CN110952059B - Preparation method of corrosion-resistant nuclear shielding material - Google Patents
Preparation method of corrosion-resistant nuclear shielding material Download PDFInfo
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- CN110952059B CN110952059B CN201910831337.XA CN201910831337A CN110952059B CN 110952059 B CN110952059 B CN 110952059B CN 201910831337 A CN201910831337 A CN 201910831337A CN 110952059 B CN110952059 B CN 110952059B
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 33
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 22
- 229910052582 BN Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 238000007750 plasma spraying Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 7
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 3
- 230000008313 sensitization Effects 0.000 claims abstract description 3
- 230000001235 sensitizing effect Effects 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 238000007772 electroless plating Methods 0.000 claims 2
- 230000005855 radiation Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000001185 bone marrow Anatomy 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 230000009693 chronic damage Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000007614 genetic variation Effects 0.000 description 1
- 210000002149 gonad Anatomy 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 210000005075 mammary gland Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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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
- G21F1/12—Laminated shielding materials
- G21F1/125—Laminated shielding materials comprising metals
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- Chemical Kinetics & Catalysis (AREA)
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- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a preparation method of a corrosion-resistant nuclear shielding material, which comprises the following operation steps: (1) cleaning and drying boron nitride, and then carrying out sensitization treatment and chemical cobalt plating to obtain modified boron nitride; (2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 10-15:6:3:0.01 for ball milling treatment to obtain mixed powder; (3) adding the obtained mixed powder into a polyvinyl alcohol solution, performing ultrasonic dispersion uniformly, adding the mixed powder into the ball mill again for ball milling for 2-3 hours, performing spray drying, and mixing the powder with modified boron nitride and the like to obtain spraying powder; (4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material. The corrosion-resistant nuclear shielding material prepared by the method has extremely excellent shielding effect on small-dose nuclear radiation, and simultaneously has excellent corrosion resistance and long service life.
Description
Technical Field
The invention belongs to the technical field of nuclear shielding material preparation, and particularly relates to a preparation method of a corrosion-resistant nuclear shielding material.
Background
Radiation can cause genetic variation, radiation sickness, and even death in humans. Research shows that medium and high dose systemic irradiation has the greatest harm, and excessive small dose irradiation can cause diseases of gonads, red bone marrow, bones, lungs, thyroid glands, mammary glands, skins, eye crystals and the like of people. The latent period of these diseases is long, the effect appears late, and the diseases are easy to be ignored by people, but the harm to people is great. Excessive small doses of radiation are more noticeable for chronic injury and late-stage effects in humans. In the prior art, boron carbide powder is often thermally sprayed on the surface of a substrate to prepare a nuclear shielding material, which can effectively shield small-dose nuclear radiation, but the corrosion resistance of a coating is poor, and the corroded coating does not have the nuclear shielding capacity, so that the service life of the nuclear shielding material is shortened.
Disclosure of Invention
The invention provides a preparation method of a corrosion-resistant nuclear shielding material, aiming at improving the corrosion resistance of a surface coating of the nuclear shielding material and prolonging the service life of the nuclear shielding material.
The invention is realized by the following technical scheme.
A preparation method of the corrosion-resistant nuclear shielding material comprises the following operation steps:
(1) adding boron nitride into an ethanol solution for cleaning, then putting the mixture into clear water for cleaning, drying the mixture, then adding the mixture into a sensitizing solution, after the sensitizing treatment, adding the mixture into a chemical plating solution with the pH value of 9.5-10.5, and carrying out chemical cobalt plating to obtain the modified boron nitride, wherein the chemical plating solution is prepared from the following components in parts by weight: 18-22 parts of cobalt sulfate, 40-45 parts of sodium citrate, 0.1-0.5 part of thiourea and 0.1-0.3 part of sodium hexafluorophosphate;
(2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 10-15:6:3:0.01 for ball milling treatment to obtain mixed powder;
(3) adding the obtained mixed powder into a polyvinyl alcohol solution with the weight 2-4 times of that of the mixed powder and the weight of the mixed powder being 3-6wt%, adding the mixed powder into a ball mill again after uniform ultrasonic dispersion, carrying out ball milling treatment for 2-3 hours, carrying out spray drying, and mixing the mixed powder with modified boron nitride and the like to obtain spraying powder;
(4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material.
