CN113511867A - Radiation-proof concrete doped with rare earth composite material - Google Patents
Radiation-proof concrete doped with rare earth composite material Download PDFInfo
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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
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0625—Polyalkenes, e.g. polyethylene
- C04B16/0633—Polypropylene
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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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
- C04B2111/34—Non-shrinking or non-cracking materials
- C04B2111/343—Crack resistant materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
Abstract
The invention provides radiation-proof concrete doped with rare earth composite material, belonging to the field of radiation-proof concrete. The radiation-proof concrete comprises the following raw materials in parts by weight: 150-300 parts of cement, 600-900 parts of fine aggregate, 1150-1600 parts of coarse aggregate, 2-8 parts of water reducing agent, 2-5 parts of modified polypropylene fiber, 40-60 parts of radiation-proof material and 150-180 parts of water; the radiation-proof material is a rare earth polymer composite material; the modified polypropylene fiber is added with boron carbide micro powder. The radiation-proof concrete can play a good role in protecting X rays, gamma rays and neutrons simultaneously, and can reduce the pollution of heavy metals to the environment caused by the abandonment of concrete buildings; the modified polypropylene fiber is added, so that the crack resistance of the concrete can be improved, and the neutron protection effect of the concrete can be further improved.
Description
Technical Field
The invention belongs to the technical field of concrete, particularly relates to the technical field of radiation-proof concrete, and particularly relates to radiation-proof concrete doped with a rare earth composite material.
Background
The existence of many radioactive sources on the earth can cause the human body to be affected by radiation, and the radiation can be roughly divided into natural radiation and artificial radiation, and the natural radiation and the artificial radiation can emit rays with radioactive properties to a certain extent. In order to prevent various rays in the environment from damaging human bodies, radiation-proof materials are generally required to be arranged to shield various rays when radiation source buildings are built, and concrete materials are the most widely used radiation-proof materials at present and are mainly used for radiation source buildings of education, scientific research and medical institutions and the protection of inner and outer shells of nuclear reactors.
The traditional radiation-proof concrete is prepared by adding heavy metal into aggregate, and barite and ettringite are also used as the aggregate. For example, patent application CN108424017A discloses a radiation-proof concrete, which is prepared by preparing radiation-proof active aggregate and then preparing concrete by using the radiation-proof active aggregate. The radiation-proof active aggregate contains a large amount of lead powder, the lead powder is bonded together to form an inner core of the radiation-proof active aggregate when the high-iron phosphoaluminate cement is hydrated, and the high-iron phosphoaluminate cement can also react with barium hydrogen phosphate added into the radiation-proof active aggregate to generate barium aluminate calcium and barium calcium phosphoaluminate, so that the radiation-proof performance of concrete can be effectively improved. Patent application CN108793894A discloses a barite radiation-proof concrete, which takes barite sand and barite as heavy aggregates, adds lead-containing glass into the concrete, and optimizes the proportion of the heavy aggregates and the particle size of the lead-containing glass to ensure that the apparent density of the concrete reaches 3500kg/m3Thus, radiation protection performance is improved. Patent application CN108484088A discloses an ettringite radiation-proof concrete, which comprises the following raw materials in parts by weight: 10-20 parts of water, 30-50 parts of high-iron phosphoaluminate cement, 30-65 parts of fine aggregate, 35-70 parts of coarse aggregate, 0.1-1 part of water reducing agent and 2-5 parts of fiber; the coarse and fine aggregates mainly comprise ettringite. Because 32 moles of crystal water are contained in each mole of ettringite, the prepared concrete can effectively capture neutrons without forming secondary gamma rays, and has higher shielding performance on the neutrons; the aggregate is a cement hydration product, has good compatibility with cement slurry in concrete, can effectively prevent the concrete from segregation, has compact and uniform structure, and can prevent the penetration of alpha, beta and gamma rays.
However, there are problems associated with either leaded concrete or barite and kieserite concrete. Lead has high backscattering performance to low-energy X-rays, cannot bear a high-temperature environment, has low hardness and toxicity, has a weak absorption area to 40-88 keV rays, and is limited in use environment. The barite has good protection effect on X rays and gamma rays, and the protection effect on neutrons hardly meets the requirement. Although the ettringite has high hydrogen content and can effectively protect neutron radiation, the protection effect on X rays and gamma rays is difficult to meet the requirement.
