so that the uniform and stable system is facilitated. However, in the combination process of the hybrid hexagonal boron nitride and the organic polymer, the organic polymer needs to be dissolved in a solvent to achieve the optimal dispersing effect. The high atomic number tungsten in the hybrid hexagonal boron nitride is difficult to uniformly disperse in the polymer solution, and the tungsten is easy to form a network between the hexagonal boron nitride through bonding, so that the dispersion is more difficult. Therefore, the invention uses the mustard-based primary amine to carry out functionalization treatment on the hybridized hexagonal boron nitride, the non-covalent functionalized mustard-based primary amine molecules increase the solubility of the non-covalent functionalized mustard-based primary amine molecules in a solution, and the non-covalent interaction can inhibit the interaction of the hybridized hexagonal boron nitride, so that the combination process of the non-covalent functionalized mustard-based primary amine molecules and the polymer is easier.
Preferably, the radiation-proof functional polymer is prepared from an organic polymer and functionalized boron nitride; wherein the organic polymer is a copolymer obtained by polymerizing acrylic acid and styrene, and the functionalized boron nitride is hexagonal boron nitride which is subjected to tungsten hybridization and mustard-based primary amine non-covalent treatment in sequence.
Specifically, the preparation method of the radiation-proof functional polymer comprises the following steps:
l1, mixing water, acrylic acid and styrene under the anaerobic condition to form uniform reaction dispersion; adding an initiator into the reaction dispersion liquid, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving tungstic acid in ammonia water to obtain a tungstic acid solution; dispersing hexagonal boron nitride in water to obtain boron nitride dispersion liquid; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
l3, dispersing the hybridized boron nitride powder in a mustard-based primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain functionalized boron nitride for later use;
and L4, dissolving a copolymerization product in an organic solvent, then continuously adding functional boron nitride, and removing the organic solvent through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
Further, the preparation method of the radiation-proof functional polymer comprises the following steps of:
l1, mixing 100-150 parts of water, 1-1.5 parts of acrylic acid and 4-6 parts of styrene under the anaerobic condition to form uniform reaction dispersion; adding 0.06-0.09 part of potassium persulfate into the reaction dispersion liquid, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving 0.25-0.5 part of tungsten acid in 75-150 parts of ammonia water to obtain a tungstic acid solution; dispersing 0.15-0.3 part of hexagonal boron nitride in 100-200 parts of water to obtain boron nitride dispersion liquid; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
l3, dispersing 1-2 parts of the hybridized boron nitride powder in 50-100 parts of mustard-based primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain functionalized boron nitride for later use;
and L4, dissolving 13.5-27 parts of a copolymerization product in 150-300 parts of ethanol, then continuously adding 1.5-3 parts of functionalized boron nitride, and removing the ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
Preferably, the polymerization conditions in step L1 are: reacting for 12-36 h at 75-90 ℃.
Preferably, the calcination conditions in step L2 are: heating to 550-700 ℃ and calcining for 0.5-2 h.
Preferably, the conditions of the reduction reaction in step L2 are: reacting for 1-4 h at 750-850 ℃.
Preferably, the primary mustard amine solution in step L3 is prepared from primary mustard amine and ethanol in a volume ratio of 1:2 to 4.
Preferably, the conditions of the functionalization treatment in step L3 are: treating at 25-40 deg.c for 1-5 hr.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the following description and functions of partial raw materials in the formula:
asphalt cold-patch: the asphalt material is prepared by mixing and stirring matrix asphalt, a separating agent and an additive in an asphalt stirring tank according to a proportion to prepare asphalt cold-filling liquid, and then mixing and stirring the cold-filling liquid and aggregate in a mixing plant.
Hexagonal boron nitride: the simplest boron-nitrogen macromolecule is similar to hexagonal carbon network in graphite, and nitrogen and boron in hexagonal boron nitride also form hexagonal network layers which are mutually overlapped to form crystals. The crystal is similar to graphite, has diamagnetism and high anisotropy, and the crystal parameters are quite similar. Boron nitride is mainly used for refractory materials, semiconductor solid-phase doping sources, structural materials of atomic stacks, neutron radiation-proof packaging materials, rocket engine constituent materials, high-temperature lubricants and release agents.
