CN111847940A - Aggregate with irradiation resistance function and preparation method thereof, irradiation-resistant concrete and preparation method thereof - Google Patents

Aggregate with irradiation resistance function and preparation method thereof, irradiation-resistant concrete and preparation method thereof Download PDF

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CN111847940A
CN111847940A CN202010779309.0A CN202010779309A CN111847940A CN 111847940 A CN111847940 A CN 111847940A CN 202010779309 A CN202010779309 A CN 202010779309A CN 111847940 A CN111847940 A CN 111847940A
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aggregate
cement
water reducing
water
reducing agent
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曹银
王玲
王振地
王蒙
姚燕
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China Building Materials Academy CBMA
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China Building Materials Academy CBMA
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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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
    • 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
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1077—Cements, e.g. waterglass
    • 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
    • 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
    • C04B28/06—Aluminous cements
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00862—Uses not provided for elsewhere in C04B2111/00 for nuclear applications, e.g. ray-absorbing concrete
    • 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
    • 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
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides an aggregate with an irradiation-resistant function, a preparation method thereof, irradiation-resistant concrete and a preparation method thereof. The aggregate comprises boron industrial waste residue regenerated aggregate and a cement-based shell layer coated on the surface of the boron industrial waste residue regenerated aggregate; the boron industrial waste residue regenerated aggregate comprises the following raw materials in percentage by weight: 41-48% of boric sludge, 15-20% of cement, 18-25% of mineral admixture, 5-7% of sodium silicate, 3.9-5.2% of expanding agent, 8-15% of water and 2.0-3.5% of water reducing agent; the cement-based shell layer comprises the following raw materials in percentage by weight: 46-50% of cement, 10-13% of fly ash, 4.2-5.1% of silica fume, 25.6-30.7% of water, 1.0-1.6% of water reducing agent and 3.9-5.2% of expanding agent. The cement-based material is adopted to carry out surface modification on the boron industrial waste residue regenerated aggregate, so that the surface structure and the performance of the aggregate can be optimized, the porosity and the water absorption are reduced, the compactness is improved, and the mechanical property, the durability and the irradiation resistance of the aggregate are further enhanced.

Description

Aggregate with irradiation resistance function and preparation method thereof, irradiation-resistant concrete and preparation method thereof
Technical Field
The invention relates to the field of solid waste utilization and radiation-proof materials, in particular to aggregate with an irradiation-resistant function and a preparation method thereof, irradiation-resistant concrete and a preparation method thereof.
Background
At present, when preparing high-neutron irradiation resistant concrete, high-density natural ore aggregates (hematite, limonite, barite and the like) are widely adopted in China as coarse and fine aggregates, and fast neutrons are moderated into slow neutrons through inelastic scattering; adding boron-containing substance (such as borax, boron carbide, etc.) as neutron absorber. However, since the bulk density of the natural high-density aggregate is much greater than that of the cement paste, the natural high-density aggregate is easy to settle and separate in concrete vibration construction, and the construction operability is poor; and the natural ores with high density and radiation-proof property have limited reserves, cannot meet the increasing engineering requirements and are not suitable for being used in large quantities. On one hand, the boron-containing substance used as the neutron absorber is expensive, and on the other hand, the boron-containing substance can delay the hydration of cement after being added, so that the phenomenon of delayed coagulation or even no coagulation is caused.
The boron industrial waste residue is also called boron mud, is waste residue produced in the borax production process of boron-magnesium ore, is alkaline, and mainly comprises MgO and SiO2And a certain amount of B2O3(2-8%); china's boron mineral data are mainly distributed in Liaoning area, and 5t of boron mud is produced when 1t of borax is produced; currently boron sludge to be treated reaches 1000 million t, and is increased by 100 million t every year. The accumulation of a large amount of boric sludge can cause serious water and soil pollution and seriously affect the health and safety of surrounding life.
Therefore, how to effectively utilize boric sludge in the preparation of high-neutron irradiation resistant concrete with excellent performance is a topic worthy of study.
Disclosure of Invention
Therefore, the invention aims to solve the technical problem of overcoming the defect that the concrete has poor homogeneity and a weak shielding area due to the fact that the density of the aggregate used for preparing the radiation-resistant concrete is too high in the prior art, and thus provides the aggregate with the radiation-resistant function.
The invention also provides a preparation method of the aggregate with the irradiation resistance function.
The invention also provides radiation-resistant concrete.
The invention also provides a preparation method of the radiation-resistant concrete.