Disclosure of Invention
In order to improve the radiation protection performance of concrete, not only can the concrete play a better role in protecting X rays, gamma rays and neutrons, but also can reduce the harm to the environment while meeting the mechanical property of the concrete, the invention provides the radiation protection concrete doped with the rare earth composite material, which comprises the following raw materials in parts by weight: 150-300 parts of cement, 600-900 parts of fine aggregate, 1150-1600 parts of coarse aggregate, 2-8 parts of water reducing agent, 2-5 parts of modified polypropylene fiber, 40-60 parts of radiation-proof material and 150-180 parts of water; the radiation-proof material is a rare earth composite material prepared by taking gadolinium oxide, hydrogenated nitrile rubber, stearic acid and lanthanum oxide as main raw materials; the preparation method of the modified polypropylene fiber comprises the following steps:
(1) crushing boron carbide into boron carbide micro powder with the particle size less than 1.5 mu m for later use;
(2) heating polypropylene fibers to be in a molten state, adding the boron carbide micro powder prepared in the step (1), uniformly stirring, and carrying out spinning on the molten mixture to prepare filaments with the diameter of 0.8-1.5 mm and the length of 18-25 mm, so as to obtain the modified polypropylene fibers; the addition amount of the boron carbide micro powder is 30-40% of the total mass of the modified polypropylene fiber.
Preferably, the preparation method of the radiation protection material is as follows:
s1, slowly adding the gadolinium oxide into 1.0mol/L hydrochloric acid in batches, heating to 45-55 ℃ while stirring, stopping heating when the solution is colorless and transparent while stirring, and filtering to obtain a filtrate;
s2, dropwise adding alkali liquor into the filtrate obtained in the step S1, adjusting the pH value of the solution to 8.5, filtering, washing the precipitate with water for 3-5 times, drying, and crushing to obtain powder for later use;
s3, adding methacrylic acid into hot water at the temperature of 60-70 ℃, adding the powder obtained in the step S2 in batches under a stirring state, and continuously stirring until the solution is clear; filtering, and distilling under reduced pressure to remove water; adding an organic solvent into the concentrate, keeping the temperature at 60-70 ℃, stirring until the concentrate is completely dissolved, and distilling under reduced pressure to remove the organic solvent; cooling, filtering, drying and crushing to obtain powder for later use;
s4, plasticating the hydrogenated nitrile rubber, adding stearic acid and lanthanum oxide, uniformly mixing, adding the powder obtained in the step S3 in batches, and continuously and uniformly mixing; and adding an accelerator and sulfur, continuously mixing uniformly, taking out the mixture, and crushing to obtain the radiation-proof material.
Preferably, the volume ratio of the mass of the gadolinium oxide to the hydrochloric acid in the step S1 is (0.04-0.06) kg/L.
Preferably, the alkali solution in step S2 is a sodium hydroxide solution or/and a potassium hydroxide solution.
Preferably, the ratio of the amount of methacrylic acid substance in step S3 to the amount of gadolinium oxide substance in step S1 is (2.2 to 2.6): 1.
preferably, the organic solvent in step S3 is one or more of absolute ethyl alcohol, diethyl ether and ethyl acetate.
Preferably, the mass ratio of the hydrogenated nitrile rubber, the stearic acid, the lanthanum oxide, the accelerator, the sulfur and the powder in the step S3 in the step S4 is 1 (0.02-0.05): (0.05-0.1): (0.015-0.025): 0.02-0.05): 0.2-0.4).
Further preferably, the accelerators are 2, 2' -dithiodibenzothiazyl and N-cyclohexyl-2-benzothiazylsulfenamide.
Still more preferably, the mass ratio of the 2, 2' -dithiodibenzothiazole to the N-cyclohexyl-2-benzothiazole sulfonamide is 0.5: 1.