Tungstic acid: mWO of the general formula 3 ·nH 2 The O, known tungstic acid is a plurality of kinds, namely a polymer compound formed by combining tungsten trioxide and water in different ratios and different forms, and known tungstic acid is yellow tungstic acid, white tungstic acid, metatungstic acid and the like. The present invention uses yellow tungstic acid.
The invention has the beneficial effects that:
compared with the prior art, the asphalt cold patch is added into the concrete, so that the effective atomic coefficient of a concrete system is increased, and the radiation-proof capability of the concrete is enhanced; in addition, the asphalt cold patch is introduced to increase the water penetration resistance of the concrete, so that the radiation-proof silicate exterior wall concrete is beneficial to maintaining excellent long-term performance and durability.
Compared with the prior art, the radiation-proof functional polymer prepared from the organic polymer and the functionalized boron nitride is introduced into a concrete system. The radiation-proof functional polymer has good binding capability with concrete, wherein the hexagonal boron nitride is hybridized and functionalized, and the operability of mixing with the polymer is optimized; the prepared functionalized boron nitride has stable form, the sectional area of the functionalized boron nitride reacting with radiation is maximized, and the radiation-proof performance of the concrete is further improved.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The comparative example and the examples of the present invention have the following parameters of part of raw materials:
asphalt cold-patch, residual stability: 91.7, oil-stone ratio: 5.8%, particle size: AC-10, adhesion rating: grade 5, stability: 3.8, taian Taiyi engineering materials Co., ltd;
middlings, apparent density: 2560kg/m 3 Mud content: 0.1%, water content: 0.1%, firmness index: 99%, outline dimension: 70-120 meshes, and is provided by a Hendel product processing plant in the Mingshou county;
hexagonal boron nitride, model: ZD-BN-1, purity 99.9%, average particle size: 100nm, specific surface area: 19m 2 /g, bulk density: 0.30g/cm 3 Available from new materials, bisli, su;
methyl allyl polyoxyethylene ether, hydroxyl number: 21-26 mgKOH/g, molecular weight: 2160-2640, nantong Runfeng petrochemical Co.
Example 1
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 0.3kg of asphalt cold patch, 4kg of medium sand and 5.5kg of crushed stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber and 0.06kg of methyl allyl polyoxyethylene ether into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
Example 2
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 4kg of medium sand and 5.5kg of broken stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber, 0.06kg of methyl allyl polyoxyethylene ether and 0.25kg of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
The preparation method of the radiation-proof functional polymer comprises the following steps:
l1, mixing 10kg of water, 0.1kg of acrylic acid and 0.4kg of styrene under the protection of nitrogen to form a uniform reaction dispersion; adding 0.006kg of potassium persulfate into the reaction dispersion, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving 0.025kg of tungstic acid in 7.5kg of ammonia water to obtain a tungstic acid solution; dispersing 0.015kg of hexagonal boron nitride in 10kg of water to obtain boron nitride dispersion; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
and L3, dissolving 1.35kg of copolymerization product in 15kg of ethanol, then continuously adding 0.15kg of hybridized boron nitride powder, and removing the ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
The polymerization conditions in step L1 are: the reaction was carried out at 85℃for 18h.
The conditions for the calcination in step L2 are: heating to 650 ℃ and calcining for 1h.
The conditions for the reduction reaction in step L2 are: the reaction was carried out at 750℃for 2h.
Example 3
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 0.3kg of asphalt cold patch, 4kg of medium sand and 5.5kg of crushed stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber, 0.06kg of methyl allyl polyoxyethylene ether and 0.25kg of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
The preparation method of the radiation-proof functional polymer comprises the following steps:
l1, mixing 10kg of water, 0.1kg of acrylic acid and 0.4kg of styrene under the protection of nitrogen to form a uniform reaction dispersion; adding 0.006kg of potassium persulfate into the reaction dispersion, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving 0.025kg of tungstic acid in 7.5kg of ammonia water to obtain a tungstic acid solution; dispersing 0.015kg of hexagonal boron nitride in 10kg of water to obtain boron nitride dispersion; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
and L3, dissolving 1.35kg of copolymerization product in 15kg of ethanol, then continuously adding 0.15kg of hybridized boron nitride powder, and removing the ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
The polymerization conditions in step L1 are: the reaction was carried out at 85℃for 18h.
