CN109592961B - High-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete - Google Patents

High-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete Download PDF

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CN109592961B
CN109592961B CN201910026857.3A CN201910026857A CN109592961B CN 109592961 B CN109592961 B CN 109592961B CN 201910026857 A CN201910026857 A CN 201910026857A CN 109592961 B CN109592961 B CN 109592961B
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strontium
boron
radiation
phosphoaluminate
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CN109592961A (en
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王守德
毕海峰
刘浩
黄永波
芦令超
程新
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University of Jinan
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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
    • C04B28/34—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 cold phosphate binders
    • C04B28/344—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 cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
    • 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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/02—Phosphate cements
    • C04B12/022—Al-phosphates
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/32—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
    • 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
    • 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
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses high-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete which comprises the following components in parts by weight: 30-50 parts of boron-containing strontium phosphoaluminate cement, 45-70 parts of radiation-proof coarse aggregate, 35-55 parts of radiation-proof fine aggregate, 0.5-1 part of additive and 15-25 parts of water. The boron-containing strontium phosphoaluminate cement used in the invention can effectively shield and protect alpha, beta, gamma and X rays, can also absorb and protect neutron radiation, and combines the radiation protection performance of the aggregate, so that the boron-containing strontium phosphoaluminate cement-based nuclear power concrete has stronger radiation protection performance, and meanwhile, the cement clinker has excellent high temperature resistance, so that the condition of shortening the service life of a concrete structure is avoided. In a word, the invention is excellent high-quality concrete which can be used for nuclear power engineering protection and nuclear waste treatment, and has wide application prospect in the aspect of nuclear power radiation protection.

Description

High-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete
Technical Field
The invention relates to high-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete, and belongs to the technical field of special cement concrete.
Background
With the development of society, the traditional fossil fuel is increasingly deficient, and nuclear energy as an efficient energy source gradually draws attention of all countries in the world. In order for the core to develop efficiently and quickly, the problems caused by the core energy must be handled correctly. The nuclear reaction of nuclear energy generates a great deal of radiation, such as alpha, beta, gamma, X-ray and neutron ray, which can induce a variety of diseases and genetic variation, and pose a great threat to the environment and human health. In order to prevent the radiation from damaging the human body and the environment, a protective body must be arranged when a building provided with a radiation source is built. Cement concrete is currently the most widely used radiation shielding material, such as for the fabrication of the inner and outer shells of nuclear reactors and the curing of nuclear waste. The existing radiation-proof protective materials mainly comprise steel plates, lead plates, water, concrete and the like, the sources, the cost and the implementation difficulty of the materials are comprehensively considered, and the comprehensive technical and economic effects of the concrete are undoubtedly the best among the radiation-proof protective materials.
The nuclear power protection is mostly of a multilayer structure at present, protection means such as steel plates and lead plates are arranged in front of a cement concrete structure, much heat is dissipated before radiation reaches the cement concrete structure, the temperature of the cement concrete structure can reach about 100 ℃, but even the temperature of 100 ℃ is a great test for the concrete structure, and the service life of the concrete structure can be shortened. On the other hand, the radiation protection capability of concrete is closely related to the content of heavy metal in single-component concrete, so that the traditional concrete mainly selects ore containing heavy metal elements as coarse aggregate and fine aggregate to provide radiation protection performance, and a report is made on the fact that cement clinker has the radiation protection performance. With the development of nuclear energy, the nuclear power concrete has higher requirements, so that the development of novel, economic, safe and reasonable radiation-proof concrete by preparing the high-temperature-resistant radiation-proof cement clinker has great strategic significance and positive social significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides high-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete. The concrete is mainly made of boron-strontium-containing phosphoaluminate cement (strength grade is not less than 42.5 grade, specific surface area is greater than 320 m)2And/kg), radiation-proof coarse aggregate and radiation-proof fine aggregate, and the concrete has strong absorption and shielding effects on alpha, beta, gamma, X rays and neutron rays and has excellent high-temperature resistance.
The invention adopts the following technical scheme:
the high-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete is prepared from the following raw materials in parts by weight: 30-50 parts of boron-containing strontium phosphoaluminate cement, 45-70 parts of radiation-proof coarse aggregate, 35-55 parts of radiation-proof fine aggregate, 0.5-1 part of additive and 15-25 parts of water; the clinker mineral phase of the boron-strontium-containing phosphoaluminate cement comprises the following components in percentage by mass: 32-55% of strontium calcium phosphoaluminate, 20-30% of strontium calcium aluminate, 15-20% of calcium aluminate, 5-15% of dicalcium ferrite and 5-8% of calcium borate; wherein the chemical molecular formula of the strontium calcium phosphoaluminate ore phase is C8-xSrxA6P，2<x<2.4。
The anti-radiation coarse aggregate is one or a combination of several of hematite, serpentine and limonite heavy aggregate, and the particle size range is 4.75 mm-26.5 mm.
The radiation-proof fine aggregate is a mixture of barite powder and hematite sand in any proportion, and the particle size range is 0.15-4.75 mm.
The additive is prepared from boric acid: lithium carbonate: the polycarboxylate superplasticizer is composed according to the mass ratio of 2-6: 2-4: 1.
The raw material oxide of the boron-strontium-containing phosphoaluminate cement clinker comprises the following components in percentage by mass: 10-25% of SrO and Al2O3 30～41％、CaO 20～38％、P2O5 5～8％、Fe2O3 4～13％、B2O3 3～8％。
The strength grade of the boron-strontium-containing phosphoaluminate cement used by the invention is not lower than 42.5 grade, and the specific surface area is more than 320m2Per kg; the radiation-proof coarse aggregate used in the invention is one or a combination of more of hematite, serpentine, limonite and the like. The hematite has large apparent density, small crushing index value and water absorption and good gamma ray prevention effect. The serpentine and the limonite both contain certain crystal water, and the neutron ray preventing effect is good. The radiation-proof fine aggregate is ground barite powder and hematite sand. The barite and the hematite have large apparent density, high crushing index value and good gamma ray prevention effect. The radiation-proof performance is better after being ground into fine aggregate, but when the hematite is used as the fine aggregate, Fe needs to be selected2O3Hematite with content not less than 60%. In order to ensure that the performance of the radiation-proof concrete meets the application standard in the nuclear power field, the particle size ranges of the coarse aggregate and the fine aggregate are respectively controlled to be 4.75-26.5 mm and 0-4.75 mm. The radiation protection performance of the traditional nuclear power concrete comes from aggregate, but the invention mixes elements such as boron, strontium and the like in the phosphoaluminate cement clinker, a large amount of light elements contained in the cement clinker and equivalent amount of bound water (such as hydration product 2 CaO. Al of calcium phosphoaluminate (strontium) calcium)2O3·8H2O contains 8 crystal waters), so the clinker itself has a strong absorption and shielding effect on alpha, beta, gamma, X-rays and neutron rays.
The invention has the beneficial effects that: the cement clinker used in the invention contains a certain amount of strontium boron element, other light elements and equivalent bound water (such as hydration product of calcium (strontium) phosphoaluminate 2 CaO. Al)2O3·8H2O contains 8 crystal water), and the concrete has radiation-proof performance, so that the concrete prepared by the O has strong absorption and shielding effects on alpha, beta, gamma, X rays and neutron rays, and can be used as buildings in the aspects of radiation protection, nuclear power and the like. Meanwhile, the cement clinker has excellent high temperature resistance, so that the condition of shortening the service life of a concrete structure is avoided. In conclusion, the invention is excellent high-quality concrete which can be used for nuclear power engineering protection and nuclear waste treatment, and is believed to have wide application prospect in the aspect of nuclear power radiation protection.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples
To fully illustrate the application value of the present invention, specific examples are now incorporated. Firstly, proportioning raw materials according to the parts by weight (unit: kg), placing the raw materials into a concrete mixer after proportioning is finished, stirring and forming the raw materials, finally placing the raw materials into a curing chamber for curing, and inspecting the performance of the concrete after the specified curing time is reached. The specific formulation is shown in table 1.
TABLE 1 raw material composition
Figure BDA0001942807920000031
The concrete test block prepared by the experimental group is subjected to performance test according to relevant standard regulations and test methods in GBT 34008-2017 radiation-proof concrete, and specific test results are shown in tables 2-3.
Table 2 results of performance testing
Figure BDA0001942807920000032
Table 3 results of performance testing
Figure BDA0001942807920000033
As can be seen from Table 2, the compressive strength and the flexural strength of each example are good, the mechanical property requirement of nuclear power cement is met, and the compressive strength is improved by 20-40% compared with that of common silicate concrete. The high-temperature compressive strength of the concrete is much higher than that of common silicate concrete, which shows that the concrete has excellent high-temperature resistance. In addition, the drying shrinkage, the apparent density, the carbonization depth and the slump of the concrete all meet the national standards of nuclear power concrete. And it can be seen from table 3 that the concrete has good radiation protection performance. The influence of various factors is considered as much as possible in the example, and the example is not an optimal scheme and is enough to illustrate the application value of the boron-containing strontium-rich sulphoaluminate cement clinker.

