CN111205067A - Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof - Google Patents
Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof Download PDFInfo
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- CN111205067A CN111205067A CN202010043549.4A CN202010043549A CN111205067A CN 111205067 A CN111205067 A CN 111205067A CN 202010043549 A CN202010043549 A CN 202010043549A CN 111205067 A CN111205067 A CN 111205067A
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C03C12/00—Powdered glass; Bead compositions
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62665—Flame, plasma or melting treatment
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
Abstract
The invention discloses a glass-ceramic material for cooperative protection of neutrons and gamma rays and a preparation method thereof. The technical scheme is as follows: and ball-milling, drying and crushing the aluminum borate powder to obtain an aluminum borate precursor. Mixing 30.0-40.0 wt% of boron oxide, 20.0-30.0 wt% of bismuth oxide, 5.0-10.0 wt% of phosphorus oxide, 5.0-10.0 wt% of silicon oxide, 10.0-15.0 wt% of barium oxide and 5.0-10.0 wt% of gadolinium oxide as raw materials, melting at 1400-1600 ℃, water quenching, drying and crushing to obtain the glass shielding agent containing the radiation shielding component. Mixing an aluminum borate precursor, a glass shielding agent containing radiation shielding components and a binding agent, carrying out mechanical pressing, drying, carrying out heat preservation at 1000-1500 ℃ for 60-300 min, and carrying out furnace cooling to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection. The product prepared by the invention has high compression strength, excellent shielding performance, strong water-heat erosion resistance, excellent irradiation resistance and good thermal shock stability.
Description
Technical Field
The invention relates to the technical field of glass-ceramic materials with cooperative protection. In particular to a glass-ceramic material for the cooperative protection of neutrons and gamma rays and a preparation method thereof.
Background
The energy shortage is a common problem facing the world, and two most effective ways for solving the energy shortage are the development of novel energy and the saving and consumption reduction of the energy. For new energy, nuclear energy has become three power energy supply pillars which are called together with thermal power and hydropower in the world due to the characteristics of less resource consumption, strong energy supply capacity and the like, and is widely used by countries in the world. In recent years, with the continuous development of nuclear power, people are aware of the service life problem of materials in nuclear reactors. As the nuclear energy reactor inevitably generates an irradiation effect in the operation process, the materials in the system are subjected to irradiation modification, the physical and chemical properties are obviously changed, and the safety operation of the reactor is influenced unpredictably, so that higher technical requirements are put forward on the materials used by the nuclear energy system.
The current preparation methods of glass-ceramic materials are as follows: melting, sintering and sol-gel processes. But the large-scale popularization is difficult due to the fact that the production process of the melting method and the sol-gel method is not easy to control and the production period is long. The sintering method is used for producing the glass-ceramic material by adding the ceramic phase into the glass powder, and has extremely high application value due to the characteristics of simple method, easy control of the production process and high yield.
The radiation shielding material is an important component of the nuclear energy system, can effectively reduce the harm of secondary radiation to workpiece equipment and operators, and can improve the safety factor of the nuclear energy system. At present, the technologies for preparing radiation shielding materials include: the patent technology of 'formulation of radiation shielding lead alloy' (CN201810476206.X) discloses a radiation shielding material with a multilayer special-shaped embedded structure and taking lead alloy as a main raw material, and although the shielding performance of a radiation protection material in the technology is enhanced, the radiation shielding material has inevitable negative effects on human bodies and the environment due to excessively high lead content. At present, materials for a nuclear energy thermal insulation system mainly comprise glass products, and although the materials have good radiation protection capability, the materials have extremely high brittleness and are not beneficial to construction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide the preparation method of the environment-friendly and simple-process glass-ceramic material for the cooperative protection of neutrons and gamma rays.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2-3: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 20-24 hours at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 30.0-40.0 wt% of boron oxide, 20.0-30.0 wt% of bismuth oxide, 5.0-10.0 wt% of phosphorus oxide, 5.0-10.0 wt% of silicon oxide, 10.0-15.0 wt% of barium oxide and 5.0-10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1400-1600 ℃, water quenching, drying at 100-120 ℃ for 10-15 h, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the binding agent according to the mass ratio of 1: 0.2-0.7: 0.006-0.0085 to obtain a mixture II; and then, carrying out mechanical pressing forming on the mixture II under the condition of 120-150 MPa, drying for 20-24 h at the temperature of 100-120 ℃, then heating to 1000-1500 ℃ under the conditions of air atmosphere and normal pressure, keeping the temperature for 60-300 min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The aluminum borate powder comprises the following components: 2Al2O3·B2O3And 9Al2O3·2B2O3Is greater than 95 wt%, Al2O3The content is less than 3 wt%, and the water content is less than 2 wt%.