Therefore, the invention provides an aggregate with an irradiation resistance function, which comprises a boron industrial waste residue regenerated aggregate and a cement-based shell layer coated on the surface of the boron industrial waste residue regenerated aggregate;
the boron industrial waste residue regenerated aggregate comprises the following raw materials in percentage by weight: 41-48% of boric sludge, 15-20% of cement, 18-25% of mineral admixture, 5-7% of sodium silicate, 3.9-5.2% of expanding agent, 8-15% of water and 2.0-3.5% of water reducing agent;
the cement-based shell layer comprises the following raw materials in percentage by weight: 46-50% of cement, 10-13% of fly ash, 4.2-5.1% of silica fume, 25.6-30.7% of water, 1.0-1.6% of water reducing agent and 3.9-5.2% of expanding agent.
Further, the thickness of the cement-based shell layer is 0.5-1.2 mm.
Further, the mineral admixture is fly ash, mineral powder, silica fume, metakaolin, limestone powder and nano SiO2One or more of them.
Further, the cement is portland cement and/or aluminate cement.
Further, the water reducing agent is a polycarboxylic acid water reducing agent and/or a naphthalene water reducing agent, and the water reducing rate is more than or equal to 30%; the expanding agent is one or more of calcium sulphoaluminate expanding agents, calcium oxide expanding agents and calcium sulphoaluminate and calcium oxide compound expanding agents.
The invention also provides a preparation method of the aggregate with the irradiation resistance function, which comprises the following steps:
1) mixing and stirring the boron mud, the cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent, and granulating to obtain boron industrial waste residue regenerated aggregate;
2) mixing the boron industrial waste residue regenerated aggregate with cement, fly ash, silica fume and an expanding agent, adding water and a water reducing agent, continuously stirring, and then spreading and maintaining the obtained product;
3) and (5) steaming the cured product, and then cooling.
Further, in the step 1), the mixing and stirring time is 5-10min, the granulation temperature is 40-60 ℃, and the particle size of the granules is 5-20 mm.
Further, the concrete preparation process of the step 2) comprises the steps of dry-mixing the boron industrial waste residue regenerated aggregate, cement, fly ash, silica fume and an expanding agent for 1-3min in a vacuum environment of 2-5kPa, adding water and a water reducing agent, continuously stirring for 3-8min, spreading the obtained product, and naturally curing for 18-24 h.
Further, the steam-curing conditions in the step 3) are as follows: the temperature is 60-80 ℃, the pressure is 1-2MPa, and the curing time is 4-12 h.
Further, the mass ratio of the total mass of the cement, the fly ash, the silica fume, the expanding agent, the water and the water reducing agent to the mass of the boron industrial waste residue regenerated aggregate is 0.22-0.45: 1.
The invention provides irradiation-resistant concrete which comprises cement, fine aggregates, functional aggregates, water and a water reducing agent, wherein the functional aggregates are the aggregates with irradiation-resistant function.
Further, the ratio of each component in the radiation-resistant concrete is as follows: based on the mass of each component in the concrete of unit volume, the cement is 360kg plus 250, the fine aggregate is 400 plus 660kg, the functional aggregate is 1200 plus 1800kg, the water is 80-160kg, and the water reducing agent is 10-15 kg.
Further, the composite material also comprises one or more of active powder, expanding agent and fiber.
Further, the ratio of each component in the radiation-resistant concrete is as follows: based on the mass of each component in the concrete of unit volume, the cement is 360kg plus one material, the fine aggregate is 400 plus one material, the functional aggregate is 1200 plus one material, the water is 80 to 160kg, the water reducing agent is 10 to 15kg, the active powder is less than or equal to 350kg, the expanding agent is less than or equal to 50kg, the fiber mixing amount is less than or equal to 0.025m3。
Further, the cement is portland cement and/or aluminate cement; the fine aggregate is quartz sand or common river sand, the grain size is less than 5mm, the fineness modulus is 2.6-3.2, and the active powder is one or more of silica fume, fly ash and ground slag; the water reducing agent is a polycarboxylic acid water reducing agent and/or a naphthalene water reducing agent, and the water reducing rate is more than or equal to 35 percent; the swelling agent is a calcium oxide swelling agent or a compound swelling agent; the fibers are polypropylene fibers and/or steel fibers.
The invention also provides a preparation method of the radiation-resistant concrete, which comprises the following steps:
mixing the fine aggregate, the functional aggregate and the fiber, stirring for the first time, then adding the cement and the active powder, stirring for the second time, and finally adding the water, the water reducing agent and the expanding agent, and stirring for the third time.
