CN113185278A - Bismuth borate ceramic material and preparation method thereof - Google Patents
Bismuth borate ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN113185278A CN113185278A CN202110434485.5A CN202110434485A CN113185278A CN 113185278 A CN113185278 A CN 113185278A CN 202110434485 A CN202110434485 A CN 202110434485A CN 113185278 A CN113185278 A CN 113185278A
- Authority
- CN
- China
- Prior art keywords
- drying
- bismuth borate
- bismuth
- grinding material
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/453—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 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- 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
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Abstract
The invention relates to a bismuth borate ceramic material and a preparation method thereof. The technical scheme is as follows: mixing boric acid and bismuth oxide, ball-milling and drying to obtain a drying ball grinding material I; and (3) preserving the heat at 250-300 ℃, and crushing to obtain bismuth borate powder. Then mixing magnesium oxide, aluminum oxide and gadolinium oxide, ball-milling and drying to obtain a drying ball grinding material II; and then mixing the dried ball grinding material II with the dried ball grinding material I, ball-milling and drying to obtain the bismuth borate ceramic powder. And (3) mechanically pressing and molding the bismuth borate ceramic powder, carrying out isostatic pressing treatment, and carrying out heat preservation for 3-5 hours under the conditions of air atmosphere, normal pressure and 500-600 ℃ to obtain the bismuth borate ceramic material. The method has the advantages of simple process, short production period, low cost and environmental friendliness, and the prepared bismuth borate ceramic material has excellent neutron and gamma cooperative shielding performance and good heat insulation performance.
Description
Technical Field
The invention belongs to the technical field of borate ceramic materials. In particular to a bismuth borate ceramic material and a preparation method thereof.
Background
With the continuous development of production technology, the demand of human beings on energy is increasing, and compared with other novel energy, nuclear energy has incomparable superiority such as high efficiency, cleanness and the like. At present, for workers who are engaged in nuclear reaction research, shielding protection is the best mode, and materials with good heat insulation can reduce energy loss and are indispensable to improve energy utilization rate. How to improve the heat insulation performance of the material on the premise of ensuring excellent shielding capability is a problem to be researched by shielding material researchers.
In the prior art research, the Bi element has high attenuation coefficient to gamma photons and cannot cause damage to human bodies, so the Bi element can be used as a good gamma ray shielding material. Among a plurality of neutron shielding materials, B has the highest absorption cross section to thermal neutrons, the generated secondary gamma rays are only 0.479MeV at most, meanwhile, boron-containing compounds are abundant in natural storage, and compared with other neutron moderators such as gadolinium, cadmium and lithium, boron is low in price, so that B can be used as an ideal thermal neutron shielding material. For the bismuth borate ceramic material containing boron and bismuth, the neutron and gamma synergistic shielding performance is worthy of being researched.
At present, the preparation of bismuth borate powder usually adopts a molten salt method, a sol-gel method, a hydrothermal method and a solid-phase sintering method, but the batch production is difficult due to the low yield, the complex process and the overlong production period of the molten salt method, the sol-gel method and the hydrothermal method. The solid-phase sintering method is concerned by technicians in the field because boric acid can directly react with bismuth oxide to produce bismuth borate, and the method is simple, short in preparation period, low in cost and high in synthesis purity.
The patent technology of 'a lead-aluminum-boron composite nuclear shielding material and a preparation method thereof' (CN104150859A) utilizes boron powder to carry out surface treatment, extrusion forming, protective atmosphere sintering and lead coating treatment, and the composite material prepared by the technology has good shielding performance due to high boron content, but has common gamma shielding performance; in addition, because the material preparation process adopts lead-coated treatment, lead has certain toxicity, is easy to cause harm to human bodies in the manufacturing process and the using process, strong acid and strong alkali can be used in the material preparation process, potential safety hazards exist to human bodies in the preparation process, and meanwhile, the composite material has general thermal conductivity and can cause a large amount of heat loss.
The patent technology of 'a preparation method of carbon fiber reinforced aluminum-based boron carbide neutron shielding material' (CN109680227A) is characterized in that composite powder which is uniformly mixed by ball milling is arranged in a prefabricated graphite grinding tool to be subjected to surface activation and plasma activation sintering, and a sintered sample is subjected to heat treatment to obtain the composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of a bismuth borate ceramic material, which has the advantages of simple process, short production period, low cost and environmental friendliness; the bismuth borate ceramic material prepared by the method has excellent neutron and gamma cooperative shielding performance and good heat insulation performance.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of 0.40-0.66: 1 of boric acid to bismuth oxide to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 2-4 h, and drying is carried out to obtain a drying ball grinding material I; and then, preserving the heat of the drying ball grinding material I for 3-5 hours at the temperature of 250-300 ℃, and crushing to obtain bismuth borate powder.