Compared with the prior art, the invention has the beneficial effects that: the radiation-proof concrete provided by the invention mainly uses a rare earth polymer composite material as a radiation-proof agent, and the rare earth element has a special electronic layer structure, so that the weak absorption area of lead in the energy of X rays of 40-88 keV can be made up, and the rare earth element has the advantages of light weight and no toxicity, so that the radiation-proof concrete can play a good role in protecting X rays, gamma rays and neutrons at the same time, and can reduce the pollution of heavy metals to the environment caused by the abandonment of concrete buildings; the modified polypropylene fiber is added, so that the crack resistance of the concrete can be improved, and the neutron protection effect of the concrete can be further improved.
Detailed Description
The technical solution of the present invention is described in detail and fully with reference to the following examples, it is obvious that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Any equivalent changes or substitutions by those skilled in the art according to the following embodiments are within the scope of the present invention.
Example 1
The radiation-proof concrete provided by the embodiment comprises the following raw materials in parts by weight: 255 parts of P.O42.5-grade portland cement, 750 parts of river sand with the particle size smaller than 5mm, 1300 parts of crushed stone with the particle size of 5-8 mm, 5 parts of a polycarboxylic acid water reducing agent, 4 parts of modified polypropylene fiber, 50 parts of a radiation-proof material, 85 parts of fly ash with the fineness of 6.4 and 170 parts of water.
The preparation method of the modified polypropylene fiber comprises the following steps:
(1) crushing boron carbide into boron carbide micro powder with the particle size less than 1.5 mu m for later use;
(2) heating polypropylene fibers to be in a molten state, adding the boron carbide micro powder prepared in the step (1), uniformly stirring, pressing the mixture in the molten state into a spinning nozzle by using a spinning pump, and condensing filaments which flow out of the spinning nozzle and have the diameter of 3-5 mu m and the length of 5-8 mm to obtain the modified polypropylene fibers; the addition amount of the boron carbide micro powder is 35% of the total mass of the modified polypropylene fiber.
The preparation method of the radiation-proof material comprises the following steps:
s1, slowly adding 5kg of gadolinium oxide into 100L of 1.0mol/L hydrochloric acid in batches, heating to 50 +/-1 ℃ while stirring, stopping heating when stirring until the solution is colorless and transparent, and filtering to obtain a filtrate;
s2, dropwise adding a 10% sodium hydroxide solution into the filtrate obtained in the step S1, adjusting the pH value of the solution to 8.5, performing suction filtration, washing the precipitate with water for 4 times, drying, and crushing to obtain powder for later use;
s3, adding 2.8kg of methacrylic acid into 23L of hot water at 65 ℃, slowly adding the powder obtained in the step S2 in batches under the stirring state, and continuously stirring until the solution is clear; filtering, and distilling under reduced pressure to remove water; adding 25L of anhydrous ethanol into the concentrate, keeping the temperature at 65 + -2 deg.C, stirring until the concentrate is completely dissolved, and distilling under reduced pressure to remove anhydrous ethanol; cooling, filtering, drying and crushing to obtain powder for later use;
s4, plasticating 11kg of hydrogenated nitrile rubber on an open mill, adding 330g of stearic acid and 770g of lanthanum oxide, uniformly mixing, slowly adding 3.3kg of the powder obtained in the step S3 in batches, and continuously and uniformly mixing; then adding 110g of N-cyclohexyl-2-benzothiazole sulfonamide, 55g of 2, 2' -dithiodibenzothiazyl and 330g of sulfur, continuously mixing uniformly, taking out tablets, and crushing into particles with the particle size of less than 5mm to obtain the radiation-proof material.
Example 2
The radiation-proof concrete provided by the embodiment comprises the following raw materials in parts by weight: 150 parts of P.O42.5-grade portland cement, 600 parts of river sand with the particle size smaller than 5mm, 1150 parts of crushed stone with the particle size of 5-8 mm, 2 parts of a polycarboxylic acid water reducing agent, 2 parts of modified polypropylene fiber, 40 parts of a radiation-proof material, 85 parts of fly ash with the fineness of 6.4 and 150 parts of water.
The preparation method of the modified polypropylene fiber comprises the following steps:
(1) crushing boron carbide into boron carbide micro powder with the particle size less than 1.5 mu m for later use;
(2) heating polypropylene fibers to be in a molten state, adding the boron carbide micro powder prepared in the step (1), uniformly stirring, pressing the mixture in the molten state into a spinning nozzle by using a spinning pump, and condensing filaments which flow out of the spinning nozzle and have the diameter of 3-5 mu m and the length of 5-8 mm to obtain the modified polypropylene fibers; the addition amount of the boron carbide micro powder is 30% of the total mass of the modified polypropylene fiber.
