CN114408973B - Nuclear radiation shielding material and preparation method thereof - Google Patents
Nuclear radiation shielding material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000005855 radiation Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 131
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 55
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 55
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 43
- 239000010937 tungsten Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 124
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 16
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- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 5
- 231100000956 nontoxicity Toxicity 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
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- 239000011259 mixed solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000005251 gamma ray Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241001198704 Aurivillius Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002123 erbium compounds Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nuclear radiation shielding material and a preparation method thereof. The K layers of tungsten and bismuth have the absorption edges of 69.5KeV and 90.5KeV respectively, the K layers of erbium have the absorption edges of 57.5KeV, and erbium has the lower K layers. The preparation method provided by the invention has the advantages of simple process, low energy consumption, no toxicity, no harm and easy realization, and can provide a beneficial reference for the development of environment-friendly and efficient radiation protection materials.
Description
Technical Field
The invention relates to the field of nuclear radiation shielding materials, in particular to a nuclear radiation shielding material and a preparation method thereof.
Background
The nuclear energy and nuclear technology application is a double-edged sword, and when people enjoy huge well-being, if the use or protection is improper, the generated high-energy rays (X, gamma rays, neutrons and the like) can cause great harm to human health and ecological environment. Lead (Pb) is a widely used X/gamma ray protection material, but lead is toxic, and has a weak absorption area for rays with energy between 40 and 88KeV, so that the novel, environment-friendly and efficient ray shielding material has important significance for guaranteeing the life health of nuclear personnel and the public.
The weakening effect of the traditional radiation protection theory on the substances on rays mainly depends on factors such as the types of particles, energy, elemental composition and density of materials and the like. As a shielding material for Pb, the use of tantalum, tungsten, bismuth, and rare earth metals in X/gamma radiation protection has received great attention. Chinese patent No. CN107910089a discloses a method for manufacturing a novel flexible leadless radiation protective garment, which uses non-toxic environmental protection materials such as tantalum, tungsten, barium, etc. as functional filler, and has the performance of shielding X/gamma rays equivalent to lead, so as to effectively protect nuclear radiation hazard. The us RST company developed a lead-free nuclear radiation protective fabric named Demron by doping tantalum modified polyvinyl chloride and polyethylene, which has been used in a number of fields.
However, the X-rays are continuous spectra, the energy range is wider, the energy of gamma rays emitted by different nuclides is different, and the shielding effect of the nuclear radiation protection material based on high atomic coefficient elements such as lead, bismuth and the like on low-energy rays needs to be improved.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a nuclear radiation shielding material and a preparation method thereof, which aims to solve the problem that the shielding effect of the existing elements such as lead, bismuth and the like on low-energy rays is poor.
The technical scheme of the invention is as follows:
in a first aspect of the invention, there is provided a nuclear radiation shielding material, wherein the nuclear radiation shielding material comprises erbium doped bismuth tungstate.
Optionally, the nuclear radiation shielding material is erbium doped bismuth tungstate.
Optionally, the molar ratio of erbium to bismuth tungstate in the erbium-doped bismuth tungstate is (2-15): 100.
Optionally, the microstructure of the erbium-doped bismuth tungstate is a flower-sphere structure formed by stacking sheets, the thickness of the sheets is 50-80 nm, the diameter of the flower sphere is 0.5-2.0 μm, and the crystal phase of the erbium-doped bismuth tungstate is an orthorhombic phase.
In a second aspect of the present invention, there is provided a method for producing a nuclear radiation shielding material, comprising the steps of:
providing a bismuth source, a tungsten source, an erbium source, an acid solution and water;
dissolving the bismuth source in an acid solution to obtain a bismuth source acid solution;
dissolving the tungsten source in water to obtain a tungsten source water solution;
dissolving the erbium source in water to obtain an erbium source water solution;
mixing the bismuth source acid solution and the tungsten source water solution, and regulating the pH value of the system to 5-7 to obtain bismuth tungstate precursor solution;
and adding the erbium source water solution into the bismuth tungstate precursor solution, and performing hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
Alternatively, the process may be carried out in a single-stage,
the bismuth source is selected from one or two of bismuth nitrate and bismuth oxide; and/or the number of the groups of groups,
the tungsten source is selected from tungstate, and the tungstate is selected from one or two of sodium tungstate and ammonium tungstate; and/or the number of the groups of groups,
the erbium source is one or two selected from erbium nitrate and erbium oxide; and/or the number of the groups of groups,
the acid solution is nitric acid aqueous solution or acetic acid aqueous solution.