Step two, mixing 30-36 wt% of magnesium oxide, 52-58 wt% of aluminum oxide and 6-18 wt% of gadolinium oxide to obtain a mixture II; and then ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 2-4 h, and drying is carried out to obtain a dried ball grinding material II.
Step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 0.6-1.8: 1 to obtain a mixed ball grinding material; and then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 2-4 h, and drying is carried out, so as to obtain the bismuth borate ceramic powder.
And fourthly, mechanically pressing the bismuth borate ceramic powder under the condition of 10-30 MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 150-350 MPa to obtain a bismuth borate ceramic blank.
And fifthly, heating the bismuth borate ceramic blank to 500-600 ℃ under the conditions of air atmosphere and normal pressure, and preserving heat for 3-5 hours to obtain the bismuth borate ceramic material.
The purity of the bismuth oxide is more than 99.9%; the particle size of the bismuth oxide is less than 5 μm.
The purity of the boric acid is more than 99.0%; the particle size of the boric acid is less than 100 mu m.
The purity of the magnesium oxide is more than 99.9%; the particle size of the magnesium oxide is less than 100 μm.
The purity of the alumina is more than 99.9%; the particle size of the alumina is less than 5 μm.
The purity of the gadolinium oxide is more than 99.9%; the particle size of the gadolinium oxide is less than 5 μm.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the method is different from a molten salt method and a sol-gel method, does not need to add an additional cleaning procedure, shortens the production period, is simple to operate, has low cost and is convenient for batch production.
2. The invention is different from shielding materials containing lead elements, and has no toxicity and harm in the manufacturing and using processes and environmental protection.
3. The bismuth borate ceramic material containing the radiation shielding component is prepared by taking boric acid, bismuth oxide, aluminum oxide, magnesium oxide and gadolinium oxide as raw materials, can fully utilize the synergistic shielding effect of each element on neutrons and gamma rays, and has excellent shielding performance and good heat insulation performance.
The bismuth borate ceramic material prepared by the invention is detected as follows: the bulk density is 3.75 to 4.51g/cm3(ii) a The normal-temperature breaking strength is 52.2-84.5 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the prepared bismuth borate ceramic material (with the thickness of 2mm), and the penetration rate of neutrons and gamma rays is 6.8-7.5%; the coefficient of thermal conductivity at room temperature is 0.23-0.44W/(mK).
Therefore, the method has the advantages of simple process, short production period, low cost and environmental friendliness, and the prepared bismuth borate ceramic material has excellent neutron and gamma cooperative shielding performance and good heat insulation performance.
Detailed Description
The invention is further described with reference to specific embodiments, which do not limit the scope of the invention.
A bismuth borate ceramic material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of 0.40-0.66: 1 of boric acid to bismuth oxide to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 2-4 h, and drying is carried out to obtain a drying ball grinding material I; and then, preserving the heat of the drying ball grinding material I for 3-5 hours at the temperature of 250-300 ℃, and crushing to obtain bismuth borate powder.
Step two, mixing 30-36 wt% of magnesium oxide, 52-58 wt% of aluminum oxide and 6-18 wt% of gadolinium oxide to obtain a mixture II; and then ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 2-4 h, and drying is carried out to obtain a dried ball grinding material II.
Step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 0.6-1.8: 1 to obtain a mixed ball grinding material; and then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 2-4 h, and drying is carried out, so as to obtain the bismuth borate ceramic powder.
And fourthly, mechanically pressing the bismuth borate ceramic powder under the condition of 10-30 MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 150-350 MPa to obtain a bismuth borate ceramic blank.
And fifthly, heating the bismuth borate ceramic blank to 500-600 ℃ under the conditions of air atmosphere and normal pressure, and preserving heat for 3-5 hours to obtain the bismuth borate ceramic material.
In this embodiment:
the purity of the bismuth oxide is more than 99.9%; the grain diameter of the bismuth oxide is less than 5 mu m;
the purity of the boric acid is more than 99.0%; the particle size of the boric acid is less than 100 mu m;
the purity of the magnesium oxide is more than 99.9%; the particle size of the magnesium oxide is less than 100 mu m;
the purity of the alumina is more than 99.9%; the grain diameter of the alumina is less than 5 μm;
the purity of the gadolinium oxide is more than 99.9%; the particle size of the gadolinium oxide is less than 5 μm.