Claims (3)

1. The high-temperature-resistant boron-strontium-containing phosphoaluminate cement-based nuclear power concrete is characterized by comprising the following raw materials in parts by weight: 30-50 parts of boron-containing strontium phosphoaluminate cement, 45-70 parts of radiation-proof coarse aggregate, 35-55 parts of radiation-proof fine aggregate, 0.5-1 part of additive and 15-25 parts of water; the clinker mineral phase of the boron-strontium-containing phosphoaluminate cement comprises the following components in percentage by mass: 32-55% of strontium calcium phosphoaluminate, 20-30% of strontium calcium aluminate, 15-20% of calcium aluminate, 5-15% of dicalcium ferrite and 5-8% of calcium borate; wherein the chemical molecular formula of the strontium calcium phosphoaluminate ore phase is C8-xSrxA6P，2<x<2.4; the anti-radiation coarse aggregate is one or a combination of more of hematite, serpentine and limonite heavy aggregate, and the particle size range is 4.75-26.5 mm; the radiation-proof fine aggregate is a mixture of barite powder and hematite sand in any proportion, and the particle size range is 0.15-4.75 mm; the additive is prepared from boric acid: lithium carbonate: the polycarboxylate superplasticizer is composed according to the mass ratio of 2-6: 2-4: 1.
2. According to claim 1The boron-containing strontium-rich phosphoaluminate cement-based nuclear power concrete is characterized in that Fe in hematite sand2O3The content is more than or equal to 60 percent.
3. The boron-containing strontium-rich phosphoaluminate cement-based nuclear power concrete according to claim 1, wherein the raw material oxide composition and the mass percentage of the boron-containing strontium phosphoaluminate cement clinker are as follows: 10-25% of SrO and Al2O3 30～41％、CaO 20～38％、P2O5 5～8％、Fe2O3 4～13％、B2O3 3～8％。
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