Alternatively, the process may be carried out in a single-stage,
the molar ratio of bismuth in the bismuth source to tungsten in the tungsten source is (2-2.2): 1-1.2; and/or the number of the groups of groups,
the molar ratio of erbium in the erbium source to tungsten in the tungsten source is (2-15): 100.
Optionally, adjusting the pH of the system to 5-7 by adding NaOH aqueous solution;
and/or the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 24-48 h.
Alternatively, the process may be carried out in a single-stage,
mixing the bismuth source acid solution and the tungsten source water solution under the stirring condition, stirring for 30-60 min, regulating the pH value of the system to 7, and continuing stirring for 1-2 h to obtain a bismuth tungstate precursor solution; and/or the number of the groups of groups,
and under the stirring condition, adding the erbium source aqueous solution into the bismuth tungstate precursor solution, stirring for 1-2 h, and performing hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
Optionally, the hydrothermal reaction further comprises the steps of: and (3) sequentially carrying out centrifugal separation, washing and drying on the solution after the hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
The beneficial effects are that: the invention provides a nuclear radiation shielding material and a preparation method thereof, wherein the 'absorption edges' of K layers of tungsten and bismuth are 69.5KeV and 90.5KeV respectively, the 'absorption edge' of K layers of erbium is 57.5KeV, and erbium has lower 'absorption edge' of the K layers. The preparation method provided by the invention has the advantages of simple process, low energy consumption, no toxicity, no harm and easy realization, and can provide a beneficial reference for the development of environment-friendly and efficient radiation protection materials.
Drawings
Fig. 1 is an XRD pattern of erbium-doped bismuth tungstate prepared in example 1 of the present invention.
Fig. 2 (a) and (b) are SEM images of erbium-doped bismuth tungstate prepared in example 1 of the present invention.
Fig. 3 is a graph showing EDS results of erbium-doped bismuth tungstate prepared in example 1 of the present invention.
Fig. 4 is a graph showing the results of gamma-ray shielding performance test of erbium-doped bismuth tungstate prepared in examples 1 to 4 of the present invention.
Detailed Description
The invention provides a nuclear radiation shielding material and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the prior art, bismuth tungstate (Bi 2 WO 6 ) Is a typical Aurivillius oxide having a composition of Bi 2 O 2 2+ And WO 4 2- The perovskite layered structure formed by alternating layers along the c axis is widely applied to the field of photocatalysis due to the characteristics of safety, no toxicity, easy adjustment of structural morphology, excellent photocatalysis performance, stable physicochemical properties and the like. The inventor finds that bismuth tungstate has high atomic coefficient tungsten and bismuth simultaneously, has high density and has important application value in the aspect of high-energy ray protection. But bismuth tungstate has poor shielding performance on low-energy rays, and based on the bismuth tungstate, the invention provides a nuclear radiation shielding material, wherein the nuclear radiationThe radiation shielding material comprises erbium doped bismuth tungstate.