The detailed description is omitted in the embodiments.
Example 1
A bismuth borate ceramic material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of 0.40: 1 to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 2 hours, and drying is carried out to obtain a drying ball grinding material I; and then, preserving the heat of the drying ball grinding material I for 3 hours at the temperature of 250 ℃, and crushing to obtain bismuth borate powder.
Step two, mixing 30 wt% of magnesium oxide, 52 wt% of aluminum oxide and 18 wt% of gadolinium oxide to obtain a mixture II; and then ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 2 hours, and drying is carried out to obtain a dried ball grinding material II.
Step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 0.6: 1 to obtain a mixed ball grinding material; and then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 2 hours, and drying is carried out, so as to prepare the bismuth borate ceramic powder.
And step four, mechanically pressing the bismuth borate ceramic powder under the condition of 10MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 150MPa to obtain a bismuth borate ceramic blank.
And fifthly, heating the bismuth borate ceramic blank to 500 ℃ under the conditions of air atmosphere and normal pressure, and preserving heat for 3 hours to obtain the bismuth borate ceramic material.
The bismuth borate ceramic material prepared in the embodiment is detected as follows: the bulk density was 4.51g/cm3(ii) a The bending strength at normal temperature is 84.5 MPa; the prepared bismuth borate ceramic material (with the thickness of 2mm) is irradiated by an Am-Be neutron ray source and a Co60 gamma ray source, and the penetration rate of neutrons and gamma rays is 6.8%; the thermal conductivity at room temperature is 0.44W/(mK).
Example 2
A bismuth borate ceramic material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of boric acid to bismuth oxide of 0.53: 1 to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 3 hours, and drying is carried out to obtain a drying ball grinding material I; and then, preserving the heat of the drying ball grinding material I for 4 hours at 275 ℃, and crushing to obtain bismuth borate powder.
Step two, mixing 33 wt% of magnesium oxide, 55 wt% of aluminum oxide and 12 wt% of gadolinium oxide to obtain a mixture II; and then ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 3 hours, and drying is carried out to obtain a dried ball grinding material II.
Step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 1.0: 1 to obtain a mixed ball grinding material; and then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 3 hours, and drying is carried out, so as to prepare the bismuth borate ceramic powder.
And step four, mechanically pressing the bismuth borate ceramic powder under the condition of 20MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 250MPa to obtain a bismuth borate ceramic blank.
And fifthly, heating the bismuth borate ceramic blank to 550 ℃ under the conditions of air atmosphere and normal pressure, and preserving heat for 4 hours to obtain the bismuth borate ceramic material.
The bismuth borate ceramic material prepared in the embodiment is detected as follows: the bulk density is 4.06g/cm3(ii) a The normal temperature bending strength is 68.5 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the prepared bismuth borate ceramic material (with the thickness of 2mm), and the penetration rate of neutrons and gamma rays is 7.2%; the thermal conductivity at room temperature is 0.34W/(mK).
Example 3
A bismuth borate ceramic material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of 0.66: 1 to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 4 hours, and drying is carried out to obtain a drying ball grinding material I; and then, preserving the heat of the drying ball grinding material I for 5 hours at the temperature of 300 ℃, and crushing to obtain bismuth borate powder.
Step two, mixing 36 wt% of magnesium oxide, 58 wt% of aluminum oxide and 6 wt% of gadolinium oxide to obtain a mixture II; and then ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 4 hours, and drying is carried out to obtain a dried ball grinding material II.
Step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 1.8: 1 to obtain a mixed ball grinding material; and then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 4 hours, and drying is carried out, so as to prepare the bismuth borate ceramic powder.
And step four, mechanically pressing the bismuth borate ceramic powder under the condition of 30MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 350MPa to obtain a bismuth borate ceramic blank.
And fifthly, heating the bismuth borate ceramic blank to 600 ℃ under the conditions of air atmosphere and normal pressure, and preserving the heat for 5 hours to obtain the bismuth borate ceramic material.
The bismuth borate ceramic material prepared in the embodiment is detected as follows: the bulk density is 3.75g/cm3(ii) a The normal temperature rupture strength is 52.2 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the prepared bismuth borate ceramic material (with the thickness of 2mm), and the penetration rate of neutrons and gamma rays is 7.5%; the thermal conductivity at room temperature is 0.23W/(mK).