The purity of the boron oxide is more than 99.9 percent, and the particle size is less than 0.5 um.
The bismuth oxide is analytically pure.
The purity of the phosphorus oxide is more than 99.9 percent, and the particle size is less than 0.5 um.
The purity of the silicon oxide is more than 99.9 percent, and the particle size is less than 0.5 um.
The purity of the barium oxide is analytically pure.
The purity of the gadolinium oxide is more than 99%, and the particle size is less than 2.5 um.
The binding agent is one of polyvinyl alcohol solution, carboxymethyl cellulose and aluminum sol.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the glass-ceramic material for neutron and gamma ray cooperative protection, which is prepared by the invention, does not contain lead, is not easy to cause harm to human bodies, and is environment-friendly compared with the existing radiation shielding material with a multilayer special-shaped embedded structure, in which lead alloy is used as a main raw material; the invention adopts a sintering method, does not need a nucleation process, has simple process and shortens the production period.
2. The invention takes the aluminum borate precursor and the glass shielding agent containing the radiation shielding component as main raw materials, the aluminum borate precursor can form a columnar, rod-shaped or flaky crystal structure at high temperature, the crack expansion of the product under load can be obviously reduced, the compression resistance of the product is improved, and the compression strength is high.
3. After the glass-ceramic material with the cooperative protection of neutrons and gamma rays, which is prepared by the invention, is irradiated for a long time at a high dose, generated helium bubbles are easy to slowly release along a crystal boundary, so that the swelling and peeling of a product can be reduced, and the shielding performance and the irradiation resistance are improved.
4. The glass-ceramic material with the cooperative protection of neutrons and gamma rays, prepared by the invention, still has high strength retention rate after multiple thermal shock experiments, and has good thermal shock stability; in addition, due to the natural hydrophobicity of the glass shielding agent, the product has strong hot erosion resistance.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays, which is prepared by the invention, is detected as follows: the bulk density is 3.1 to 4.7g/cm3The normal-temperature compressive strength is 296-468 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 2.4-7.6%; placing the glass-ceramic material with the synergistic protection of neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 3.5-6.4%, and the strength loss rate is 2.2-8.1%; the strength loss rate of the steel sheet is 8.7-10.5% in the case of heat cycling (air cooling) at 200 ℃ for five times, 12.6-18.4% in the case of heat cycling (air cooling) at 300 ℃ for five times, and 21.9-25.1% in the case of heat cycling (air cooling) at 400 ℃ for five times.
Therefore, the invention has the characteristics of environmental friendliness and simple process; the prepared glass-ceramic material for the cooperative protection of neutrons and gamma rays has the advantages of high compressive strength, excellent shielding performance, strong hot erosion resistance, excellent irradiation resistance and good thermal shock stability.
Detailed Description
The invention is further described with reference to specific embodiments, which do not limit the scope of the invention.
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method comprises the following steps:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2-3: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 20-24 hours at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 30.0-40.0 wt% of boron oxide, 20.0-30.0 wt% of bismuth oxide, 5.0-10.0 wt% of phosphorus oxide, 5.0-10.0 wt% of silicon oxide, 10.0-15.0 wt% of barium oxide and 5.0-10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1400-1600 ℃, water quenching, drying at 100-120 ℃ for 10-15 h, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the binding agent according to the mass ratio of 1: 0.2-0.7: 0.006-0.0085 to obtain a mixture II; and then, carrying out mechanical pressing forming on the mixture II under the condition of 120-150 MPa, drying for 20-24 h at the temperature of 100-120 ℃, then heating to 1000-1500 ℃ under the conditions of air atmosphere and normal pressure, keeping the temperature for 60-300 min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The binding agent is one of polyvinyl alcohol solution, carboxymethyl cellulose and aluminum sol.