The inventors found through a great deal of research that the K layer "absorption edge" effect of an element is an important factor for improving the shielding performance of a material, and the K layer "absorption edge" refers to a phenomenon that when the energy of an incident photon is equal to the binding energy of K layer electrons, the cross section of a photoelectric effect is increased sharply. In bismuth tungstate, the K layers of tungsten and bismuth have "absorption edges" of 69.5KeV and 90.5KeV, respectively, and the shielding capability to 69.5-88.0 KeV and 90.5KeV or more rays is better than that of lead. However, the X-ray and the gamma-ray are continuous spectrums, the energy range is wider, the absorption edge of the K layer of the rare earth element is lower (for example, the absorption edge of the K layer of erbium is 57.5 KeV), and if the rare earth elements such as strontium and erbium are doped into bismuth tungstate, the shielding performance of the material on low-energy rays can be effectively improved by utilizing the complementary effect of the absorption edge of the K layer of erbium. Therefore, according to the embodiment of the invention, erbium is doped into bismuth tungstate, the erbium has a lower K layer absorption edge, and the shielding performance of the bismuth tungstate material on low-energy rays is effectively improved by utilizing the complementary effect of the K layer absorption edge of erbium.
In one embodiment, the nuclear radiation shielding material is erbium doped bismuth tungstate.
In one embodiment, the molar ratio of erbium to bismuth tungstate in the erbium-doped bismuth tungstate is (2-15): 100. In the erbium-doped bismuth tungstate nuclear radiation shielding material in the embodiment, the molar ratio of erbium to bismuth tungstate is (2-15): 100, that is, the molar doping amount of erbium accounts for 2% -15% of the molar number of bismuth tungstate, the doping ratio does not influence the shielding performance of bismuth tungstate on high-energy rays, and the shielding efficiency of erbium-doped bismuth tungstate on low-energy rays is obviously increased along with the increase of the molar doping amount of erbium in the range of the doping ratio. The low-energy rays are low-energy X rays or low-energy gamma rays. The nuclear radiation shielding material provided by the embodiment can realize effective shielding of low-energy X-rays or low-energy gamma rays with the energy of 59.5 KeV.
In one embodiment, the microstructure of the erbium-doped bismuth tungstate is a flower-sphere structure formed by stacking sheets, the thickness of the sheets is 50-80 nm, the diameter of the flower sphere is 0.5-2.0 mu m, and the crystal phase of the erbium-doped bismuth tungstate is orthogonalIn the present embodiment, bismuth tungstate in the erbium-doped bismuth tungstate is orthorhombic bismuth tungstate (Bi 2 WO 6 ) Erbium is doped into the crystal lattice of bismuth tungstate, and the doping of erbium does not affect the crystal phase of bismuth tungstate, but the specific surface area of the material is increased, so that the probability of the material acting with high-energy particles is increased.
Bismuth tungstate (Bi) 2 WO 6 ) Is a typical Aurivillius oxide, has a perovskite layered structure, and is widely applied to the field of photocatalysis due to the characteristics of safety, innocuity, excellent photocatalysis performance, stable physicochemical property and the like. The preparation method of the bismuth tungstate photocatalytic material comprises a solid-phase sintering method, a solvothermal method, a sol-gel method and the like, and the methods have different defects: the solid phase sintering method has higher requirement on the environmental temperature, large energy consumption and low energy utilization rate; organic solvents required by the solvothermal method are generally toxic and are easy to damage the body and the environment due to improper use, and the reaction solvents bring potential safety hazards to the stability of a reaction system; the sol-gel method consumes more raw materials in the preparation process and has poor economic benefit. In the prior art, the preparation method is designed and developed aiming at bismuth tungstate photocatalytic materials. At present, a preparation method which is simple to operate, low in energy consumption, nontoxic and harmless is not provided for preparing erbium-doped bismuth tungstate with excellent nuclear radiation shielding performance, and based on the preparation method, the embodiment of the invention also provides a preparation method of a nuclear radiation shielding material, which comprises the following steps:
s1, providing a bismuth source, a tungsten source, an erbium source, an acid solution and water;
s2, dissolving the bismuth source in an acid solution to obtain a bismuth source acid solution;
s3, dissolving the tungsten source in water to obtain a tungsten source water solution;
s4, dissolving the erbium source in water to obtain an erbium source water solution;
s5, mixing the bismuth source acid solution and the tungsten source water solution, and regulating the pH value of the system to 5-7 to obtain a bismuth tungstate precursor solution;
and S6, adding the erbium source water solution into the bismuth tungstate precursor solution, and performing hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
The preparation method provided by the embodiment of the invention has the advantages of simple process, low energy consumption, no toxicity, no harm and easy realization, and can provide a beneficial reference for the development of environment-friendly and efficient radiation protection materials. The erbium-doped bismuth tungstate prepared by the embodiment has a good shielding effect on low-energy rays.