Further, in the step (1), the sensitizing solution comprises stannous chloride of 10g/L and hydrochloric acid of 40mL/L with volume fraction of 37%.
Further, in the step (1), the sensitization process includes: adding boron nitride into the sensitizing solution, heating to 27 ℃, and performing magnetic stirring treatment for 20min to complete the sensitizing treatment.
Further, in the step (1), 60-70g of boron nitride is added into each liter of chemical plating solution, the temperature of the chemical plating solution is 80 ℃, and the time for chemically plating cobalt is 40-50 min.
Further, in the step (2) and the step (3), during ball milling treatment, the grinding balls are zirconia ceramic balls with the diameter of 10mm, the ball-to-material ratio is 4:1, and the ball milling time in the step (2) is 7 hours.
Further, in the step (3), a centrifugal granulation spray dryer is adopted for spray drying, and the specific parameters are as follows: the inlet temperature is 210 ℃, the outlet temperature is 115 ℃, and the centrifugal turntable is 17500 r/min.
Further, in the step (4), the voltage is 145V, the current is 375A, and the distance of the plasma spraying is 105 mm.
According to the technical scheme, the beneficial effects of the invention are as follows:
the corrosion-resistant nuclear shielding material prepared by the method has extremely excellent shielding effect on small-dose nuclear radiation, and simultaneously has excellent corrosion resistance and long service life. The chemical plating solution in the step (1) can effectively deposit a cobalt simple substance in boron nitride, and the cobalt simple substance and the boron nitride act together to effectively shield small-dose radiation, wherein sodium hexafluorophosphate can improve the plating speed, improve the infiltration capacity of the plating solution on the boron nitride and improve the chemical plating effect; the addition of the graphene oxide and the hydroxylated multi-wall carbon nano tube can effectively improve the compactness of the coating, effectively avoid the contact of oxidizing substances in the environment and reducing substances in the coating, and further effectively improve the oxidation resistance of the coating.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of the corrosion-resistant nuclear shielding material comprises the following operation steps:
(1) adding boron nitride into an ethanol solution, cleaning, then putting into clear water, cleaning, drying, then adding into a sensitizing solution, sensitizing, adding into a chemical plating solution with a pH value of 9.5, adding 60g of boron nitride into each liter of chemical plating solution, and chemically plating cobalt to obtain modified boron nitride, wherein the sensitizing solution comprises 10g/L stannous chloride and 40mL/L hydrochloric acid with a volume fraction of 37%, and the specific operation of the sensitizing is as follows: adding boron nitride into a sensitizing solution, heating to 27 ℃, performing magnetic stirring treatment for 20min, and completing the sensitizing treatment, wherein the chemical plating solution is prepared from the following components in parts by weight: 18 parts of cobalt sulfate, 40 parts of sodium citrate, 0.1 part of thiourea and 0.1 part of sodium hexafluorophosphate, wherein the temperature of the chemical plating solution is 80 ℃, and the time for chemically plating cobalt is 40 min;
(2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 10:6:3:0.01 for ball milling treatment to obtain mixed powder;
(3) adding the obtained mixed powder into a polyvinyl alcohol solution with the weight 2 times that of the mixed powder and the weight of 3-6wt%, adding the mixed powder into a ball mill again after ultrasonic dispersion is uniform, carrying out ball milling treatment for 2 hours, carrying out spray drying, mixing the mixed powder with modified boron nitride and the like to obtain spraying powder, wherein the spray drying adopts a centrifugal granulation spray dryer, and the specific parameters are as follows: the inlet temperature is 210 ℃, the outlet temperature is 115 ℃, and the centrifugal turntable is 17500 r/min;
(4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material, wherein during plasma spraying, the voltage is 145V, the current is 375A, and the spraying distance is 105 mm.
In the step (2) and the step (3), during ball milling treatment, the grinding balls are zirconia ceramic balls with the diameter of 10mm, the ball-to-material ratio is 4:1, and the ball milling time in the step (2) is 7 hours.