In this embodiment:
the aluminum borate powder comprises the following components: 2Al2O3·B2O3And 9Al2O3·2B2O3Is greater than 95 wt%, Al2O3The content is less than 3wt percent,the water content is less than 2 wt%;
the purity of the boron oxide is more than 99.9 percent, and the particle size is less than 0.5 um;
the bismuth oxide is analytically pure;
the purity of the phosphorus oxide is more than 99.9 percent, and the particle size is less than 0.5 um;
the purity of the silicon oxide is more than 99.9 percent, and the particle size is less than 0.5 um;
the purity of the barium oxide is analytically pure;
the purity of the gadolinium oxide is more than 99%, and the particle size is less than 2.5 um.
The detailed description is omitted in the embodiments.
Example 1
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method in this example is:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 20h at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 30.0 wt% of boron oxide, 30.0 wt% of bismuth oxide, 10.0 wt% of phosphorus oxide, 10.0 wt% of silicon oxide, 10.0 wt% of barium oxide and 10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1400 ℃, performing water quenching, drying for 15 hours at 100 ℃, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the bonding agent according to the mass ratio of 1: 0.4: 0.007 to obtain a mixture II; and then, performing mechanical pressing molding on the mixture II under the condition of 120MPa, drying for 22h at the temperature of 110 ℃, then heating to 1000 ℃ under the conditions of air atmosphere and normal pressure, preserving heat for 300min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The binding agent is polyvinyl alcohol solution.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays prepared in the embodiment is detected as follows: the bulk density is 3.8g/cm3The normal-temperature compressive strength is 388 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 4.8%; placing the glass-ceramic material cooperatively protected by neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 6.4%, and the strength loss rate is 2.2%; the strength loss rate was 9.1% for five cycles of 200 ℃ heat cycle (air-cooling), 12.6% for five cycles of 300 ℃ heat cycle (air-cooling), and 21.9% for five cycles of 400 ℃ heat cycle (air-cooling).
Example 2
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method in this example is:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2.3: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 22h at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 33.0 wt% of boron oxide, 27.0 wt% of bismuth oxide, 5.0 wt% of phosphorus oxide, 10.0 wt% of silicon oxide, 15.0 wt% of barium oxide and 10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1450 ℃, performing water quenching, drying for 14 hours at 110 ℃, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the bonding agent according to the mass ratio of 1: 0.2: 0.006 to obtain a mixture II; and then, performing mechanical pressing molding on the mixture II under the condition of 130MPa, drying for 20h at 100 ℃, then heating to 1125 ℃ under the conditions of air atmosphere and normal pressure, preserving heat for 240min, and cooling along with the furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The binding agent is carboxymethyl cellulose.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays prepared in the embodiment is detected as follows: the bulk density is 4.3g/cm3The normal temperature compressive strength is 425 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 3.7%; placing the glass-ceramic material cooperatively protected by neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 4.4%, and the strength loss rate is 3.7%; the strength loss rate was 10.1% for five cycles of 200 ℃ heat cycle (air-cooling), 13.8% for five cycles of 300 ℃ heat cycle (air-cooling), and 23.5% for five cycles of 400 ℃ heat cycle (air-cooling).
Example 3
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method in this example is:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2.5: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 21h at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 36.0 wt% of boron oxide, 29.0 wt% of bismuth oxide, 7.0 wt% of phosphorus oxide, 5.0 wt% of silicon oxide, 15.0 wt% of barium oxide and 8.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1500 ℃, performing water quenching, drying at 105 ℃ for 12h, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the binding agent according to the mass ratio of 1: 0.3: 0.0065 to obtain a mixture II; and then, performing mechanical pressing molding on the mixture II under the condition of 150MPa, drying for 21h at 105 ℃, then heating to 1375 ℃ under the conditions of air atmosphere and normal pressure, preserving heat for 120min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The bonding agent is alumina sol.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays prepared in the embodiment is detected as follows: the bulk density is 4.7g/cm3The normal temperature compressive strength is 468 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 2.4%; placing the glass-ceramic material cooperatively protected by neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 3.5%, and the strength loss rate is 6.4%; the strength loss rate was 10.5% for five cycles of 200 ℃ heat cycle (air-cooling), 17.3% for five cycles of 300 ℃ heat cycle (air-cooling), and 25.1% for five cycles of 400 ℃ heat cycle (air-cooling).