In step S1, in one embodiment, the bismuth source is selected from one or both of bismuth nitrate and bismuth oxide, but is not limited thereto. Wherein bismuth nitrate [ Bi (NO) 3 ) 3 ·5H 2 O]Or bismuth oxide (Bi) 2 O 3 ) Purity of (3)>99%. In the present embodiment, bismuth nitrate [ Bi (NO 3 ) 3 ·5H 2 O]Or bismuth oxide (Bi) 2 O 3 ) A bismuth source is provided for the erbium-doped bismuth tungstate nuclear radiation shielding material.
In one embodiment, the tungsten source is selected from a tungstate selected from one or both of sodium tungstate and ammonium tungstate, but not limited thereto, wherein sodium tungstate (Na 2 WO 4 ·2H 2 O) or ammonium tungstate [ (NH) 4 ) 6 W 7 O 24 ·6H 2 O]Purity of (3)>99%. In the present embodiment, sodium tungstate (Na 2 WO 4 ·2H 2 O) or ammonium tungstate [ (NH) 4 ) 6 W 7 O 24 ·6H 2 O]A tungsten source is provided for the erbium doped bismuth tungstate nuclear radiation shielding material.
In one embodiment, the erbium source is selected from one or two of erbium nitrate and erbium oxide, but is not limited thereto.
In one embodiment, the acid solution is an aqueous nitric acid solution or an aqueous acetic acid solution, but is not limited thereto.
In one embodiment, the bismuth source is selected from one or two of bismuth nitrate and bismuth oxide, the tungsten source is selected from tungstate, the tungstate is selected from one or two of sodium tungstate and ammonium tungstate, the erbium source is selected from erbium nitrate, and the acid solution is nitric acid aqueous solution or acetic acid aqueous solution, but is not limited to the above.
In the step S2, the bismuth source is dissolved in an acid solution to obtain a bismuth source acid solution; when the bismuth source is selected from bismuth nitrate and the acid solution is selected from aqueous nitric acid, the bismuth nitrate is dissolved in aqueous nitric acid to obtain an acidic bismuth nitrate solution, in order to avoid hydrolysis of the bismuth nitrate prior to the reaction. When the bismuth source is selected from bismuth oxide and the acid solution is selected from aqueous nitric acid, bismuth oxide is dissolved in aqueous nitric acid solution and can react to generate bismuth nitrate, and the generated bismuth nitrate is dissolved in aqueous nitric acid solution to obtain acidic bismuth nitrate solution, so that hydrolysis of the generated bismuth nitrate can be avoided.
In steps S1-S6, in one embodiment, the molar ratio of bismuth in the bismuth source to tungsten in the tungsten source is (2-2.2): 1-1.2.
In one embodiment, the molar ratio of erbium in the erbium source to tungsten in the tungsten source is (2-15): 100. In this embodiment, the molar ratio of erbium to bismuth tungstate in the finally obtained erbium-doped bismuth tungstate is set to (2 to 15): 100.
In one embodiment, the molar ratio of bismuth in the bismuth source to tungsten in the tungsten source is (2-2.2): (1-1.2), and the molar ratio of erbium in the erbium source to tungsten in the tungsten source is (2-15): 100.
In step S5, in one embodiment, the pH of the system is adjusted to 5 to 7 by adding an aqueous NaOH solution.
In one embodiment, the bismuth source acid solution and the tungsten source aqueous solution are mixed under the stirring condition, the mixture is stirred for 30-60 min, the pH value of the system is regulated to 7, and the mixture is continuously stirred for 1-2 h to obtain the bismuth tungstate precursor solution, wherein the reaction can be more thorough under the condition.