Example 2
A preparation method of the corrosion-resistant nuclear shielding material comprises the following operation steps:
(1) adding boron nitride into an ethanol solution, cleaning, then putting into clear water, cleaning, drying, then adding into a sensitizing solution, sensitizing, adding into a chemical plating solution with a pH value of 10.0, adding 65g of boron nitride into each liter of chemical plating solution, and chemically plating cobalt to obtain modified boron nitride, wherein the sensitizing solution comprises 10g/L stannous chloride and 40mL/L hydrochloric acid with a volume fraction of 37%, and the specific operation of the sensitizing is as follows: adding boron nitride into a sensitizing solution, heating to 27 ℃, performing magnetic stirring treatment for 20min, and completing the sensitizing treatment, wherein the chemical plating solution is prepared from the following components in parts by weight: 20 parts of cobalt sulfate, 43 parts of sodium citrate, 0.3 part of thiourea and 0.2 part of sodium hexafluorophosphate, wherein the temperature of the chemical plating solution is 80 ℃, and the time for chemically plating cobalt is 45 min;
(2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 13:6:3:0.01 for ball milling treatment to obtain mixed powder;
(3) adding the obtained mixed powder into 5wt% polyvinyl alcohol solution with the weight 3 times of that of the mixed powder, performing ultrasonic dispersion uniformly, adding the mixed powder into the ball mill again for ball milling for 2.5 hours, performing spray drying, mixing the powder with modified boron nitride and the like to obtain spraying powder, wherein the spray drying adopts a centrifugal granulation spray dryer, and the specific parameters are as follows: the inlet temperature is 210 ℃, the outlet temperature is 115 ℃, and the centrifugal turntable is 17500 r/min;
(4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material, wherein during plasma spraying, the voltage is 145V, the current is 375A, and the spraying distance is 105 mm.
In the step (2) and the step (3), during ball milling treatment, the grinding balls are zirconia ceramic balls with the diameter of 10mm, the ball-to-material ratio is 4:1, and the ball milling time in the step (2) is 7 hours.
Example 3
A preparation method of the corrosion-resistant nuclear shielding material comprises the following operation steps:
(1) adding boron nitride into an ethanol solution, cleaning, then putting into clear water, cleaning, drying, then adding into a sensitizing solution, sensitizing, adding into a chemical plating solution with a pH value of 10.5, adding 70g of boron nitride into each liter of chemical plating solution, and chemically plating cobalt to obtain modified boron nitride, wherein the sensitizing solution comprises 10g/L stannous chloride and 40mL/L hydrochloric acid with a volume fraction of 37%, and the specific operation of the sensitizing is as follows: adding boron nitride into a sensitizing solution, heating to 27 ℃, performing magnetic stirring treatment for 20min, and completing the sensitizing treatment, wherein the chemical plating solution is prepared from the following components in parts by weight: 22 parts of cobalt sulfate, 45 parts of sodium citrate, 0.5 part of thiourea and 0.3 part of sodium hexafluorophosphate, wherein the temperature of the chemical plating solution is 80 ℃, and the time for chemically plating cobalt is 50 min;
(2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 15:6:3:0.01 for ball milling treatment to obtain mixed powder;
(3) adding the obtained mixed powder into a polyvinyl alcohol solution with the weight 4 times that of the mixed powder and the weight of the mixed powder being 6wt%, adding the mixed powder into a ball mill again after ultrasonic dispersion is uniform, carrying out ball milling treatment for 3 hours, carrying out spray drying, mixing the mixed powder with modified boron nitride and the like to obtain spraying powder, wherein the spray drying adopts a centrifugal granulation spray dryer, and the specific parameters are as follows: the inlet temperature is 210 ℃, the outlet temperature is 115 ℃, and the centrifugal turntable is 17500 r/min;
(4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material, wherein during plasma spraying, the voltage is 145V, the current is 375A, and the spraying distance is 105 mm.
In the step (2) and the step (3), during ball milling treatment, the grinding balls are zirconia ceramic balls with the diameter of 10mm, the ball-to-material ratio is 4:1, and the ball milling time in the step (2) is 7 hours.
Comparative example 1
In the step (3), the spray powder contained only modified boron nitride, and the rest of the operation steps were completely the same as those in example 1.
The lead-based composite nuclear shielding material was prepared by the methods of the examples and comparative examples, and the nuclear shielding material was tested for various properties, the test results are shown in table 1:
TABLE 1 Nuclear Shielding Material Performance test results
| Item | Simulating seawater immersion for 12 months | Neutron absorption rate% | Gamma ray absorption rate% |
| Example 1 | No pitting phenomenon on the surface | 93.1 | 23.5 |
| Comparative example 1 | Severe surface pitting | 82.2 | 20.1 |
| Example 2 | No pitting phenomenon on the surface | 93.6 | 24.1 |
| Example 3 | No pitting phenomenon on the surface | 93.9 | 24.8 |
The simulated seawater was 3.5wt% sodium chloride solution, water temperature was 28 deg.C, pH was 7.0, and oxygen content was 4.8 mg/L.
As can be seen from Table 1, the nuclear shielding material prepared by the invention has excellent performance, the coating on the surface of the nuclear shielding material has excellent corrosion resistance, and meanwhile, the nuclear shielding material has excellent shielding performance on nuclear radiation.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (7)
1. The preparation method of the corrosion-resistant nuclear shielding material is characterized by comprising the following operation steps:
(1) adding boron nitride into an ethanol solution for cleaning, then putting the mixture into clear water for cleaning, drying the mixture, then adding the mixture into a sensitizing solution, after the sensitizing treatment, adding the mixture into a chemical plating solution with the pH value of 9.5-10.5, and carrying out chemical cobalt plating to obtain the modified boron nitride, wherein the chemical plating solution is prepared from the following components in parts by weight: 18-22 parts of cobalt sulfate, 40-45 parts of sodium citrate, 0.1-0.5 part of thiourea and 0.1-0.3 part of sodium hexafluorophosphate;
(2) adding lead powder, molybdenum powder, graphene oxide and hydroxylated multi-walled carbon nanotubes into a ball mill according to the mass ratio of 10-15:6:3:0.01 for ball milling treatment to obtain mixed powder;
(3) adding the obtained mixed powder into a polyvinyl alcohol solution with the weight 2-4 times of that of the mixed powder and the weight of the mixed powder being 3-6wt%, adding the mixed powder into a ball mill again after uniform ultrasonic dispersion, carrying out ball milling treatment for 2-3 hours, carrying out spray drying, and mixing the mixed powder with modified boron nitride and the like to obtain spraying powder;
(4) and spraying the spraying powder on the surface of the matrix by using plasma spraying equipment to obtain the corrosion-resistant nuclear shielding material.
2. The method for preparing a corrosion-resistant nuclear shielding material according to claim 1, wherein in the step (1), the sensitizing solution comprises 10g/L stannous chloride and 40mL/L hydrochloric acid with a volume fraction of 37%.
3. The method for preparing a corrosion-resistant nuclear shielding material according to claim 1, wherein in the step (1), the sensitization process comprises the following specific operations: adding boron nitride into the sensitizing solution, heating to 27 ℃, and performing magnetic stirring treatment for 20min to complete the sensitizing treatment.
4. The method for preparing a corrosion-resistant nuclear shielding material according to claim 1, wherein in the step (1), 60-70g of boron nitride is added to each liter of electroless plating solution, the temperature of the electroless plating solution is 80 ℃, and the time for electroless cobalt plating is 40-50 min.
5. The method for preparing a corrosion-resistant nuclear shielding material according to claim 1, wherein in the step (2) and the step (3), the grinding balls are zirconia ceramic balls with a diameter of 10mm during ball milling treatment, the ball-to-material ratio is 4:1, and the ball milling time in the step (2) is 7 hours.
6. The method for preparing the corrosion-resistant nuclear shielding material according to claim 1, wherein in the step (3), the spray drying is performed by using a centrifugal granulation spray dryer, and the specific parameters are as follows: the inlet temperature is 210 ℃, the outlet temperature is 115 ℃, and the centrifugal turntable is 17500 r/min.
7. The method according to claim 1, wherein in the step (4), the voltage is 145V, the current is 375A, and the spraying distance is 105 mm.
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