Furthermore, the time for the first stirring is 15-30s, the time for the second stirring is 15-30s, and the time for the third stirring is 90-180 s.
The technical scheme of the invention has the following advantages:
1. the aggregate with the irradiation resistance function provided by the invention comprises boron industrial waste residue regenerated aggregate and a cement-based shell layer coated on the surface of the boron industrial waste residue regenerated aggregate, the surface of the boron industrial waste residue regenerated aggregate is modified by adopting a cement-based material, the surface structure and the performance of the aggregate can be optimized, the porosity and the water absorption are reduced, the compactness is improved, the mechanical property, the durability and the irradiation resistance of the aggregate are further enhanced, meanwhile, the coated aggregate has good adhesion with cement slurry in the using process, an interface transition region between the aggregate and the slurry can be optimized in the preparation of concrete, and the compactness and the integral strength of the irradiation-resistant concrete are ensured; the aggregate has low density, can replace the traditional natural high-density ore aggregate, and solves the problems of poor homogeneity and the like of the traditional irradiation-resistant concrete caused by the high-density aggregate. Boron mud containing B element is selected as main raw material of aggregate, the B element has a large neutron absorption cross section, can play a role of neutron absorber, serves as a thermal neutron absorber in the aggregate, improves the neutron irradiation resistance of the aggregate, avoids the influence on cement hydration when in direct use, solves the problem of disposal of the boron mud, and is beneficial to ecological environment protection.
2. According to the aggregate with the irradiation resistance function, the regenerated aggregate ensures the feasibility of stable balling and granulation of boron industrial waste residue through the synergistic hydration and cementation of a plurality of active components such as cement, mineral admixture, sodium silicate, expanding agent and the like, and the obtained regenerated aggregate is easy to ball, compact in structure and easy to regulate and control the particle size of the aggregate; in addition, irradiation-resistant functional aggregates with different irradiation shielding grades can be produced by adjusting the boron mud doping amount, and the boron mud solid waste utilization method is high in boron mud doping amount, high in boron mud treatment capacity and low in treatment cost, and is superior to the existing boron mud solid waste utilization method in the market at present.
3. According to the preparation method of the aggregate with the irradiation resistance, high-temperature sintering is not needed in the process of preparing the boron industrial waste residue regenerated aggregate, the process is simple, and the energy consumption is low; when the cement-based shell is prepared, all raw materials are stirred under vacuum, so that bubbles can be prevented from being introduced in the stirring process, cement paste and boron industrial waste residue regenerated aggregate are ensured to be fully infiltrated and surface pores are filled, and the compactness of a shell layer and the integral strength of aggregate can be improved. And a certain amount of expanding agent is added, so that the shrinkage in the slurry hydration process is compensated, the slurry and the interface microstructure of the slurry and the sintered aggregate are improved, and the overall compactness and strength are improved.
4. According to the preparation method of the aggregate with the irradiation resistance function, provided by the invention, the hydration degree of cement and mineral admixture can be improved through high-temperature autoclaved curing, the activity of the expanding agent is fully excited, and the microstructure and compactness of slurry are improved. In addition, the interface bonding property of the sintered aggregate and the surface shell can be greatly improved, and the overall performance of the prepared aggregate is improved.
5. According to the preparation method of the aggregate with the irradiation resistance function, provided by the invention, the granulation temperature of 40-60 ℃ is selected, so that on one hand, the full hydration of cement and other powder is ensured, and the structural cracks caused by overhigh temperature are avoided.
6. The radiation-resistant functional aggregate provided by the invention has excellent performance indexes, apparent density of 2200-.
7. The radiation-resistant concrete provided by the invention has excellent neutron irradiation resistance and high temperature resistance, and the weight ratio of the concrete to the weight ratio of the concrete is 1 x 1015After n neutron ray radiation, the strength is reduced by not more than 15 percent after the high temperature of 300 ℃ and 40 hours, and the density of the concrete is more than 2350kg/m3The compressive strength is not lower than 35MPa, and the material can be used as a raw material of a spent fuel storage container.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a neutron irradiation experimental apparatus in an experimental example of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
Preparing raw materials of boron industrial waste residue regenerated aggregates: 41kg of boric sludge, 15kg of Portland cement, 25kg of mineral admixture fly ash, 5kg of sodium silicate, 4kg of UEA type expanding agent, 8kg of water and 2kg of polycarboxylic acid type water reducing agent (the water reducing rate is 32%).