In step S6, in one embodiment, the hydrothermal reaction is performed at a temperature of 160 to 200℃for a period of 24 to 48 hours. The hydrothermal reaction condition can prepare the erbium-doped bismuth tungstate nuclear radiation shielding material with microstructure of a flower-sphere structure formed by stacking lamellar layers, thickness of the lamellar layers of 50-80 nm, diameter of the flower spheres of 0.5-2.0 mu m and orthorhombic phase.
In one embodiment, the erbium source aqueous solution is added into the bismuth tungstate precursor solution under the stirring condition, and the mixture is stirred for 1 to 2 hours to perform hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material. In one embodiment, the hydrothermal reaction further comprises the steps of: and (3) sequentially carrying out centrifugal separation, washing and drying on the solution after the hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
The invention is further illustrated by the following specific examples.
Example 1
(1) 48.51g (0.1 mol) of Bi (NO 3 ) 3 ·5H 2 O was dissolved in 250mL 1mol/L HNO 3 In the solution, magnetically stirring until the solution is completely dissolved, and marking as solution A; 16.5g (0.05 mol) of Na was weighed 2 WO 4 ·2H 2 O is dissolved in 50mL of deionized water, and is magnetically stirred until the O is completely dissolved, and the solution is marked as solution B; 0.443g (0.001 mol) Er (NO 3 ) 3 ·5H 2 O was dissolved in 25mL deionized water and magnetically stirred until completely dissolved, designated as solution C.
(2) Slowly dropwise adding the solution A into the solution B under the magnetic stirring condition, dropwise adding the solution A at the speed of 10mL/min, continuously stirring for 30min until the solution is fully mixed, dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of a solution system to 7, and obtaining the bismuth tungstate precursor solution.
(3) And (3) dropwise adding the solution C into the bismuth tungstate precursor solution under the magnetic stirring condition, and continuously stirring for 30min until the solution is fully mixed to obtain a mixed solution.
(4) And (3) placing the mixed solution in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying oven at 180 ℃ for reaction for 24 hours, then centrifugally separating a reaction product, washing the reaction product with ethanol and distilled water for 3 times respectively, and vacuum-drying the obtained solid at 80 ℃ for 10 hours to obtain the erbium-doped bismuth tungstate.
Example 2
(1) 48.51g (0.1 mol) of Bi (NO 3 ) 3 ·5H 2 O was dissolved in 250mL 1mol/L HNO 3 In the solution, magnetically stirring until the solution is completely dissolved, and marking as solution A; 16.5g (0.05 mol) of Na was weighed out 2 WO 4 ·2H 2 O is dissolved in 50mL of deionized water, and is magnetically stirred until the O is completely dissolved, and the solution is marked as solution B; 1.108g (0.0025 mol) Er (NO 3 ) 3 ·5H 2 O was dissolved in 25mL deionized water and magnetically stirred until completely dissolved, designated as solution C.
(2) Slowly dropwise adding the solution A into the solution B under the magnetic stirring condition, dropwise adding the solution A at the speed of 10mL/min, continuously stirring for 30min until the solution is fully mixed, dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of a solution system to 7, and obtaining the bismuth tungstate precursor solution.
(3) And (3) dropwise adding the solution C into the bismuth tungstate precursor solution under the magnetic stirring condition, and continuously stirring for 30min until the solution is fully mixed to obtain a mixed solution.
(4) And (3) placing the mixed solution in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying oven at 180 ℃ for reaction for 24 hours, then centrifugally separating a reaction product, washing the reaction product with ethanol and distilled water for 3 times respectively, and vacuum-drying the obtained solid at 80 ℃ for 10 hours to obtain the erbium-doped bismuth tungstate.
Example 3
(1) 48.51g (0.1 mol) of Bi (NO 3 ) 3 ·5H 2 O was dissolved in 250mL 1mol/L HNO 3 In the solution, magnetically stirring until the solution is completely dissolved, and marking as solution A; 16.5g (0.05 mol) of Na was weighed 2 WO 4 ·2H 2 O is dissolved in 50mL of deionized water, and is magnetically stirred until the O is completely dissolved, and the solution is marked as solution B; 2.217g (0.005 mol) Er (NO 3 ) 3 ·5H 2 O was dissolved in 25mL deionized water and magnetically stirred until completely dissolved, designated as solution C.