The preparation method of the radiation-proof material comprises the following steps:
s1, slowly adding 5kg of gadolinium oxide into 90L of 1.0mol/L hydrochloric acid in batches, heating to 46 +/-1 ℃ while stirring, stopping heating when stirring until the solution is colorless and transparent, and filtering to obtain a filtrate;
s2, dropwise adding a 10% sodium hydroxide solution into the filtrate obtained in the step S1, adjusting the pH value of the solution to 8.5, filtering, washing the precipitate with water for 3 times, drying, and crushing to obtain powder for later use;
s3, adding 2.6kg of methacrylic acid into 23L of hot water with the temperature of 60 ℃, slowly adding the powder obtained in the step S2 in batches under the stirring state, and continuously stirring until the solution is clear; filtering, and distilling under reduced pressure to remove water; adding 25L diethyl ether into the concentrate, maintaining the temperature at 62 + -2 deg.C, stirring until the concentrate is completely dissolved, and distilling under reduced pressure to remove diethyl ether; cooling, filtering, drying and crushing to obtain powder for later use;
s4, plasticating 11kg of hydrogenated nitrile rubber on an open mill, adding 220g of stearic acid and 550g of lanthanum oxide, uniformly mixing, slowly adding 2.2kg of the powder obtained in the step S3 in batches, and continuously and uniformly mixing; then adding 110g of N-cyclohexyl-2-benzothiazole sulfonamide, 33g of 2, 2' -dithiodibenzothiazyl and 220g of sulfur, continuously mixing uniformly, taking out tablets, and crushing into particles with the particle size of less than 5mm to obtain the radiation-proof material.
Example 3
The radiation-proof concrete provided by the embodiment comprises the following raw materials in parts by weight: 300 parts of P.O42.5-grade portland cement, 900 parts of river sand with the particle size smaller than 5mm, 1600 parts of crushed stone with the particle size of 5-8 mm, 8 parts of polycarboxylic acid water reducing agent, 5 parts of modified polypropylene fiber, 60 parts of radiation-proof material, 85 parts of fly ash with the fineness of 6.4 and 180 parts of water.
The preparation method of the modified polypropylene fiber comprises the following steps:
(1) crushing boron carbide into boron carbide micro powder with the particle size less than 1.5 mu m for later use;
(2) heating polypropylene fibers to be in a molten state, adding the boron carbide micro powder prepared in the step (1), uniformly stirring, pressing the mixture in the molten state into a spinning nozzle by using a spinning pump, and condensing filaments which flow out of the spinning nozzle and have the diameter of 3-5 mu m and the length of 5-8 mm to obtain the modified polypropylene fibers; the addition amount of the boron carbide micro powder is 40% of the total mass of the modified polypropylene fiber.
The preparation method of the radiation-proof material comprises the following steps:
s1, slowly adding 5kg of gadolinium oxide into 125L of 1.0mol/L hydrochloric acid in batches, heating to 54 +/-1 ℃ while stirring, stopping heating when stirring until the solution is colorless and transparent, and filtering to obtain a filtrate;
s2, dropwise adding a 10% potassium hydroxide solution into the filtrate obtained in the step S1, adjusting the pH value of the solution to 8.5, performing suction filtration, washing the precipitate with water for 5 times, drying, and crushing to obtain powder for later use;
s3, adding 3.1kg of methacrylic acid into 23L of hot water at 70 ℃, slowly adding the powder obtained in the step S2 in batches under the stirring state, and continuously stirring until the solution is clear; filtering, and distilling under reduced pressure to remove water; adding 25L ethyl acetate into the concentrate, maintaining the temperature at 68 + -2 deg.C, stirring until the concentrate is completely dissolved, and distilling under reduced pressure to remove ethyl acetate; cooling, filtering, drying and crushing to obtain powder for later use;
s4, plasticating 11kg of hydrogenated nitrile rubber on an open mill, adding 550g of stearic acid and 1.1kg of lanthanum oxide, uniformly mixing, slowly adding 4.4kg of the powder obtained in the step S3 in batches, and continuously uniformly mixing; then adding 110g of N-cyclohexyl-2-benzothiazole sulfonamide, 44g of 2, 2' -dithiodibenzothiazyl and 550g of sulfur, continuously mixing uniformly, taking out tablets, and crushing into particles with the particle size of less than 5mm to obtain the radiation-proof material.