Preparing raw materials of a cement-based shell layer: 12.7kg of Portland cement, 3.51kg of fly ash, 1.13kg of silica fume, 8.29kg of water, 0.27kg of polycarboxylic acid type water reducing agent (water reducing rate is 32 percent) and 1.06kg of UEA type expanding agent.
Mixing and stirring the boron mud, the portland cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent for 5min, and then preparing a non-fired regenerated aggregate by a rolling granulator, wherein the temperature of a feeding device of the granulator is set to be 40 ℃, and the discharge particle size is a continuous particle size of 5-20mm, so as to obtain the boron industrial waste residue regenerated aggregate; and (2) carrying out dry mixing on the boron industrial waste residue regenerated aggregate, the cement, the fly ash, the silica fume and the expanding agent with the mass for 2min under a vacuum environment of 2kPa, adding water and a water reducing agent, continuously stirring for 8min, spreading the obtained regenerated lead material coated with the cement-based material shell to avoid mutual cementation, naturally curing for 24h, carrying out high-temperature high-pressure steam curing for 4h under the conditions of the temperature of 80 ℃ and the pressure of 2MPa, and cooling to room temperature to obtain the high neutron irradiation resistance aggregate prepared from the boron industrial waste residue, wherein the thickness of the cement-based material shell of the aggregate is 0.68 mm.
Example 2
Preparing raw materials of boron industrial waste residue regenerated aggregates: 45kg of boric sludge, 15kg of aluminate cement, 18kg of mineral admixture mineral powder, 5kg of sodium silicate, 3.9kg of UEA type expanding agent, 9.6kg of water and 3.5kg of polycarboxylic acid type water reducing agent (the water reducing rate is 32%).
Preparing raw materials of a cement-based shell layer: 11.5kg of aluminate cement, 2.88kg of fly ash, 1.17kg of silica fume, 5.89kg of water, 0.37kg of polycarboxylic acid type water reducing agent (water reducing rate is 32 percent) and 1.19kg of UEA type expanding agent.
Mixing and stirring the boron mud, the portland cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent for 10min, then preparing the non-fired regenerated aggregate by a rolling granulator, setting the temperature of a feeding device of the granulator to be 60 ℃, and obtaining the boron industrial waste residue regenerated aggregate with the discharge particle size of 5-20 mm; and (2) carrying out dry mixing on the boron industrial waste residue regenerated aggregate, the cement, the fly ash, the silica fume and the expanding agent with the mass for 1min under a vacuum environment of 5kPa, adding water and a water reducing agent, continuously stirring for 3min, spreading the obtained regenerated lead material coated with the cement-based material shell to avoid mutual cementation, naturally curing for 18h, carrying out high-temperature high-pressure steam curing at the temperature of 65 ℃ and under the pressure of 1MPa for 12h, and cooling to room temperature to obtain the high neutron irradiation resistance aggregate prepared from the boron industrial waste residue, wherein the thickness of the cement-based material shell of the obtained aggregate is 0.51 mm.
Example 3
Preparing raw materials of boron industrial waste residue regenerated aggregates: 48kg of boric sludge, 15kg of Portland cement, 18kg of mineral admixture silica fume, 5kg of sodium silicate, 4kg of UEA type expanding agent, 8kg of water and 2kg of polycarboxylic acid type water reducing agent (the water reducing rate is 32%).
Preparing raw materials of a cement-based shell layer: 15.2kg of Portland cement, 3.76kg of fly ash, 1.68kg of silica fume, 10.1kg of water, 0.53kg of polycarboxylic acid type water reducing agent (water reducing rate is 32 percent) and 1.72kg of UEA type expanding agent.
Mixing and stirring the boron mud, the portland cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent for 8min, then preparing a non-fired regenerated aggregate by a rolling granulator, setting the temperature of a feeding device of the granulator to be 50 ℃, and obtaining a continuous particle size of the discharged particle size of 5-20mm to obtain the boron industrial waste residue regenerated aggregate; and (2) carrying out dry mixing on the boron industrial waste residue regenerated aggregate, the cement, the fly ash, the silica fume and the expanding agent with the mass for 3min under a vacuum environment of 4kPa, adding water and a water reducing agent, continuously stirring for 5min, spreading the obtained regenerated lead material coated with the cement-based material shell to avoid mutual cementation, naturally curing for 20h, carrying out high-temperature high-pressure steam curing at the temperature of 70 ℃ and the pressure of 1.5MPa for 8h, and cooling to room temperature to obtain the high neutron irradiation resistance aggregate prepared from the boron industrial waste residue, wherein the thickness of the cement-based material shell of the obtained aggregate is 0.98 mm.