Example 4
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method in this example is:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2.8: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 23 hours at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 40.0 wt% of boron oxide, 24.0 wt% of bismuth oxide, 9.0 wt% of phosphorus oxide, 9.0 wt% of silicon oxide, 13.0 wt% of barium oxide and 5.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1550 ℃, water-quenching, drying at 115 ℃ for 13h, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Step three, mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the bonding agent according to the mass ratio of 1: 0.6: 0.008 to obtain a mixture II; and then, performing mechanical pressing molding on the mixture II under the condition of 140MPa, drying for 23h at the temperature of 115 ℃, then heating to 1250 ℃ under the conditions of air atmosphere and normal pressure, preserving heat for 180min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The binding agent is polyvinyl alcohol solution.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays prepared in the embodiment is detected as follows: the bulk density is 3.5g/cm3The normal-temperature compressive strength is 339 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 6.3%; placing the glass-ceramic material cooperatively protected by neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 5.1%, and the strength loss rate is 8.1%; the strength loss rate was 9.6% for five cycles of 200 ℃ heat cycle (air-cooling), 18.4% for five cycles of 300 ℃ heat cycle (air-cooling), and 24.4% for five cycles of 400 ℃ heat cycle (air-cooling).
Example 5
A glass-ceramic material for neutron and gamma ray cooperative protection and a preparation method thereof. The preparation method in this example is:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 3: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; and then drying the ball grinding material for 24 hours at normal temperature, and crushing to obtain the aluminum borate precursor.
Step two, uniformly mixing 38.0 wt% of boron oxide, 20.0 wt% of bismuth oxide, 10.0 wt% of phosphorus oxide, 10.0 wt% of silicon oxide, 12.0 wt% of barium oxide and 10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; and melting the mixture I at 1600 ℃, water quenching, drying for 10 hours at 120 ℃, and crushing until the particle size is less than 0.147mm to obtain the glass shielding agent containing the radiation shielding component.
Mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the binding agent according to the mass ratio of 1: 0.7: 0.0085 to obtain a mixture II; and then, performing mechanical pressing molding on the mixture II under the condition of 135MPa, drying for 24 hours at the temperature of 120 ℃, then heating to 1500 ℃ under the conditions of air atmosphere and normal pressure, preserving heat for 60 minutes, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
The binding agent is carboxymethyl cellulose.
The glass-ceramic material for the cooperative protection of neutrons and gamma rays prepared in the embodiment is detected as follows: the bulk density is 3.1g/cm3The normal-temperature compressive strength is 296 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 7.6%; placing the glass-ceramic material cooperatively protected by neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 5.8%, and the strength loss rate is 4.9%; the strength loss rate was 8.7% for five cycles of 200 ℃ heat cycle (air-cooling), 15.5% for five cycles of 300 ℃ heat cycle (air-cooling), and 22.8% for five cycles of 400 ℃ heat cycle (air-cooling).
Compared with the prior art, the specific implementation mode has the following positive effects:
1. the glass-ceramic material for neutron and gamma ray cooperative protection prepared by the specific embodiment does not contain lead, is not easy to cause harm to human bodies, and is environment-friendly compared with the existing radiation shielding material with a multilayer special-shaped embedded structure and taking lead alloy as a main raw material; the specific embodiment adopts a sintering method, does not need a nucleation process, has simple process and shortens the production period.
2. The specific embodiment takes an aluminum borate precursor and a glass shielding agent containing radiation shielding components as main raw materials, and the aluminum borate precursor can form a columnar, rod-shaped or flaky crystal structure at high temperature, so that crack propagation of a product under load can be remarkably reduced, the compression resistance of the product is improved, and the compression strength of the product is high.
3. After the glass-ceramic material with the cooperative protection of neutrons and gamma rays, which is prepared by the specific embodiment, is irradiated at a high dose for a long time, generated helium bubbles are easy to slowly release along a grain boundary, so that the swelling and peeling of a product can be reduced, and the shielding performance and the irradiation resistance are improved.