Comparative example 1
The radiation-proof concrete prepared by the comparative example comprises the following raw materials in parts by weight: 255 parts of P.O42.5-grade portland cement, 750 parts of river sand with the particle size smaller than 5mm, 1300 parts of crushed stone with the particle size of 5-8 mm, 5 parts of a polycarboxylic acid water reducing agent, 50 parts of a radiation-proof material, 85 parts of fly ash with the fineness of 6.4 and 170 parts of water. Compared with the example 1, the radiation-proof concrete of the comparative example does not add the modified polypropylene fiber; the preparation method of the radiation protective material is the same as that of the embodiment 1.
Comparative example 2
The radiation-proof concrete prepared by the comparative example comprises the following raw materials in parts by weight: 255 parts of P.O42.5-grade portland cement, 750 parts of river sand with the particle size smaller than 5mm, 1300 parts of crushed stone with the particle size of 5-8 mm, 5 parts of a polycarboxylic acid water reducing agent, 4 parts of modified polypropylene fiber, 85 parts of fly ash with the fineness of 6.4 and 170 parts of water. That is, compared with example 1, the radiation-proof concrete of this comparative example does not have a radiation-proof material added; the modified polypropylene fiber was prepared in the same manner as in example 1.
Comparative example 3
The radiation protective concrete prepared in this comparative example is the same as example 1 except that: in the step (1), the boron carbide is crushed into boron carbide micro powder with the grain diameter of 5 mu m.
Performance testing
The radiation-proof performance of the radiation-proof concrete prepared in each embodiment and comparative example is measured according to the national standard GB18871-2002 basic standard for ionizing radiation protection and radiation source safety, and the test results are shown in Table 1; the mechanical properties of the radiation-proof concrete prepared in each example and comparative example are measured according to GB/T50081-2019 'test method Standard for physical mechanical Properties of concrete', and the test results are shown in Table 2.
TABLE 1 Linear attenuation coefficient (cm) of radiation-proof concrete-1)
TABLE 2 mechanical testing results of radiation-proof concrete
| 28d compressive Strength (MPa) | 28d breaking strength (MPa) | |
| Example 1 | 34.8 | 8.2 |
| Example 2 | 32.5 | 7.6 |
| Example 3 | 35.9 | 9.1 |
| Comparative example 1 | 29.6 | 6.2 |
| Comparative example 2 | 31.4 | 7.3 |
| Comparative example 3 | 28.3 | 5.9 |
As can be seen from the data in tables 1 and 2, in comparison with example 1, in comparative example 1, when no modified polypropylene fiber is added, the concrete is easy to crack, the radiation protection performance is obviously reduced, and the 28d compressive flexural strength is also obviously reduced. Compared with the embodiment 1, the comparative example 2 has the advantages that the radiation-proof performance of the concrete is greatly reduced only by the radiation-proof performance of the modified polypropylene fiber and the concrete without adding the radiation-proof material; the 28d compressive and flexural strength was slightly reduced. Compared with the embodiment 1, the granularity of the boron carbide micro powder is increased, the strength performance of the modified polypropylene fiber is obviously poor, and the strength performance of the concrete is also obviously poor, and although the radiation-proof material and the modified polypropylene fiber are added, the radiation-proof performance is still reduced due to the problem of cracking of the concrete.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The present invention may be subject to various modifications and changes by any person skilled in the art. Any simple equivalent changes and modifications made in accordance with the protection scope of the present application and the content of the specification are intended to be included within the protection scope of the present invention.