Example 4
Preparing raw materials of boron industrial waste residue regenerated aggregates: 41kg of boric sludge, 19kg of Portland cement, 18kg of limestone powder as a mineral admixture, 6.5kg of sodium silicate, 5kg of UEA type expanding agent, 8kg of water and 2.2kg of polycarboxylic acid type water reducing agent (the water reducing rate is 32%).
Preparing raw materials of a cement-based shell layer: 20.2kg of Portland cement, 4.2kg of fly ash, 2.01kg of silica fume, 12.7kg of water, 0.67kg of polycarboxylic acid type water reducing agent (water reducing rate is 32 percent) and 2.2kg of UEA type expanding agent.
Mixing and stirring the boron mud, the portland cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent for 8min, then preparing a non-fired regenerated aggregate by a rolling granulator, setting the temperature of a feeding device of the granulator to be 50 ℃, and obtaining a continuous particle size of the discharged particle size of 5-20mm to obtain the boron industrial waste residue regenerated aggregate; and (2) carrying out dry mixing on the boron industrial waste residue regenerated aggregate, the cement, the fly ash, the silica fume and the expanding agent with the mass for 2min under a vacuum environment of 2kPa, adding water and a water reducing agent, continuously stirring for 8min, spreading the obtained regenerated lead material coated with the cement-based material shell to avoid mutual cementation, naturally curing for 24h, carrying out high-temperature high-pressure steam curing for 4h under the conditions of the temperature of 80 ℃ and the pressure of 2MPa, and cooling to room temperature to obtain the high neutron irradiation resistance aggregate prepared from the boron industrial waste residue, wherein the thickness of the cement-based material shell of the aggregate is 1.18 mm.
Example 5
Preparing raw materials of boron industrial waste residue regenerated aggregates: 41kg of boric sludge, 15kg of Portland cement and mineral admixture nano SiO218kg, 5.1kg of sodium silicate, 3.9kg of UEA type expanding agent, 15kg of water and 2kg of polycarboxylic acid type water reducing agent (water reducing rate is 32%).
Preparing raw materials of a cement-based shell layer: 14.35kg of Portland cement, 3.4kg of fly ash, 1.31kg of silica fume, 8.12kg of water, 0.38kg of polycarboxylic acid type water reducing agent (water reducing rate is 32 percent) and 1.45kg of UEA type expanding agent.
Mixing and stirring the boron mud, the portland cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent for 8min, then preparing a non-fired regenerated aggregate by a rolling granulator, setting the temperature of a feeding device of the granulator to be 50 ℃, and obtaining a continuous particle size of the discharged particle size of 5-20mm to obtain the boron industrial waste residue regenerated aggregate; and (2) carrying out dry mixing on the boron industrial waste residue regenerated aggregate, the cement, the fly ash, the silica fume and the expanding agent with the mass for 2min under a vacuum environment of 2kPa, adding water and a water reducing agent, continuously stirring for 8min, spreading the obtained regenerated lead material coated with the cement-based material shell to avoid mutual cementation, naturally curing for 24h, carrying out high-temperature high-pressure steam curing for 4h under the conditions of the temperature of 60 ℃ and the pressure of 2MPa, and cooling to room temperature to obtain the high neutron irradiation resistance aggregate prepared from the boron industrial waste residue, wherein the thickness of the cement-based material shell of the aggregate is 0.72 mm.
Example 6
Preparing raw materials: 250kg of portland cement, 660kg of fine aggregate quartz sand (particle size < 5mm, fineness modulus 2.6), 1800kg of the functional aggregate obtained in example 1, 160kg of water, 10kg of polycarboxylic acid type water reducing agent (water reducing rate 32%), 100kg of active powder (silica fume: fly ash: ground slag: 1: 4: 5), 50kg of UEA type expanding agent, and 0.025m polypropylene fiber3。
Mixing quartz sand, functional aggregate and polypropylene fiber, stirring for 15s, adding portland cement and active powder, stirring for 30s, finally adding water, a water reducing agent and an expanding agent, and stirring for 90s to obtain the concrete.