4. The glass-ceramic material for neutron and gamma ray cooperative protection prepared by the embodiment has high strength retention rate after multiple thermal shock experiments, and has good thermal shock stability; in addition, due to the natural hydrophobicity of the glass shielding agent, the product has strong hot erosion resistance.
The glass-ceramic material for neutron and gamma ray cooperative protection prepared by the embodiment is detected as follows: the bulk density is 3.1 to 4.7g/cm3The normal-temperature compressive strength is 296-468 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the glass-ceramic material (with the thickness of 2cm) with the cooperative protection of neutrons and gamma rays, and the penetration rate of the neutrons and the gamma rays is 2.4-7.6%; placing the glass-ceramic material with the synergistic protection of neutrons and gamma rays in a hydrothermal kettle, and irradiating for 15 days at 180 ℃, wherein the mass loss rate is 3.5-6.4%, and the strength loss rate is 2.2-8.1%; the strength loss rate of the steel sheet is 8.7-10.5% in the case of heat cycling (air cooling) at 200 ℃ for five times, 12.6-18.4% in the case of heat cycling (air cooling) at 300 ℃ for five times, and 21.9-25.1% in the case of heat cycling (air cooling) at 400 ℃ for five times.
Therefore, the specific implementation mode has the characteristics of environmental friendliness and simple process; the prepared glass-ceramic material for the cooperative protection of neutrons and gamma rays has the advantages of high compressive strength, excellent shielding performance, strong hot erosion resistance, excellent irradiation resistance and good thermal shock stability.
Claims (10)
1. A preparation method of a glass-ceramic material for cooperative protection of neutrons and gamma rays is characterized by comprising the following steps:
step one, taking ethanol as a ball milling medium, and ball milling aluminum borate powder to obtain a ball grinding material, wherein the mass ratio of zirconium oxide grinding balls to aluminum borate powder is 2-3: 1, and the particle size of the aluminum borate powder is less than 0.147 mm; then drying the ball grinding material for 20-24 hours at normal temperature, and crushing to obtain an aluminum borate precursor;
step two, uniformly mixing 30.0-40.0 wt% of boron oxide, 20.0-30.0 wt% of bismuth oxide, 5.0-10.0 wt% of phosphorus oxide, 5.0-10.0 wt% of silicon oxide, 10.0-15.0 wt% of barium oxide and 5.0-10.0 wt% of gadolinium oxide serving as raw materials to obtain a mixture I; melting the mixture I at 1400-1600 ℃, water quenching, drying at 100-120 ℃ for 10-15 h, and crushing until the particle size is less than 0.147mm to obtain a glass shielding agent containing a radiation shielding component;
mixing the aluminum borate precursor, the glass shielding agent containing the radiation shielding component and the binding agent according to the mass ratio of 1: 0.2-0.7: 0.006-0.0085 to obtain a mixture II; and then, carrying out mechanical pressing forming on the mixture II under the condition of 120-150 MPa, drying for 20-24 h at the temperature of 100-120 ℃, then heating to 1000-1500 ℃ under the conditions of air atmosphere and normal pressure, keeping the temperature for 60-300 min, and cooling along with a furnace to obtain the glass-ceramic material with the neutron and gamma ray cooperative protection.
2. The method for preparing the glass-ceramic material for the cooperative protection of neutrons and gamma rays according to claim 1, wherein the aluminum borate powder comprises: 2Al2O3·B2O3And 9Al2O3·2B2O3Is greater than 95 wt%, Al2O3The content is less than 3 wt%, and the water content is less than 2 wt%.
3. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the purity of boron oxide is more than 99.9%, and the particle size is less than 0.5 um.
4. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the bismuth oxide is analytically pure.
5. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the phosphorus oxide has a purity of more than 99.9% and a particle size of less than 0.5 um.
6. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the purity of the silicon oxide is more than 99.9%, and the particle size is less than 0.5 um.
7. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the purity of the barium oxide is analytical grade.
8. The method for preparing glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the gadolinium oxide has a purity of more than 99% and a particle size of less than 2.5 um.