Claims (9)
1. The radiation-proof concrete doped with the rare earth composite material is characterized by comprising the following raw materials in parts by weight: 150-300 parts of cement, 600-900 parts of fine aggregate, 1150-1600 parts of coarse aggregate, 2-8 parts of water reducing agent, 2-5 parts of modified polypropylene fiber, 40-60 parts of radiation-proof material and 150-180 parts of water; the radiation-proof material is a rare earth composite material prepared by taking gadolinium oxide, hydrogenated nitrile rubber, stearic acid and lanthanum oxide as main raw materials; the preparation method of the modified polypropylene fiber comprises the following steps:
(1) crushing boron carbide into boron carbide micro powder with the particle size less than 1.5 mu m for later use;
(2) heating polypropylene fibers to be in a molten state, adding the boron carbide micro powder prepared in the step (1), uniformly stirring, and carrying out spinning on the molten mixture to prepare filaments with the diameter of 0.8-1.5 mm and the length of 18-25 mm, so as to obtain the modified polypropylene fibers; the addition amount of the boron carbide micro powder is 30-40% of the total mass of the modified polypropylene fiber.
2. The radiation protection concrete doped with rare earth composite material of claim 1 is characterized in that the preparation method of the radiation protection material is as follows:
s1, slowly adding the gadolinium oxide into 1.0mol/L hydrochloric acid in batches, heating to 45-55 ℃ while stirring, stopping heating when the solution is colorless and transparent while stirring, and filtering to obtain a filtrate;
s2, dropwise adding alkali liquor into the filtrate obtained in the step S1, adjusting the pH value of the solution to 8.5, filtering, washing the precipitate with water for 3-5 times, drying, and crushing to obtain powder for later use;
s3, adding methacrylic acid into hot water at the temperature of 60-70 ℃, adding the powder obtained in the step S2 in batches under a stirring state, and continuously stirring until the solution is clear; filtering, and distilling under reduced pressure to remove water; adding an organic solvent into the concentrate, keeping the temperature at 60-70 ℃, stirring until the concentrate is completely dissolved, and distilling under reduced pressure to remove the organic solvent; cooling, filtering, drying and crushing to obtain powder for later use;
s4, plasticating the hydrogenated nitrile rubber, adding stearic acid and lanthanum oxide, uniformly mixing, adding the powder obtained in the step S3 in batches, and continuously and uniformly mixing; and adding an accelerator and sulfur, continuously mixing uniformly, taking out the mixture, and crushing to obtain the radiation-proof material.
3. The radiation-proof concrete doped with rare earth composite material as claimed in claim 2, wherein the volume ratio of the mass of gadolinium oxide to hydrochloric acid in step S1 is (0.04-0.06) kg/L.
4. The radiation protective concrete doped with rare earth composite material as claimed in claim 2, wherein the alkali solution in step S2 is sodium hydroxide solution or/and potassium hydroxide solution.
5. The radiation protective concrete doped with rare earth composite material as claimed in claim 2, wherein the ratio of the amount of methacrylic acid substance in step S3 to the amount of gadolinium oxide substance in step S1 is (2.2-2.6): 1.
6. the radiation-proof concrete doped with rare earth composite material as claimed in claim 2, wherein the organic solvent in step S3 is one or more of absolute ethyl alcohol, ethyl ether and ethyl acetate.
7. The anti-radiation concrete doped with rare earth composite material as claimed in claim 2, wherein the mass ratio of the hydrogenated nitrile rubber, the stearic acid, the lanthanum oxide, the accelerator, the sulfur and the powder in the step S3 in the step S4 is 1 (0.02-0.05): 0.05-0.1): 0.015-0.025): 0.02-0.05): 0.2-0.4.
8. The radiation protective concrete doped with rare earth composite material as claimed in claim 7, wherein the accelerant is 2, 2' -dithiodibenzothiazyl and N-cyclohexyl-2-benzothiazole sulfenamide.
9. The radiation protective concrete doped with rare earth composite material as claimed in claim 8, wherein the mass ratio of the 2, 2' -dithiodibenzothiazyl to the N-cyclohexyl-2-benzothiazole sulfenamide is 0.5: 1.
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| CN115140985A (en) * | 2022-08-08 | 2022-10-04 | 华北水利水电大学 | Boron carbide ultra-high performance concrete and preparation method and application thereof |
| CN116553886A (en) * | 2023-04-22 | 2023-08-08 | 北京民佳混凝土有限公司 | Crack-resistant waterproof concrete and preparation method thereof |
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