Compared with the prior art, the specific implementation mode has the following positive effects:
1. the specific implementation mode is different from a molten salt method and a sol-gel method, does not need to add an additional cleaning procedure, shortens the production period, is simple to operate, has low cost and is convenient for batch production.
2. The specific implementation mode is different from a shielding material containing lead elements, and is non-toxic, harmless and environment-friendly in the manufacturing and using processes.
3. According to the specific embodiment, the bismuth borate ceramic material containing the radiation shielding component is prepared from boric acid, bismuth oxide, aluminum oxide, magnesium oxide and gadolinium oxide, the synergistic shielding effect of each element on neutrons and gamma rays can be fully utilized, the shielding performance is excellent, and the heat insulation performance is good.
The bismuth borate ceramic material prepared by the specific embodiment is detected as follows: the bulk density is 3.75 to 4.51g/cm3(ii) a The normal-temperature breaking strength is 52.2-84.5 MPa; an Am-Be neutron ray source and a Co60 gamma ray source are adopted to irradiate the prepared bismuth borate ceramic material (with the thickness of 2mm), and the penetration rate of neutrons and gamma rays is 6.8-7.5%; the coefficient of thermal conductivity at room temperature is 0.23-0.44W/(mK).
Therefore, the specific implementation method has the advantages of simple process, short production period, low cost and environmental friendliness, and the prepared bismuth borate ceramic material has excellent neutron and gamma cooperative shielding performance and good heat insulation performance.
Claims (7)
1. The preparation method of the bismuth borate ceramic material is characterized by comprising the following steps:
step one, mixing boric acid and bismuth oxide according to the mass ratio of 0.40-0.66: 1 of boric acid to bismuth oxide to obtain a mixture I; then, ball milling is carried out on the mixture I by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture I is 2-4 h, and drying is carried out to obtain a drying ball grinding material I; then, preserving the heat of the drying ball grinding material I for 3-5 hours at the temperature of 250-300 ℃, and crushing to obtain bismuth borate powder;
step two, mixing 30-36 wt% of magnesium oxide, 52-58 wt% of aluminum oxide and 6-18 wt% of gadolinium oxide to obtain a mixture II; then, ball milling is carried out on the mixture II by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixture II is 2-4 h, and drying is carried out to obtain a drying ball grinding material II;
step three, mixing the drying ball grinding material II and the drying ball grinding material I according to the mass ratio of the drying ball grinding material II to the drying ball grinding material I of 0.6-1.8: 1 to obtain a mixed ball grinding material; then, ball milling is carried out on the mixed ball grinding material by taking absolute ethyl alcohol as a ball milling medium, the ball milling time of the mixed ball grinding material is 2-4 h, and drying is carried out to prepare bismuth borate ceramic powder;
fourthly, mechanically pressing the bismuth borate ceramic powder under the condition of 10-30 MPa, and carrying out isostatic pressing treatment on the formed primary blank under the conditions of room temperature and 150-350 MPa to obtain a bismuth borate ceramic blank;
and fifthly, heating the bismuth borate ceramic blank to 500-600 ℃ under the conditions of air atmosphere and normal pressure, and preserving heat for 3-5 hours to obtain the bismuth borate ceramic material.
2. The method for preparing the bismuth borate ceramic material according to claim 1, wherein the purity of the bismuth oxide is more than 99.9%; the particle size of the bismuth oxide is less than 5 μm.
3. The method for preparing the bismuth borate ceramic material according to claim 1, wherein the purity of the boric acid is more than 99.0%; the particle size of the boric acid is less than 100 mu m.
4. The method for preparing the bismuth borate ceramic material according to claim 1, wherein the purity of the magnesium oxide is more than 99.9%; the particle size of the magnesium oxide is less than 100 μm.
5. The method for preparing the bismuth borate ceramic material according to claim 1, wherein the purity of the aluminum oxide is more than 99.9%; the particle size of the alumina is less than 5 μm.
6. The method for preparing the bismuth borate ceramic material according to claim 1, wherein the purity of the gadolinium oxide is more than 99.9%; the particle size of the gadolinium oxide is less than 5 μm.