(2) Slowly dropwise adding the solution A into the solution B under the magnetic stirring condition, dropwise adding the solution A at the speed of 10mL/min, continuously stirring for 30min until the solution is fully mixed, dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of a solution system to 7, and obtaining the bismuth tungstate precursor solution.
(3) And (3) dropwise adding the solution C into the bismuth tungstate precursor solution under the magnetic stirring condition, and continuously stirring for 30min until the solution is fully mixed to obtain a mixed solution.
(4) And (3) placing the mixed solution in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying oven at 180 ℃ for reaction for 24 hours, then centrifugally separating a reaction product, washing the reaction product with ethanol and distilled water for 3 times respectively, and vacuum-drying the obtained solid at 80 ℃ for 10 hours to obtain the erbium-doped bismuth tungstate.
Example 4
(1) 48.51g (0.1 mol) of Bi (NO 3 ) 3 ·5H 2 O was dissolved in 250mL 1mol/L HNO 3 In the solution, magnetically stirring until the solution is completely dissolved, and marking as solution A; 16.5g (0.05 mol) of Na was weighed 2 WO 4 ·2H 2 O is dissolved in 50mL of deionized water, and is magnetically stirred until the O is completely dissolved, and the solution is marked as solution B; 3.325g (0.0075 mol) Er (NO 3 ) 3 ·5H 2 O was dissolved in 25mL deionized water and magnetically stirred until completely dissolved, designated as solution C.
(2) Slowly dropwise adding the solution A into the solution B under the magnetic stirring condition, dropwise adding the solution A at the speed of 10mL/min, continuously stirring for 30min until the solution is fully mixed, dropwise adding 2mol/L sodium hydroxide solution to adjust the pH value of a solution system to 7, and obtaining the bismuth tungstate precursor solution.
(3) And (3) dropwise adding the solution C into the bismuth tungstate precursor solution under the magnetic stirring condition, and continuously stirring for 30min until the solution is fully mixed to obtain a mixed solution.
(4) And (3) placing the mixed solution in a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature drying oven at 180 ℃ for reaction for 24 hours, then centrifugally separating a reaction product, washing the reaction product with ethanol and distilled water for 3 times respectively, and vacuum-drying the obtained solid at 80 ℃ for 10 hours to obtain the erbium-doped bismuth tungstate.
And (3) testing:
(1) XRD, SEM and EDS tests were performed on the erbium-doped bismuth tungstate prepared in example 1
From XRD, SEM and EDS tests, as can be seen in figures 1, 2, 3:
1) By comparing PDF standard card, the erbium-doped bismuth tungstate prepared in example 1 has an orthorhombic phase structure (with JCPLDS: 79-2381Bi 2 WO 6 Identical), FIG. 1 does not have diffraction peaks of erbium simple substance or erbium compound, and doping of erbium does not cause Bi 2 WO 6 The diffraction peak position of the (a) is changed, which indicates that Er ions possibly enter bismuth tungstate lattices;
2) Under neutral conditions, as shown in fig. 2 (a) and (b), erbium-doped bismuth tungstate generated by hydrothermal reaction is a flower-sphere structure with stacked sheets, the thickness of the sheets is 50-80 nm, and the diameter of flower-sphere particles is about 0.5-2.0 μm.
3) From the EDS results, fig. 3 can be derived: the Er element can be tested in the erbium-doped bismuth tungstate sample, and further proves that Er ions are indeed introduced into bismuth tungstate crystal lattices.
(2) Gamma ray shielding performance test:
the erbium-doped bismuth tungstate pair 59.5KeV prepared in examples 1-4 was measured using a high purity germanium gamma spectrometer 241 Am) shielding properties for gamma rays.
As a result, as shown in fig. 4, the shielding efficiency of the material against 59.5KeV gamma rays increases significantly with increasing erbium doping content.