The conditions for the calcination in step L2 are: heating to 650 ℃ and calcining for 1h.
The conditions for the reduction reaction in step L2 are: the reaction was carried out at 750℃for 2h.
Example 4
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 0.3kg of asphalt cold patch, 4kg of medium sand and 5.5kg of crushed stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber, 0.06kg of methyl allyl polyoxyethylene ether and 0.25kg of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
The preparation method of the radiation-proof functional polymer comprises the following steps:
l1, mixing 10kg of water, 0.1kg of acrylic acid and 0.4kg of styrene under the protection of nitrogen to form a uniform reaction dispersion; adding 0.006kg of potassium persulfate into the reaction dispersion, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dispersing 0.1kg of hexagonal boron nitride in 5kg of mustard-based primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain functionalized boron nitride for later use;
and L3, dissolving 1.35kg of copolymerization product in 15kg of ethanol, then continuously adding 0.15kg of functionalized boron nitride, and removing the ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
The polymerization conditions in step L1 are: the reaction was carried out at 85℃for 18h.
The primary mustard-based amine solution in step L2 is prepared from primary mustard-based amine and ethanol in a volume ratio of 1:3, mixing to obtain the product.
The conditions of the functionalization treatment in the step L2 are as follows: the treatment was carried out at 25℃for 3h.
Example 5
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 0.3kg of asphalt cold patch, 4kg of medium sand and 5.5kg of crushed stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber, 0.06kg of methyl allyl polyoxyethylene ether and 0.25kg of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
The preparation method of the radiation-proof functional polymer comprises the following steps:
l1, mixing 10kg of water, 0.1kg of acrylic acid and 0.4kg of styrene under the protection of nitrogen to form a uniform reaction dispersion; adding 0.006kg of potassium persulfate into the reaction dispersion, heating and starting the polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving 0.025kg of tungstic acid in 7.5kg of ammonia water to obtain a tungstic acid solution; dispersing 0.015kg of hexagonal boron nitride in 10kg of water to obtain boron nitride dispersion; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
l3, dispersing 0.1kg of the hybridized boron nitride powder in 5kg of mustard-based primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain functionalized boron nitride for later use;
l4, dissolving 1.35kg of copolymerization product in 15kg of ethanol, then continuously adding 0.15kg of functionalized boron nitride, and removing the ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
The polymerization conditions in step L1 are: the reaction was carried out at 85℃for 18h.
The conditions for the calcination in step L2 are: heating to 650 ℃ and calcining for 1h.
The conditions for the reduction reaction in step L2 are: the reaction was carried out at 750℃for 2h.
The primary mustard-based amine solution in step L3 is prepared from primary mustard-based amine and ethanol in a volume ratio of 1:3, mixing to obtain the product.
The conditions of the functionalization treatment in the step L3 are as follows: the treatment was carried out at 25℃for 3h.
Comparative example 1
The radiation-proof silicate exterior wall concrete is prepared by the following method:
s1, mixing 3kg of ordinary Portland cement P.O42.5, 4kg of medium sand and 5.5kg of broken stone, then adding 1.8kg of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 0.1kg of polypropylene anti-cracking fiber and 0.06kg of methyl allyl polyoxyethylene ether into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing, covering a film and sprinkling water for curing the concrete mortar, wherein the curing times are 3 times/day, and the curing period is 28 days, so that the radiation-proof silicate exterior wall concrete is obtained.
The broken stone in the step S1 is continuous graded broken stone, and the mass ratio of the broken stone with the diameter of 5-10 mm to the broken stone with the diameter of 10-20 mm to the broken stone with the diameter of 20-30 mm is 1:2.5:0.5 blending to obtain the final product.
The length of the polypropylene anti-cracking fiber in the step S2 is 6mm.
Test example 1
The specific steps in the shielding performance test reference of the radiation-proof silicate exterior wall concrete (Guo Wenjiang, dan Jianjun, marshal, etc.) are carried out in the shielding performance test of different aggregate radiation-proof concrete [ J ] concrete 2016 (8): 84-86.DOI:10.3969/J. Issn.1002-3550.2016.08.022. The concrete prepared in each of the above examples and comparative examples was poured into test pieces having dimensions of 300mm×250mm×100mm, and two pieces were prepared for each group. The radioactive source for the shielding performance test is Cs-137, and the activity is 20mCi; the measuring instrument is a Monte ET-451 ionization chamber patrol instrument. In the test, the distance between the measuring instrument and the radioactive source is 65cm, and the test block is placed at a position 5cm away from the measuring instrument. And calculating the linear attenuation coefficient mu of each concrete according to a formula:
wherein ρ is the sample density, t is the sample thickness, A and A 0 Radiant flux with and without the shielded sample, respectively.
Each group was tested 5 times, the results were arithmetically averaged, and the shielding performance test results of the radiation-proof silicate exterior wall concrete are shown in table 1.
Table 1: radiation-proof silicate exterior wall concrete shielding performance test result table
| Name of the name | μ/cm -1 |
| Example 1 | 0.051 |
| Example 2 | 0.071 |
| Example 3 | 0.085 |
| Example 4 | 0.058 |
| Example 5 | 0.092 |
| Comparative example 1 | 0.034 |
The higher linear attenuation coefficient represents the stronger radiation shielding capability of the radiation-proof silicate exterior wall concrete. As can be seen from a comparison of example 1 and comparative example 1, the introduction of asphalt cold feed helps to improve the radiation protection of the concrete system, probably because the effective atomic coefficient of the concrete system increases, the linear attenuation coefficient increases, and macroscopic performance is enhanced in radiation shielding performance of the concrete. As can be seen from the comparison between the embodiment 2 and the comparative example 1, the radiation-proof functional polymer composed of the hybrid hexagonal boron nitride and the polymer is also beneficial to the improvement of the radiation shielding performance, probably because the metal tungsten is uniformly attached to the hybrid hexagonal boron nitride, so that the morphology of the hexagonal boron nitride is more stable, and the sectional area of the radiation reaction is maximized; the tungsten element has high atomic number and high electron density, has good absorption capacity to gamma rays, and further enhances the radiation protection performance of hexagonal boron nitride. Finally, as can be seen from the comparison of example 3 and example 5, example 5 was subsequently functionalized to exhibit better shielding performance than the hybrid hexagonal boron nitride; this is probably because the non-covalent functionalized primary mustard-based amine molecules increase the solubility of hexagonal boron nitride in the polymer solution, while the non-covalent interactions can inhibit the interactions of the hybridized hexagonal boron nitride, making the binding process with the polymer easier, the component distribution more uniform and the linear attenuation coefficient higher in example 5 than in example 3.
Test example 2
The test of the water penetration resistance of the radiation-proof silicate exterior wall concrete is carried out by a specific method in reference standard GB/T50082-2009 test method Standard for the long-term performance and durability of common concrete. The preparation and maintenance of the concrete test piece meet the regulations in the standard GB/T50081-2019 "test method Standard for physical and mechanical Properties of concrete". The water penetration resistance test adopts a step-by-step pressurizing method, when the water pressure starts from 0.1MPa, the water pressure is increased by 0.1MPa every 8 hours later, and the water penetration condition of the end face of the test piece is observed at any time. When water seepage occurs on the surfaces of 3 test pieces in the 6 test pieces or when the surface water seepage test pieces in the 6 test pieces are less than 3 when the specified pressure is added, stopping the test, and recording the water pressure at the moment. The level of impermeability of the concrete should be determined by multiplying the maximum water pressure at which no water penetration occurs for 4 of the 6 test pieces in each group by 10. The concrete's level of resistance to penetration should be calculated as follows:
P＝10H-1
wherein P is the impervious grade of the concrete, and H is the water pressure (MPa) when 3 test pieces out of 6 test pieces permeate water.
Each example and comparative example were classified into six classes P4, P6, P8, P10, P12, and greater than P12 according to the level of permeation resistance according to the test results. The water penetration resistance test of the radiation-proof silicate exterior wall concrete is shown in Table 2.
Table 2: water penetration resistance test meter for radiation-proof silicate exterior wall concrete
As can be seen from a comparison of the above examples and comparative examples, the concrete has an increased level of resistance to penetration after the concrete has been introduced into the asphalt cold mix, with the increase being most pronounced in example 5. The reason for this phenomenon may be that asphalt cold patch makes the interval between concretes more compact, preventing the passage of water molecules; in addition, the component of example 5 has the best overall dispersibility, the most uniform and stable components, and after the concrete is cured, the radiation-proof functional polymer has strong binding capacity with the concrete, fewer formed passages and shows the best impermeability.
Claims (10)
1. The preparation method of the radiation-proof silicate exterior wall concrete is characterized by comprising the following steps of: adding radiation-proof functional polymer into the concrete mortar; the radiation-proof functional polymer is prepared from an organic polymer and functionalized boron nitride; wherein the organic polymer is a copolymer obtained by polymerizing acrylic acid and styrene, and the functionalized boron nitride is hexagonal boron nitride which is subjected to tungsten hybridization and mustard-based primary amine non-covalent treatment in sequence;
the preparation method of the functionalized boron nitride comprises the following steps: dissolving 0.25-0.5 part of tungsten acid in 75-150 parts of ammonia water by weight to obtain a tungstic acid solution; dispersing 0.15-0.3 part of hexagonal boron nitride in 100-200 parts of water to obtain boron nitride dispersion liquid; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use; dispersing 1-2 parts of the hybridized boron nitride powder in 50-100 parts of mustard primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain the functionalized boron nitride.
2. The method for preparing the radiation-proof silicate exterior wall concrete according to claim 1, which is characterized by comprising the following steps in parts by weight:
s1, mixing 300-480 parts of cement, 30-50 parts of asphalt cold patch, 400-600 parts of sand and 550-800 parts of crushed stone, then adding 180-240 parts of water, and continuously stirring to obtain concrete coarse material for later use;
s2, adding 10-25 parts of polypropylene anti-cracking fiber, 6-12 parts of water reducer and 25-50 parts of radiation-proof functional polymer into the concrete coarse material, and mixing to obtain concrete mortar for later use;
and S3, pouring, curing and curing the concrete mortar by construction to obtain the radiation-proof silicate exterior wall concrete.
3. The method for preparing the radiation-proof silicate exterior wall concrete according to claim 2, which is characterized in that: the type of cement in the step S1 is any one of Portland cement P.I 42.5, portland cement P.I 42.5R, portland cement P.I 52.5R, portland cement P.I 62.5R, portland cement P.II 42.5R, portland cement P.II 52.5R, portland cement P.II 62.5R, ordinary Portland cement P.O42.5R, ordinary Portland cement P.O52.5 and ordinary Portland cement P.O 52.5R.
4. The method for preparing the radiation-proof silicate exterior wall concrete according to claim 2, which is characterized in that: the crushed stone in the step S1 is continuous graded crushed stone, and the crushed stone with the mass ratio of 5-10 mm, 10-20 mm and 20-30 mm is formed by the following components in percentage by mass: 2.5:0.5 blending to obtain the final product.
5. The method for preparing the radiation-proof silicate exterior wall concrete according to claim 2, which is characterized in that: the water reducer is any one of naphthalene-based high-efficiency water reducer, aliphatic high-efficiency water reducer, amino high-efficiency water reducer and polycarboxylic acid high-performance water reducer.