Example 7
Preparing raw materials: 360kg of Portland cement, 400kg of fine aggregate river sand (particle size < 5mm, fineness modulus 3.2), 1200kg of the functional aggregate obtained in example 2, 80kg of water, 15kg of polycarboxylic acid type water reducing agent (water reducing rate 32%), 200kg of active powder (silica fume: 1: 9 of ground slag), 10kg of UEA type expanding agent and 0.015m steel fiber3。
Mixing quartz sand, functional aggregate and polypropylene fiber, stirring for 30s, adding portland cement and active powder, stirring for 15s, finally adding water, a water reducing agent and an expanding agent, and stirring for 180s to obtain the concrete.
Example 8
Preparing raw materials: 300kg of aluminate cement, 500kg of fine aggregate river sand (particle size < 5mm, fineness modulus 3.2), 1500kg of the functional aggregate obtained in example 3, 120kg of water, 5kg of polycarboxylic acid type water reducing agent (water reducing rate 32%), 50kg of active powder (silica fume), 10kg of UEA type expanding agent and 0.005m of steel fiber3。
Mixing quartz sand, functional aggregate and polypropylene fiber, stirring for 30s, adding aluminate cement and active powder, stirring for 15s, finally adding water, a water reducing agent and an expanding agent, and stirring for 180s to obtain the concrete.
Example 9
Preparing raw materials: 300kg of aluminate cement, 500kg of fine aggregate river sand (the grain diameter is less than 5mm, the fineness modulus is 3.2), 1500kg of the functional aggregate obtained in example 4, 120kg of water and 15kg of polycarboxylic acid type water reducing agent (the water reducing rate is 32%).
Mixing quartz sand and functional aggregate, stirring for 30s, adding aluminate cement, stirring for 15s, finally adding water and a water reducing agent, and stirring for 180s to obtain the concrete.
Comparative example 1
The raw material proportion and the preparation process of the radiation-resistant functional aggregate prepared from the baking-free boron industrial slag are almost the same as those of the embodiment 1, and the difference is that the high-temperature high-pressure curing process is not carried out after the cement shell layer is coated by the regenerated aggregate.
Comparative example 2
The raw material proportion and the preparation process of the radiation-resistant functional aggregate prepared from the baking-free boron industrial slag are almost the same as those in the embodiment 3, and the difference is that the dosage of boron mud and Portland cement is different: 35kg of boric sludge and 28kg of Portland cement.
Comparative example 3
The component proportion and the mixing method of the concrete mixed by the irradiation-resistant functional aggregate prepared by the baking-free boron industry are completely the same as those of experimental example 6, and the only difference is that the irradiation-resistant functional aggregate obtained in the comparative example 1 is selected as the functional aggregate.
Comparative example 4
The component proportion and the mixing method of the concrete mixed by the irradiation-resistant functional aggregate prepared by the baking-free boron industry are completely the same as those of the experimental example 8, and the only difference is that the irradiation-resistant functional aggregate obtained in the comparative example 2 is selected as the functional aggregate.
Examples of the experiments
The high neutron irradiation resistance functional aggregate obtained in the above examples and comparative examples is tested for B element content, density, cylinder pressure strength, crushing index, water absorption and porosity, and the testing method is as follows:
(1) the content of B element: and testing by inductively coupled plasma atomic emission spectrometry (ICP-AES).
(2) The testing methods of density, crushing index and water absorption rate are tested according to the standard method specified in GBT25177-2010 recycled coarse aggregate for concrete;
(3) the test method of the cylinder pressure strength is carried out according to the standard method specified in GB/T17431.2-2010 lightweight aggregate and the test method thereof (part 2), lightweight aggregate test method;
(4) and (3) porosity testing:
and (3) measuring porosity by using a drainage method, namely randomly extracting 3 functional aggregates, putting a functional aggregate sample into vacuum water saturation equipment for vacuum water saturation, keeping the vacuum degree at 1-5 kPa, and keeping a water saturation test piece for 4 hours. Taking out the functional aggregate sample, and weighing the water retention mass MsTo the nearest 0.1 g.
Placing a water container on an electronic scale, binding functional aggregate by using a string, hanging the string above the water container, keeping the functional aggregate submerged by water in the container, not sinking to the bottom and not contacting with the wall of the container, and obtaining the real volume V of the aggregate by the difference of electronic scale readings before and after the aggregate is added.
All the aggregates were placed in an oven, the oven temperature was adjusted to 105 ℃, and drying was continued for 48 h. Taking the sample out of the oven, naturally cooling to room temperature, and weighing the mass MdTo the nearest 0.1 g. And calculating the porosity according to a formula.
Figure BDA0002619619810000141
The concrete obtained in the above examples and comparative examples was tested for compressive strength, irradiation resistance and high temperature resistance by the following test methods:
(1) compressive strength: the concrete test block compressive strength is tested according to the standard method specified in GB/T50081-2016 Standard test method for mechanical Properties of ordinary concrete.