9. The method for preparing a glass-ceramic material for cooperative protection of neutron and gamma ray according to claim 1, wherein the binder is one of polyvinyl alcohol solution, carboxymethyl cellulose and aluminum sol.
10. The glass-ceramic material for the cooperative protection of neutrons and gamma rays is characterized by being prepared by the preparation method of the glass-ceramic material for the cooperative protection of neutrons and gamma rays according to any one of claims 1 to 9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250298A (en) * | 2020-10-28 | 2021-01-22 | 中国建筑材料科学研究总院有限公司 | Radiation-proof glass and preparation method and application thereof |
| CN113185278A (en) * | 2021-04-22 | 2021-07-30 | 武汉科技大学 | Bismuth borate ceramic material and preparation method thereof |
| CN113277844A (en) * | 2021-05-28 | 2021-08-20 | 武汉科技大学 | Boron phosphate ceramic material and preparation method thereof |
| CN113674889A (en) * | 2021-07-30 | 2021-11-19 | 海南大学 | X-ray radiation protection module and manufacturing method thereof |
| CN114426432A (en) * | 2022-02-14 | 2022-05-03 | 安徽工业大学 | Fiber-reinforced radiation shielding/heat insulation integrated composite material and preparation method thereof |
| CN116655241A (en) * | 2023-04-23 | 2023-08-29 | 西北核技术研究所 | High-temperature-resistant high-boron glass sand neutron absorption material and preparation method thereof |
| CN116655241B (en) * | 2023-04-23 | 2024-04-26 | 西北核技术研究所 | High-temperature-resistant high-boron glass sand neutron absorption material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005162509A (en) * | 2003-12-01 | 2005-06-23 | Denki Kagaku Kogyo Kk | Hydraulic material |
| CN1730427A (en) * | 2005-06-20 | 2006-02-08 | 武汉科技大学 | Aluminium borate composite porous ceramics and its preparation method |
| CN101100368A (en) * | 2007-07-26 | 2008-01-09 | 济南大学 | Ceramic-base wave-permeation material and preparing process thereof |
| CN108623146A (en) * | 2018-06-26 | 2018-10-09 | 成都光明光电有限责任公司 | Environmentally friendly special type protection glass |
-
2020
- 2020-01-15 CN CN202010043549.4A patent/CN111205067B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005162509A (en) * | 2003-12-01 | 2005-06-23 | Denki Kagaku Kogyo Kk | Hydraulic material |
| CN1730427A (en) * | 2005-06-20 | 2006-02-08 | 武汉科技大学 | Aluminium borate composite porous ceramics and its preparation method |
| CN101100368A (en) * | 2007-07-26 | 2008-01-09 | 济南大学 | Ceramic-base wave-permeation material and preparing process thereof |
| CN108623146A (en) * | 2018-06-26 | 2018-10-09 | 成都光明光电有限责任公司 | Environmentally friendly special type protection glass |
Non-Patent Citations (2)
| Title |
|---|
| HAN LUO: ""Microstructural evolution and kinetics analysis of aluminum borate ceramics via solid‐state reaction synthesis"，Han Luo，《ORIGINAL ARTICLE》，第16(6)卷，第2457-2466页", 《ORIGINAL ARTICLE》 * |
| M.I. SAYYED: ""Comparative study of gamma-ray shielding and elastic properties of BaO–Bi2O3–B2O3 and ZnO–Bi2O3–B2O3 glass systems"，《Materials Chemistry and Physics》，第 217卷，第11-22页", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250298A (en) * | 2020-10-28 | 2021-01-22 | 中国建筑材料科学研究总院有限公司 | Radiation-proof glass and preparation method and application thereof |
| CN112250298B (en) * | 2020-10-28 | 2022-08-12 | 中国建筑材料科学研究总院有限公司 | Radiation-proof glass and preparation method and application thereof |
| CN113185278A (en) * | 2021-04-22 | 2021-07-30 | 武汉科技大学 | Bismuth borate ceramic material and preparation method thereof |
| CN113185278B (en) * | 2021-04-22 | 2023-02-03 | 武汉科技大学 | Bismuth borate ceramic material and preparation method thereof |
| CN113277844A (en) * | 2021-05-28 | 2021-08-20 | 武汉科技大学 | Boron phosphate ceramic material and preparation method thereof |
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