In summary, the invention provides a nuclear radiation shielding material and a preparation method thereof, wherein the absorption edges of K layers of tungsten and bismuth are 69.5KeV and 90.5KeV respectively, and the absorption edge of K layers of erbium is 57.5 KeV. The preparation method provided by the invention has the advantages of simple process, low energy consumption, no toxicity, no harm and easy realization, and can provide a beneficial reference for the development of environment-friendly and efficient radiation protection materials.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (5)
1. The erbium-doped bismuth tungstate is used as a nuclear radiation shielding material, the microstructure of the erbium-doped bismuth tungstate is a flower-sphere structure formed by stacking sheets, the thickness of the sheets is 50-80 nm, and the diameter of the flower-sphere is 0.5-2.0 mu m; the molar ratio of erbium to bismuth tungstate in the erbium-doped bismuth tungstate is (2-15) 100; the erbium-doped bismuth tungstate is in an orthorhombic phase.
2. A method of preparing a nuclear radiation shielding material, comprising the steps of:
providing a bismuth source, a tungsten source, an erbium source, an acid solution and water;
dissolving the bismuth source in an acid solution to obtain a bismuth source acid solution;
dissolving the tungsten source in water to obtain a tungsten source water solution;
dissolving the erbium source in water to obtain an erbium source water solution;
mixing the bismuth source acid solution and the tungsten source water solution, and regulating the pH value of the system to 5-7 to obtain bismuth tungstate precursor solution;
adding the erbium source water solution into the bismuth tungstate precursor solution, and performing hydrothermal reaction to obtain an erbium-doped bismuth tungstate nuclear radiation shielding material; the microstructure of the erbium-doped bismuth tungstate is a flower-sphere structure formed by stacking sheets, the thickness of the sheets is 50-80 nm, and the diameter of the flower sphere is 0.5-2.0 mu m; the molar ratio of erbium in the erbium source to tungsten in the tungsten source is (2-15): 100; the temperature of the hydrothermal reaction is 160-200 ℃ and the time is 24-48 h; the erbium-doped bismuth tungstate is in an orthorhombic phase;
the bismuth source is selected from one or two of bismuth nitrate and bismuth oxide; the tungsten source is selected from tungstate, and the tungstate is selected from one or two of sodium tungstate and ammonium tungstate;
the erbium source is one or two selected from erbium nitrate and erbium oxide;
the acid solution is nitric acid aqueous solution or acetic acid aqueous solution;
the molar ratio of bismuth in the bismuth source to tungsten in the tungsten source is (2-2.2): 1-1.2.
3. The method for producing a nuclear radiation shielding material according to claim 2, wherein the pH of the system is adjusted to 5 to 7 by adding an aqueous NaOH solution.
4. The method for producing a nuclear radiation shielding material according to claim 2, wherein,
mixing the bismuth source acid solution and the tungsten source water solution under the stirring condition, stirring for 30-60 min, regulating the pH value of the system to 7, and continuing stirring for 1-2 h to obtain a bismuth tungstate precursor solution; and/or the number of the groups of groups,
and under the stirring condition, adding the erbium source aqueous solution into the bismuth tungstate precursor solution, stirring for 1-2 h, and performing hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
5. The method for preparing a nuclear radiation shielding material according to claim 4, wherein the hydrothermal reaction further comprises the steps of: and (3) sequentially carrying out centrifugal separation, washing and drying on the solution after the hydrothermal reaction to obtain the erbium-doped bismuth tungstate nuclear radiation shielding material.
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| CN107983336A (en) * | 2017-12-11 | 2018-05-04 | 湖北大学 | A kind of praseodymium doped bismuth tungstate light urges agent and preparation method thereof |
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| CN107983336A (en) * | 2017-12-11 | 2018-05-04 | 湖北大学 | A kind of praseodymium doped bismuth tungstate light urges agent and preparation method thereof |
| CN110105743A (en) * | 2019-04-12 | 2019-08-09 | 深圳大学 | A kind of unleaded X, gamma ray shielding material and preparation method thereof |
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