(2) Radiation resistance
6 concrete test blocks of 100X 100mm are prepared according to the concrete proportion in the embodiment, the test blocks are maintained to 28d age in a standard way, the test blocks are dried in an oven at 55 ℃ for 3 days, three test blocks are randomly selected and sent to a neutron irradiation experiment, and the rest three test blocks are used as comparison samples and stored in a conventional environment.
The detailed schematic diagram of the neutron irradiation experiment is shown in fig. 1, 14.8MeV fast neutrons generated by deuterium-tritium reaction of a neutron generator are selected, and the neutron yield is about 3 multiplied by 1010n/s. The neutron fluence rate of the center point of the test piece is 1.5 multiplied by 1010n/s·cm2The irradiation test time is 21 hours, and after the concrete test piece is subjected to the irradiation test, the concrete test piece is taken back to perform the compressive strength test after being confirmed to have no secondary derivative irradiation after being subjected to the existence of 22 days at the indoor temperature of 20 ℃.
And comparing the compressive strength of the neutron irradiation test block with that of the reference sample, and calculating the compressive strength loss rate after neutron irradiation.
(3) High temperature resistance
Forming a test block with the thickness of 100 multiplied by 100mm according to the concrete proportion in the embodiment, and performing a high-temperature test after 28d of age; the high temperature mechanism is that the temperature rises to 300 ℃ in a room for 10min and the temperature is kept for 40 h; and comparing the compression strength of the test block before and after high temperature, and calculating the loss rate of the compression strength.
The test results are shown in tables 1 and 2.
Table 1 test results of experimental example of neutron irradiation resistant functional aggregate in example and comparative example
Figure BDA0002619619810000151
TABLE 2 concrete test results obtained in examples and comparative examples
Numbering Compressive strength (MPa) B element content ([ permillage ] wt) Radiation resistance intensityDegree loss ratio (%) Compressive strength loss rate after high temperature (%)
Example 6 53 3.99 0.3 2.4
Example 7 55 3.60 0.5 3.6
Example 8 49 4.55 0.2 3.5
Example 9 46 3.79 0.3 4.3
Comparative example 3 41 3.96 16 8
Comparative example 4 43 2.97 8 17
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (17)

1. The aggregate with the irradiation resistance function is characterized by comprising boron industrial waste residue regenerated aggregate and a cement-based shell layer coated on the surface of the boron industrial waste residue regenerated aggregate;
the boron industrial waste residue regenerated aggregate comprises the following raw materials in percentage by weight: 41-48% of boric sludge, 15-20% of cement, 18-25% of mineral admixture, 5-7% of sodium silicate, 3.9-5.2% of expanding agent, 8-15% of water and 2.0-3.5% of water reducing agent;
the cement-based shell layer comprises the following raw materials in percentage by weight: 46-50% of cement, 10-13% of fly ash, 4.2-5.1% of silica fume, 25.6-30.7% of water, 1.0-1.6% of water reducing agent and 3.9-5.2% of expanding agent.
2. The aggregate having an irradiation resistance function according to claim 1, wherein the thickness of the cement-based shell layer is 0.5-1.2 mm.
3. The aggregate with radiation resistance function according to claim 1 or 2, wherein the mineral admixture is fly ash, mineral powder, silica fume, metakaolin, limestone powder and nano SiO2One or more of them.
4. Aggregate with radiation resistant function according to any of claims 1-3, characterized in that the cement is portland cement and/or aluminate cement.
5. The aggregate with the radiation-resistant function according to any one of claims 1 to 4, wherein the water reducing agent is a polycarboxylic acid water reducing agent and/or a naphthalene water reducing agent, and the water reducing rate is greater than or equal to 30%; the expanding agent is one or more of calcium sulphoaluminate expanding agents, calcium oxide expanding agents and calcium sulphoaluminate and calcium oxide compound expanding agents.
6. The method for preparing the aggregate with the radiation resistance function in any one of claims 1 to 5, which is characterized by comprising the following steps:
1) mixing and stirring the boron mud, the cement, the mineral admixture, the sodium silicate, the expanding agent, the water and the water reducing agent, and granulating to obtain boron industrial waste residue regenerated aggregate;
2) mixing the boron industrial waste residue regenerated aggregate with cement, fly ash, silica fume and an expanding agent, adding water and a water reducing agent, continuously stirring, and then spreading and maintaining the obtained product;
3) and (5) steaming the cured product, and then cooling.
7. The method for preparing the aggregate with the radiation resistance function according to claim 6, wherein the mixing and stirring time in the step 1) is 5-10min, the granulation temperature is 40-60 ℃, and the particle size of the granules is 5-20 mm.
8. The preparation method of the aggregate with the radiation resistance function according to the claim 6 or 7, characterized in that the concrete preparation process of the step 2) is that the boron industrial waste residue regenerated aggregate, cement, fly ash, silica fume and an expanding agent are dry-mixed for 1-3min under the vacuum environment of 2-5kPa, then water and a water reducing agent are added, the stirring is continued for 3-8min, then the obtained product is spread out and naturally cured for 18-24 h.
9. The method for preparing the aggregate with the radiation resistance function according to any one of claims 6 to 8, wherein the steam-curing condition in the step 3) is as follows: the temperature is 60-80 ℃, the pressure is 1-2MPa, and the curing time is 4-12 h.
10. The method for preparing the aggregate with the radiation resistance function according to any one of claims 6 to 9, wherein the mass ratio of the total mass of the cement, the fly ash, the silica fume, the expanding agent, the water and the water reducing agent to the mass of the boron industrial residue regenerated aggregate is 0.22-0.45: 1.
11. An irradiation-resistant concrete comprising cement, fine aggregates, functional aggregates, water and a water reducing agent, wherein the functional aggregates are the aggregates with irradiation-resistant function of any one of claims 1 to 5 or the aggregates with irradiation-resistant function prepared by the method of any one of claims 6 to 10.
12. The radiation-resistant concrete according to claim 11, wherein the proportion of each component in the radiation-resistant concrete is as follows: based on the mass of each component in the concrete of unit volume, the cement is 360kg plus 250, the fine aggregate is 400 plus 660kg, the functional aggregate is 1200 plus 1800kg, the water is 80-160kg, and the water reducing agent is 10-15 kg.
13. The radiation-resistant concrete as claimed in claim 11 or 12, further comprising one or more of reactive powder, expanding agent and fiber.
14. The radiation-resistant concrete according to claim 13, wherein the proportion of each component in the radiation-resistant concrete is as follows: based on the mass of each component in the concrete of unit volume, the cement is 360kg plus one material, the fine aggregate is 400 plus one material, the functional aggregate is 1200 plus one material, the water is 80 to 160kg, the water reducing agent is 10 to 15kg, the active powder is less than or equal to 350kg, the expanding agent is less than or equal to 50kg, the fiber mixing amount is less than or equal to 0.025m3。
15. The radiation-resistant concrete according to claim 13 or 14, wherein the cement is portland cement and/or aluminate cement; the fine aggregate is quartz sand or common river sand, the grain size is less than 5mm, the fineness modulus is 2.6-3.2, and the active powder is one or more of silica fume, fly ash and ground slag; the water reducing agent is a polycarboxylic acid water reducing agent and/or a naphthalene water reducing agent, and the water reducing rate is more than or equal to 35 percent; the swelling agent is a calcium oxide swelling agent or a compound swelling agent; the fibers are polypropylene fibers and/or steel fibers.
16. The method for preparing the radiation-resistant concrete of any one of claims 13-15, comprising:
mixing the fine aggregate, the functional aggregate and the fiber, stirring for the first time, then adding the cement and the active powder, stirring for the second time, and finally adding the water, the water reducing agent and the expanding agent, and stirring for the third time.
17. The method of claim 16, wherein the time for the first mixing is 15-30s, the time for the second mixing is 15-30s, and the time for the third mixing is 90-180 s.
CN202010779309.0A 2020-08-05 2020-08-05 Aggregate with irradiation resistance function and preparation method thereof, irradiation-resistant concrete and preparation method thereof Pending CN111847940A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103224369A (en) * 2013-04-09 2013-07-31 四川省交通运输厅公路规划勘察设计研究院 Anti-radiation concrete produced from slag aggregate, and production method thereof
CN106588117A (en) * 2016-12-12 2017-04-26 武汉理工大学 Anti-radiation functional aggregate prepared from Cr-containing and Zn-containing electroplating sludge

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103224369A (en) * 2013-04-09 2013-07-31 四川省交通运输厅公路规划勘察设计研究院 Anti-radiation concrete produced from slag aggregate, and production method thereof
CN106588117A (en) * 2016-12-12 2017-04-26 武汉理工大学 Anti-radiation functional aggregate prepared from Cr-containing and Zn-containing electroplating sludge

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