6. The method for preparing the radiation-proof silicate exterior wall concrete according to any one of claims 1 or 2, wherein the preparation method of the radiation-proof functional polymer is as follows in parts by weight:
l1, mixing 100-150 parts of water, 1-1.5 parts of acrylic acid and 4-6 parts of styrene under an anaerobic condition to form a uniform reaction dispersion; adding 0.06-0.09 part of potassium persulfate into the reaction dispersion liquid, heating and starting a polymerization reaction; after the reaction is finished, centrifugally collecting a solid product, washing and drying the solid product to obtain a copolymerization product for later use;
l2, dissolving 0.25-0.5 part of tungsten acid in 75-150 parts of ammonia water to obtain a tungstic acid solution; dispersing 0.15-0.3 part of hexagonal boron nitride in 100-200 parts of water to obtain boron nitride dispersion liquid; mixing the tungstic acid solution and the boron nitride dispersion liquid at normal temperature, and then calcining the mixed liquid of the tungstic acid solution and the boron nitride dispersion liquid to obtain oxidized powder; introducing hydrogen into the oxidized powder under the anaerobic condition for reduction reaction, and cooling to room temperature after the reaction is finished to obtain hybridized boron nitride powder for later use;
l3, dispersing 1-2 parts of the hybridized boron nitride powder into 50-100 parts of mustard-based primary amine solution, and performing functionalization treatment; filtering after the functionalization treatment is finished to obtain a filter cake, washing with alcohol, and drying to obtain functionalized boron nitride for later use;
and L4, dissolving 13.5-27 parts of a copolymerization product in 150-300 parts of ethanol, then continuously adding 1.5-3 parts of functionalized boron nitride, and removing ethanol through ultrasonic treatment and reduced pressure distillation to obtain the radiation-proof functional polymer.
7. The method for preparing radiation protection silicate exterior wall concrete according to claim 6, wherein the polymerization reaction conditions in the step L1 are as follows: and reacting for 12-36 hours at the temperature of 75-90 ℃.
8. The method for preparing radiation protection silicate exterior wall concrete according to claim 6, wherein the calcining conditions in the step L2 are: and heating to 550-700 ℃ and calcining for 0.5-2 h.
9. The method for preparing radiation-proof silicate exterior wall concrete according to claim 6, wherein the reduction reaction conditions in the step L2 are as follows: reacting for 1-4 hours at 750-850 ℃.
10. A radiation-proof silicate exterior wall concrete is characterized in that: the method according to any one of claims 1 to 9.
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Citations (5)
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|---|---|---|---|---|
| GB1260342A (en) * | 1966-08-10 | 1972-01-12 | Marxen Friedrich | Improvements relating to radiation shields |
| US5814824A (en) * | 1995-11-15 | 1998-09-29 | Commonwealth Edison Company | Composite thermal insulation and radioactive radiation shielding |
| CN105645865A (en) * | 2015-12-30 | 2016-06-08 | 上海师范大学 | Rare-earth nuclear-radiation-proof mortar and preparation method of rare-earth nuclear-radiation-proof mortar |
| CN107265987A (en) * | 2017-07-31 | 2017-10-20 | 常州聚盛节能工程有限公司 | A kind of radiation shield concrete and preparation method thereof |
| CN109796162A (en) * | 2019-04-01 | 2019-05-24 | 浙江三门永泰建材有限公司 | A kind of strong concrete and its preparation process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0637798B2 (en) * | 1985-06-22 | 1994-05-18 | 電気化学工業株式会社 | Concrete member |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1260342A (en) * | 1966-08-10 | 1972-01-12 | Marxen Friedrich | Improvements relating to radiation shields |
| US5814824A (en) * | 1995-11-15 | 1998-09-29 | Commonwealth Edison Company | Composite thermal insulation and radioactive radiation shielding |
| CN105645865A (en) * | 2015-12-30 | 2016-06-08 | 上海师范大学 | Rare-earth nuclear-radiation-proof mortar and preparation method of rare-earth nuclear-radiation-proof mortar |
| CN107265987A (en) * | 2017-07-31 | 2017-10-20 | 常州聚盛节能工程有限公司 | A kind of radiation shield concrete and preparation method thereof |
| CN109796162A (en) * | 2019-04-01 | 2019-05-24 | 浙江三门永泰建材有限公司 | A kind of strong concrete and its preparation process |
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