7. The bismuth borate ceramic material is characterized by being prepared by the preparation method of the bismuth borate ceramic material according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434485.5A CN113185278B (en) | 2021-04-22 | 2021-04-22 | Bismuth borate ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434485.5A CN113185278B (en) | 2021-04-22 | 2021-04-22 | Bismuth borate ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113185278A true CN113185278A (en) | 2021-07-30 |
| CN113185278B CN113185278B (en) | 2023-02-03 |
Family
ID=76978103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110434485.5A Active CN113185278B (en) | 2021-04-22 | 2021-04-22 | Bismuth borate ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113185278B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3364144A (en) * | 1963-10-24 | 1968-01-16 | Charles F. Pulvari | Lamellated dielectric of mixed bismuth oxides |
| KR20070021015A (en) * | 2005-08-16 | 2007-02-22 | 한국과학기술연구원 | Process of preparing low- temperature sintered microwave dielectric ceramics |
| CN104841416A (en) * | 2015-05-07 | 2015-08-19 | 南京信息工程大学 | Preparation method for novel square flaky bismuth borate oxide photocatalyst |
| CN109231967A (en) * | 2018-10-15 | 2019-01-18 | 桂林理工大学 | Bi2O3-B2O3Binary system microwave dielectric ceramic materials and preparation method thereof |
| CN110937889A (en) * | 2019-12-10 | 2020-03-31 | 武汉科技大学 | Zirconium phosphate ceramic material and preparation method thereof |
| CN111205107A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Radiation shielding composite material and preparation method thereof |
| CN111205067A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof |
-
2021
- 2021-04-22 CN CN202110434485.5A patent/CN113185278B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3364144A (en) * | 1963-10-24 | 1968-01-16 | Charles F. Pulvari | Lamellated dielectric of mixed bismuth oxides |
| KR20070021015A (en) * | 2005-08-16 | 2007-02-22 | 한국과학기술연구원 | Process of preparing low- temperature sintered microwave dielectric ceramics |
| CN104841416A (en) * | 2015-05-07 | 2015-08-19 | 南京信息工程大学 | Preparation method for novel square flaky bismuth borate oxide photocatalyst |
| CN109231967A (en) * | 2018-10-15 | 2019-01-18 | 桂林理工大学 | Bi2O3-B2O3Binary system microwave dielectric ceramic materials and preparation method thereof |
| CN110937889A (en) * | 2019-12-10 | 2020-03-31 | 武汉科技大学 | Zirconium phosphate ceramic material and preparation method thereof |
| CN111205107A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Radiation shielding composite material and preparation method thereof |
| CN111205067A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113185278B (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111205067B (en) | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof | |
| CN103045916B (en) | Composite shielding material and preparation method thereof | |
| CN103276254B (en) | A kind of composite shielding material and preparation method thereof | |
| CN101844766B (en) | Method for rapidly preparing zirconium carbide ceramics powder | |
| CN105200274B (en) | A kind of preparation method of neutron absorber material | |
| CA3089067A1 (en) | Composite moderator for nuclear reactor systems | |
| CN101967591B (en) | Method for preparing Nb3Al superconducting material by mechanical alloying method | |
| CN101734918B (en) | Compact 10 B boron carbide-rich ceramics and preparation thereof | |
| CN111968769B (en) | High-temperature-resistant fast neutron shielding material, composite shielding material and preparation method thereof | |
| CN101935037A (en) | Nuclear graphite material composition and preprocessing method | |
| CN104477977B (en) | The synthetic Dy of a kind of molten-salt growth method2TiO5The method of powder | |
| CN106986662B (en) | Solar heat-absorbing ceramic material and preparation method thereof | |
| CN109704771B (en) | Preparation method of boron carbide porous ceramic for high-temperature gas cooled reactor nuclear control rod | |
| CN111205107A (en) | Radiation shielding composite material and preparation method thereof | |
| CN113185278B (en) | Bismuth borate ceramic material and preparation method thereof | |
| CN102432295B (en) | Ceramic substrate neutron absorption ball and preparation method thereof | |
| CN101789271A (en) | Neutron absorption ball | |
| CN113277844A (en) | Boron phosphate ceramic material and preparation method thereof | |
| US20220306543A1 (en) | Method for preparing boron carbide material | |
| CN104961138A (en) | Preparation method of <10>B-enriched zirconium diboride powder | |
| CN107010962B (en) | Low-cost solar heat-absorbing ceramic material and preparation method thereof | |
| CN115572150A (en) | Barite radiation-proof ceramic plate and preparation method thereof | |
| CN110828001B (en) | Heat conductivity improved uranium dioxide-based fuel pellet for improving uranium loading and preparation method thereof | |
| CN103159222B (en) | Method of densification of lithium orthosilicate pellets used in tritium breeding | |
| CN101789272B (en) | Neutron absorption ball preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |