WO2022166142A1 - PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION - Google Patents
PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION Download PDFInfo
- Publication number
- WO2022166142A1 WO2022166142A1 PCT/CN2021/111436 CN2021111436W WO2022166142A1 WO 2022166142 A1 WO2022166142 A1 WO 2022166142A1 CN 2021111436 W CN2021111436 W CN 2021111436W WO 2022166142 A1 WO2022166142 A1 WO 2022166142A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- core
- shell structure
- gadolinium oxide
- tungsten
- structure tungsten
- Prior art date
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 122
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000010937 tungsten Substances 0.000 title claims abstract description 112
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910001938 gadolinium oxide Inorganic materials 0.000 title claims abstract description 110
- 229940075613 gadolinium oxide Drugs 0.000 title claims abstract description 110
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000003490 calendering Methods 0.000 title claims abstract description 40
- 230000005251 gamma ray Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical class NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 28
- 238000005507 spraying Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 18
- 230000001681 protective effect Effects 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 abstract description 16
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000002466 imines Chemical class 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 229920001690 polydopamine Polymers 0.000 description 24
- 229960003638 dopamine Drugs 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- -1 gadolinium ions Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0887—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
Definitions
- the application relates to the field of radiation protection, in particular to a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection.
- Radiation protection materials are mainly divided into two types: lead-containing materials and lead-free materials.
- Lead is mainly based on lead.
- the protective effect is excellent, it is toxic, has poor strength and has a large scattering of low-energy X-rays.
- Lead-free materials mainly include composite materials made of rare earth elements and heavy metal compounds such as tin, tungsten, and bismuth, which have excellent protective effects and are lightweight and safe.
- Micro-nano core-shell materials with special structures have attracted extensive attention in recent years.
- Composite particles with different core-shell microstructures have unique physical and chemical properties, which also lead to their broad application prospects in many fields such as optics, electronics, catalysis, biology, and radiation.
- the core-shell structure radiation protection material can cooperate in protection, eliminating the weak protection area and effectively absorbing the secondary radiation generated by the radiation.
- the preparation methods of core-shell structures mainly include template method, precipitation method, hydrothermal synthesis method, spray drying method, layer-by-layer self-assembly technology, etc. Li et al.
- the purpose of the present invention is to provide a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection in order to overcome the above-mentioned defects in the prior art.
- the invention provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection, the method comprising the following steps:
- step (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution, stirring, filtering, and calcining at high temperature to obtain the core-shell structure W@Gd 2 O 3 powder.
- step (3) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, and stirred evenly to prepare a core-shell structure tungsten/gadolinium oxide solution.
- step (3) The core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film, and hot-pressed to form a core-shell structure tungsten/gadolinium oxide thin skin layer.
- step (2) the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed and treated in an ultrasonic generator for a period of time, and the dimethylacetamide solution is added dropwise to continue stirring until the dispersion is uniform, Add PVC resin and continue to stir evenly, heat up to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for a period of time to obtain functional PVC adhesive coating.
- step (6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, spraying on the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by spraying process, and drying to obtain a functional PVC coating.
- step (7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC
- the layer is flat and evenly covered on the surface of the polyimide film to obtain a lead-free light-weight X and ⁇ -ray protective material formed by rolling.
- the concentration of the solution should be controlled at 1.5-2.5g/L.
- the main reason is that when the DA concentration is lower than 1.5g/L, only a small amount of PDA particles are deposited on the surface of W.
- the DA concentration is 1.5-2.5g/L, a PDA film is formed on the surface of the W powder.
- the concentration of DA was higher than 2.5 g/L, larger PDA particles were formed by self-polymerization on the surface of W powder due to the high concentration of DA, which was not conducive to the subsequent adsorption of gadolinium ions.
- tris buffer should be added to the system to adjust the pH of the solution to 8-9, because dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions.
- Polydopamine has extraordinary surface activity and adhesion on the surface of different substances, which can provide a platform for the secondary functionalization of materials.
- step (1) needs to be stirred under an electric stirrer for 18-24h.
- step (1) it is necessary to wash with water and ethanol for 2-3 times respectively.
- step (1) the specific conditions for drying described in step (1) are not specifically limited, as long as the purpose of drying the sample can be achieved.
- the concentration of the solution should be controlled at 0.3-0.5M/L. Because when the Gd + concentration is 0.02 M/L, the surface of W is coated with a small amount and sparse nano-dot-like Gd 2 O 3 particles. When the Gd + concentration increases to 0.1M/L, the Gd 2 O 3 nanoparticles on the W surface become larger and larger, which is due to the increase of Gd + concentration. The Gd 2 O 3 nanoparticles combine with each other to form larger Gd 2 O 3 particles. When the Gd + concentration increased to 0.2 M/L, the Gd 2 O 3 nanoparticles on the W surface became larger and denser.
- the Gd 2 O 3 nanoparticles on the W surface were combined with each other to form the core-shell structured W@Gd 2 O 3 .
- the Gd2O3 nanoparticles on the W surface did not change much compared to when the Gd + concentration was 0.3M/L, which was due to the chelation of Gd + by polydopamine on the W surface .
- the synergistic effect has reached saturation at Gd + concentration of 0.3M/L, and excessive concentration will cause waste.
- step (2) is not specifically limited, and only needs to be magnetically stirred for a certain period of time.
- the high-temperature calcination in step (2) needs to be calcined in a muffle furnace at 800-1000° C. for 2-3 hours, and the heating temperature is 2-4° C./min.
- the calcination in step (2) of the present invention is carried out in a protective gas, and the protective gas includes nitrogen or an inert gas, and the inert gas can be argon, helium, etc.
- the protective gas includes nitrogen or an inert gas
- the inert gas can be argon, helium, etc.
- the invention does not make any special limitation on this.
- the powder in step (3) is uniformly dispersed in absolute ethanol, and the mass ratio needs to be controlled to be 1:1 to 1:5.
- step (3) is ultrasonic stirring for 10-20 min.
- the viscosity of the solution in step (3) is 1000-10000 mPa.s.
- step (4) in the hot pressing of step (4), first preheat at 250-270° C. and 0 pressure for 20 minutes, so that the core-shell structure tungsten/gadolinium oxide powder is uniformly heated; the temperature is raised to 285-300° C., Under the mechanical pressure of 25MPa, pressing at constant temperature and pressure for 10-20min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 50-200 ⁇ m.
- the ultrasonic generator in step (5) needs to be processed for 10-20 minutes.
- the first stirring requires mechanical stirring for 1-2 hours, and the second stirring requires stirring for 20-30 minutes.
- step (5) the temperature increase in step (5) needs to be increased to 50-60°C.
- the viscosity of the PVC adhesive coating in step (5) is 1000-5000 mPa.s.
- the process parameters of spraying described in step (6) are that the amount of liquid applied is 500ml/min ⁇ 800ml/min, the air pressure is 0.3MPa ⁇ 0.7MPa, the diameter of the spray nozzle is 10cm, and the distance between the nozzle and the cloth surface is 15cm, the number of times the spray gun goes back and forth is 30 times/min to 120 times/min; the thickness of the functional PU coating is 0.1 to 0.3 mm.
- the calendering process parameters in step (7) are: the temperature of the upper roll is 80°C to 120°C, the temperature of the middle roll is 70°C to 100°C, the temperature of the lower roll is 60°C to 115°C, the roll distance is 1mm, and the rolling speed is 35°C. ⁇ 50m/min.
- the preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection of the present invention comprises the following steps:
- step (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution with a concentration of 0.3-0.5M/L, stirring magnetically for a certain period of time, filtering and separating, drying, and then the prepared sample was heated at 800-1000
- the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2-3 h (heating rate of 2-4 °C/min).
- step (3) uniformly dispersing the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) into anhydrous ethanol, controlling the mass ratio to be 1:1-1:5, and ultrasonically stirring for 10-20min, to prepare a solution with a viscosity of 1000 ⁇ 10000mPa.s core-shell tungsten/gadolinium oxide solution.
- the core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film.
- the hot press preheat at 250-270° C. and 0 pressure for 20 minutes to make the core-shell
- the structured tungsten/gadolinium oxide powder is uniformly heated; the temperature is raised to 285 ⁇ 300°C, under the mechanical pressure of 25MPa, pressed at constant temperature and constant pressure for 10 ⁇ 20min, the core-shell structured tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell Structural tungsten/gadolinium oxide thin skin layer with a thickness of 50-200 ⁇ m.
- step (2) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 10-20 min, dimethylacetamide solution is added dropwise, and mechanical stirring is performed for 1- 2h, add PVC resin and continue to stir evenly, raise the temperature to 50-60°C to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for 20-30min to obtain functional PVC adhesive coating with a viscosity of 1000-5000mPa.s.
- step (6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 500ml/min ⁇ 800ml/min, the air pressure is 0.3MPa ⁇ 0.7MPa, the diameter of the spray nozzle is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 30 times/min ⁇ 120 times/min; after drying
- the functional PVC coating is prepared, and the thickness is 0.1-0.3 mm.
- step (7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC
- the layer is flat and evenly attached to the surface of the polyimide film.
- the calendering process parameters are: the temperature of the upper roll is 80°C ⁇ 120°C, the temperature of the middle roll is 70°C ⁇ 100°C, the temperature of the lower roll is 60°C ⁇ 115°C, and the roll distance is 1mm. , the rolling speed is 35-50 m/min, and the lead-free light-weight X and ⁇ -ray protective materials are obtained by rolling.
- the core-shell structure W@Gd 2 O 3 powder prepared by the above preferred technical solution has a core-shell structure that can play a synergistic protective role in radiation protection and eliminates weak protection. At the same time, the secondary radiation generated by the radiation is effectively absorbed.
- the present invention at least has the following beneficial effects:
- the present invention firstly utilizes that dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions, and polydopamine has extraordinary adhesion on the surfaces of different substances, and can successfully coat tungsten to obtain W@PDA.
- the surface of PDA contains a large number of polar groups such as phenolic hydroxyl groups and amine groups, which provide abundant active sites for complexing various metal ions, which can effectively chelate Gd + in gadolinium nitrate solution.
- PDA forms a nitrogen-doped carbon layer attached to the surface of tungsten, and the W@PDA chelated with Gd + transforms into W@Gd 2 O 3 .
- Fig. 1 is the scanning electron microscope image of a kind of X, ⁇ -ray protective function powder prepared in Example 1.
- the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection, and the method includes the following steps:
- step (2) The W@PDA obtained in step (1) was added to a solution of gadolinium nitrate with a concentration of 0.3M/L, and after magnetic stirring for 2h, filtration and separation were performed, and dried at 80°C for 5h, and then the prepared sample was heated at 800°C.
- the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2 h (heating rate of 2 °C/min).
- step (3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed in absolute ethanol, the mass ratio is controlled to be 1:2, and ultrasonically stirred for 10 minutes to prepare a core-shell with a solution viscosity of 5000 mPa.s Structural tungsten/gadolinium oxide solution.
- step (3) Apply the core-shell tungsten/gadolinium oxide solution obtained in step (3) evenly on the polyimide film.
- the hot press preheat at 250° C. and 0 pressure for 20 minutes to make the core-shell structure tungsten /Gadolinium oxide powder is uniformly heated; raise the temperature to 285°C, press at a constant temperature and pressure for 10min under the mechanical pressure of 25MPa, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 50 ⁇ m.
- step (6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 500ml/min, the air pressure is 0.3MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of round trips of the spray gun is 30 times/min; after drying, a functional PVC coating with a thickness of 0.1mm is obtained.
- step (7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC
- the layer is flat and evenly attached to the surface of the polyimide film.
- the calendering process parameters are: the temperature of the upper roll is 80°C, the temperature of the middle roll is 70°C, the temperature of the lower roll is 60°C, the roll distance is 1mm, and the calendering speed is 35m/min.
- a lead-free light-weight X and ⁇ -ray protective material is obtained by rolling.
- the W@Gd 2 O 3 powder prepared in this example was scanned by SEM, and the obtained photo is shown in Figure 1. It can be seen from the figure that a PDA film is formed on the surface of the W powder.
- the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection, and the method includes the following steps:
- step (2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.35M/L, and after magnetic stirring for 3h, filtration and separation were carried out, and dried at 60°C for 8h, and then the prepared sample was heated at 900 °C.
- the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2.5 h (heating rate of 3 °C/min).
- step (3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, the mass ratio is controlled to be 1:3, and ultrasonically stirred for 15 minutes to prepare a core-shell with a solution viscosity of 7000 mPa.s Structural tungsten/gadolinium oxide solution.
- step (3) Apply the core-shell tungsten/gadolinium oxide solution obtained in step (3) evenly on the polyimide film.
- the hot press preheat for 20 minutes at 260° C. and 0 pressure to make the core-shell structure tungsten /Gadolinium oxide powder is heated evenly; the temperature is raised to 290°C, under the mechanical pressure of 25MPa, press at constant temperature and pressure for 15min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 100 ⁇ m.
- step (2) The core-shell structured tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 15 minutes, dimethylacetamide solution is added dropwise, mechanically stirred for 1.5 hours, and added
- the PVC resin continued to be stirred evenly, the temperature was raised to 55° C. to remove part of the dimethylacetamide, the viscosity value was adjusted, and the stirring was continued for 25 minutes to obtain a functional PVC adhesive coating with a viscosity of 3000 mPa.s.
- step (6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 700ml/min, the air pressure is 0.5MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 80 times/min; after drying, a functional PVC coating with a thickness of 0.2mm is obtained.
- the layer is flat and evenly attached to the surface of the polyimide film.
- the calendering process parameters are: the temperature of the upper roll is 100 °C, the temperature of the middle roll is 80 °C, the temperature of the lower roll is 80 °C, the roll distance is 1 mm, and the rolling speed is 40 m/min.
- the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, ⁇ -ray protection, and the method includes the following steps:
- step (2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.4M/L, magnetically stirred for 2.5h, filtered and separated, dried at 70°C for 6h, and then the prepared sample was placed in The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at 1000 °C under nitrogen for 3 h (the heating rate was 4 °C/min).
- step (3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, the mass ratio is controlled to be 1:4, and ultrasonically stirred for 20 minutes to prepare a core-shell with a solution viscosity of 10000 mPa.s Structural tungsten/gadolinium oxide solution.
- the core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film.
- the hot press preheat for 20 minutes at 270°C and 0 pressure to make the core-shell structure tungsten /Gadolinium oxide powder is heated evenly; the temperature is raised to 300°C, under the mechanical pressure of 25MPa, press at constant temperature and pressure for 20min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 200 ⁇ m.
- step (2) The core-shell structured tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 20 minutes, dimethylacetamide solution is added dropwise, mechanically stirred for 2 hours, and PVC is added The resin continued to be stirred evenly, the temperature was raised to 60° C. to remove part of the dimethylacetamide, the viscosity value was adjusted, and the stirring was continued for 30 minutes to obtain a functional PVC adhesive coating with a viscosity of 5000 mPa.s.
- step (6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 800ml/min, the air pressure is 0.7MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of round trips of the spray gun is 120 times/min; after drying, a functional PVC coating with a thickness of 0.3mm is obtained.
- the layer is flat and evenly attached to the surface of the polyimide film.
- the calendering process parameters are: the temperature of the upper roll is 120 °C, the temperature of the middle roll is 100 °C, the temperature of the lower roll is 115 °C, the roll distance is 1 mm, and the rolling speed is 50 m/min.
Abstract
A preparation method for a core-shell structure tungsten/gadolinium oxide PVC calendered material for X-ray and γ-ray protection, the method comprising: firstly, preparing a core-shell structure tungsten/gadolinium oxide powder; and preparing a core-shell structure tungsten/gadolinium oxide PVC calendered material from the powder. A polyester imine thin film is uniformly coated with the core-shell structure tungsten/gadolinium oxide powder; the core-shell structure tungsten/gadolinium oxide powder is melted into a core-shell structure tungsten/gadolinium oxide thin skin layer upon high-temperature hot pressing; the core-shell structure tungsten/gadolinium oxide powder is added into PVC resin and same is uniformly mixed; the mixture is then sprayed on the surface of the core-shell structure tungsten/gadolinium oxide thin skin layer; and after drying, fabric is subjected to calendaring molding by means of a roller of a calendaring machine to prepare a lead-free and lightweight X-ray and γ-ray protection material. The X-ray and γ-ray protection material can have a synergistic protection effect for radiation protection, and a weak protection area can be eliminated while secondary radiation generated by radiation is effectively absorbed. The functional material has the characteristics of being lead-free and light in weight, and has good application prospects in X-ray and γ-ray radiation protection.
Description
本申请涉及防辐射领域，尤其涉及一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法。The application relates to the field of radiation protection, in particular to a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection.
核技术的发展给人们带来便利的同时也产生了很多辐射危害，轻便灵活且防护性能优良的辐射防护用纺织品是当前研究的热点。辐射防护材料主要分为有铅材料和无铅两种。有铅主要以铅为主，虽防护效果优良，但具有毒性，强度较差且对低能X射线散射较大。无铅材料主要包括稀土元素以及锡、钨、铋等重金属化合物制成的复合材料，防护效果优良且轻质安全。The development of nuclear technology brings convenience to people, but also produces a lot of radiation hazards. The radiation protection textiles that are light, flexible and have excellent protective performance are the current research hotspots. Radiation protection materials are mainly divided into two types: lead-containing materials and lead-free materials. Lead is mainly based on lead. Although the protective effect is excellent, it is toxic, has poor strength and has a large scattering of low-energy X-rays. Lead-free materials mainly include composite materials made of rare earth elements and heavy metal compounds such as tin, tungsten, and bismuth, which have excellent protective effects and are lightweight and safe.
近年来具有特殊结构的微纳米核壳材料引起了人们的广泛关注。不同核壳微观结构的复合粒子会具有独特物理化学性质，这也导致其在光学、电子、催化、生物、辐射等众多领域都具有广阔的应用前景。在防辐射方面，相较于单一金属物理共混的方式，核壳结构辐射防护材料可以协同防护，消除防护弱区同时将辐射所产生的二次辐射进行有效吸收。核壳结构的制备方法主要有模板法、沉淀法、水热合成法、喷雾干燥法、层层自组装技术等。Li等人以二氧化硅为模板采用均相沉淀法制备了壳层厚度可控的氧化钆空心球。然而这些方法都存在工序多、耗时长等缺点，因此有必要指定一种有效的、简单的方法来克服这些缺陷。贻贝分泌的黏附蛋白具有很强的黏附能力，受此启发美国西北大学Messer Smith课题组在2007年发现了多巴胺(DA)在模拟海水的弱碱条件下可以在任何材料表面氧化自聚合成聚多巴胺。其聚合条件简单可控且具有优良的粘附性、亲水性、稳定性、生物相容性。同时，聚多巴胺上存在大量的酚羟基、胺基活性集团，为金属离子的络合提供了丰富的活性位点。Micro-nano core-shell materials with special structures have attracted extensive attention in recent years. Composite particles with different core-shell microstructures have unique physical and chemical properties, which also lead to their broad application prospects in many fields such as optics, electronics, catalysis, biology, and radiation. In terms of radiation protection, compared with the physical blending of a single metal, the core-shell structure radiation protection material can cooperate in protection, eliminating the weak protection area and effectively absorbing the secondary radiation generated by the radiation. The preparation methods of core-shell structures mainly include template method, precipitation method, hydrothermal synthesis method, spray drying method, layer-by-layer self-assembly technology, etc. Li et al. prepared gadolinium oxide hollow spheres with controllable shell thickness by homogeneous precipitation method using silica as template. However, these methods all have the disadvantages of many processes and time-consuming, so it is necessary to specify an effective and simple method to overcome these defects. The adhesion proteins secreted by mussels have strong adhesion ability, inspired by this, Messer Smith's research group from Northwestern University discovered in 2007 that dopamine (DA) can self-polymerize into polymers on the surface of any material under weak alkaline conditions simulating seawater. dopamine. Its polymerization conditions are simple and controllable, and it has excellent adhesion, hydrophilicity, stability and biocompatibility. At the same time, there are a large number of phenolic hydroxyl and amine active groups on polydopamine, which provide abundant active sites for the complexation of metal ions.
发明内容SUMMARY OF THE INVENTION
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法。The purpose of the present invention is to provide a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection in order to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：The object of the present invention can be realized through the following technical solutions:
本发明提供了一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，所述方法包括以下步骤：The invention provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection, the method comprising the following steps:
(1)配置多巴胺盐溶液，加入缓冲液调节PH值，然后加入钨粉，搅拌，过滤，洗涤烘干后得到W@PDA；(1) configure dopamine salt solution, add buffer to adjust pH value, then add tungsten powder, stir, filter, wash and dry to obtain W@PDA;
(2)将步骤(1)得到的W@PDA加入到硝酸钆溶液中，搅拌，过滤，经过高温煅烧得到核壳结构W@Gd
2O
3粉末。
(2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution, stirring, filtering, and calcining at high temperature to obtain the core-shell structure W@Gd 2 O 3 powder.
(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，搅拌均匀制备成核壳结构钨/氧化钆溶液。(3) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, and stirred evenly to prepare a core-shell structure tungsten/gadolinium oxide solution.
(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，热压形成核壳结构钨/氧化钆薄皮层。(4) The core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film, and hot-pressed to form a core-shell structure tungsten/gadolinium oxide thin skin layer.
(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理一段时间，滴加二甲基乙酰胺溶液继续搅拌至分散均匀，加入PVC树脂继续搅拌均匀，升温脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌一段时间，得到功能PVC胶涂料。(5) the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed and treated in an ultrasonic generator for a period of time, and the dimethylacetamide solution is added dropwise to continue stirring until the dispersion is uniform, Add PVC resin and continue to stir evenly, heat up to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for a period of time to obtain functional PVC adhesive coating.
(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，干燥后制得功能PVC涂层。(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, spraying on the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by spraying process, and drying to obtain a functional PVC coating.
(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly covered on the surface of the polyimide film to obtain a lead-free light-weight X and γ-ray protective material formed by rolling.
根据本发明，步骤(1)所述的配置多巴胺盐溶液，溶液浓度应控制在1.5-2.5g/L。主要是因为当DA浓度为低于1.5g/L时，W的表面只沉积有少量的PDA颗粒，当DA浓度为1.5-2.5g/L时，在W粉的表面才形成了PDA薄膜。当DA的浓度高于2.5g/L时，由于DA浓度过高在W粉表面自聚合形成较大的PDA颗粒，又不利于后续对钆离子的吸附。According to the present invention, in the configuration of the dopamine salt solution in step (1), the concentration of the solution should be controlled at 1.5-2.5g/L. The main reason is that when the DA concentration is lower than 1.5g/L, only a small amount of PDA particles are deposited on the surface of W. When the DA concentration is 1.5-2.5g/L, a PDA film is formed on the surface of the W powder. When the concentration of DA was higher than 2.5 g/L, larger PDA particles were formed by self-polymerization on the surface of W powder due to the high concentration of DA, which was not conducive to the subsequent adsorption of gadolinium ions.
值得注意的是，步骤(1)在配置好多巴胺盐溶液后，要向体系中加入tris缓冲液调节溶液PH值为8-9，因为多巴胺在弱碱有氧的条件下可自聚合为聚多巴胺，在不同物质表面聚多巴胺均具有非凡的表面活性和黏附性，可以为材料的二次功能化提供平台。It is worth noting that, after the dopamine salt solution is prepared in step (1), tris buffer should be added to the system to adjust the pH of the solution to 8-9, because dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions. , Polydopamine has extraordinary surface activity and adhesion on the surface of different substances, which can provide a platform for the secondary functionalization of materials.
进一步地，步骤(1)所述的搅拌，需在电动搅拌器下搅拌18-24h。Further, the stirring described in step (1) needs to be stirred under an electric stirrer for 18-24h.
此外，对于步骤(1)所述的洗涤，需用水和乙醇分别洗涤2-3次。In addition, for the washing described in step (1), it is necessary to wash with water and ethanol for 2-3 times respectively.
还有，对于步骤(1)所述的烘干具体的条件不进行具体限定，只要能实现对试样的烘干目的即可。Also, the specific conditions for drying described in step (1) are not specifically limited, as long as the purpose of drying the sample can be achieved.
根据本发明，步骤(2)所述的硝酸钆溶液，该溶液浓度应控制在0.3-0.5M/L。因为当Gd
+浓度为0.02M/L时，W的表面包覆有少量且稀疏的纳米点状Gd
2O
3颗粒。当Gd
+浓度增加到0.1M/L时，W表面的Gd
2O
3纳米颗粒变大增多，这是由于Gd
+浓度的升高Gd
2O
3纳米颗粒互相结合形成更大的Gd
2O
3颗粒。当Gd
+浓度增加到0.2M/L时，W表面的Gd
2O
3纳米颗粒变的更大且更为密集。随着Gd
+浓度增加到0.3M/L，W表面的Gd
2O
3纳米颗粒相互结合形成核壳结构的W@Gd
2O
3。继续增加Gd
+浓度到0.4M/L后，W表面的Gd
2O
3纳米颗粒相比于Gd
+浓度为0.3M/L时没有太大变化，这是由于W表面的聚多巴胺对Gd
+螯合作用在Gd
+浓度为0.3M/L已经达到了饱和，浓度过高会造成浪费。
According to the present invention, for the gadolinium nitrate solution described in step (2), the concentration of the solution should be controlled at 0.3-0.5M/L. Because when the Gd + concentration is 0.02 M/L, the surface of W is coated with a small amount and sparse nano-dot-like Gd 2 O 3 particles. When the Gd + concentration increases to 0.1M/L, the Gd 2 O 3 nanoparticles on the W surface become larger and larger, which is due to the increase of Gd + concentration. The Gd 2 O 3 nanoparticles combine with each other to form larger Gd 2 O 3 particles. When the Gd + concentration increased to 0.2 M/L, the Gd 2 O 3 nanoparticles on the W surface became larger and denser. As the Gd + concentration increased to 0.3 M/L, the Gd 2 O 3 nanoparticles on the W surface were combined with each other to form the core-shell structured W@Gd 2 O 3 . After continuing to increase the Gd + concentration to 0.4M/L, the Gd2O3 nanoparticles on the W surface did not change much compared to when the Gd + concentration was 0.3M/L, which was due to the chelation of Gd + by polydopamine on the W surface . The synergistic effect has reached saturation at Gd + concentration of 0.3M/L, and excessive concentration will cause waste.
进一步地，步骤(2)所述的搅拌，无具体限定，只需磁力搅拌一定时间即可。Further, the stirring described in step (2) is not specifically limited, and only needs to be magnetically stirred for a certain period of time.
此外，步骤(2)所述的高温煅烧，需在马弗炉里800-1000℃条件下煅烧2-3h，升温温度为2-4℃/min。为避免在反应过程中生成杂质，本发明步骤(2)所述煅烧在保护性气体中进行，所述保护性气体包括氮气或惰性气体，所述惰性气体可以为氩气、氦气等，本发明对此不作特殊限定。In addition, the high-temperature calcination in step (2) needs to be calcined in a muffle furnace at 800-1000° C. for 2-3 hours, and the heating temperature is 2-4° C./min. In order to avoid generating impurities during the reaction, the calcination in step (2) of the present invention is carried out in a protective gas, and the protective gas includes nitrogen or an inert gas, and the inert gas can be argon, helium, etc. The invention does not make any special limitation on this.
根据本发明，步骤(3)所述粉末均匀分散到无水乙醇中，需控制质量比为1:1～1:5。According to the present invention, the powder in step (3) is uniformly dispersed in absolute ethanol, and the mass ratio needs to be controlled to be 1:1 to 1:5.
进一步地，步骤(3)所述搅拌为超声搅拌10-20min。Further, the stirring in step (3) is ultrasonic stirring for 10-20 min.
此外，步骤(3)所述溶液粘度为1000～10000mPa.s。In addition, the viscosity of the solution in step (3) is 1000-10000 mPa.s.
根据本发明，步骤(4)所述热压，先在250～270℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至285～300℃，在25MPa的机械压力下，恒温恒压压制10～20min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为50～200μm。According to the present invention, in the hot pressing of step (4), first preheat at 250-270° C. and 0 pressure for 20 minutes, so that the core-shell structure tungsten/gadolinium oxide powder is uniformly heated; the temperature is raised to 285-300° C., Under the mechanical pressure of 25MPa, pressing at constant temperature and pressure for 10-20min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 50-200μm.
根据本发明，步骤(5)所述超声波发生器，需处理10～20min。According to the present invention, the ultrasonic generator in step (5) needs to be processed for 10-20 minutes.
进一步地，步骤(5)所述搅拌，第一次搅拌需机械搅拌1-2h，第二次搅拌需搅拌20～30min。Further, in the stirring in step (5), the first stirring requires mechanical stirring for 1-2 hours, and the second stirring requires stirring for 20-30 minutes.
此外，步骤(5)所述升温需升温至50-60℃。In addition, the temperature increase in step (5) needs to be increased to 50-60°C.
还有，步骤(5)所述PVC胶涂料粘度为1000～5000mPa.s。Also, the viscosity of the PVC adhesive coating in step (5) is 1000-5000 mPa.s.
根据本发明，步骤(6)所述喷涂的工艺参数为上液量为500ml/min～800ml/min，空气压力为0.3MPa～0.7MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为30次/min～120次/min；所述功能PU涂层厚度为0.1～0.3mm。According to the present invention, the process parameters of spraying described in step (6) are that the amount of liquid applied is 500ml/min～800ml/min, the air pressure is 0.3MPa～0.7MPa, the diameter of the spray nozzle is 10cm, and the distance between the nozzle and the cloth surface is 15cm, the number of times the spray gun goes back and forth is 30 times/min to 120 times/min; the thickness of the functional PU coating is 0.1 to 0.3 mm.
根据本发明，步骤(7)所述压延工艺参数为：上辊温度80℃～120℃，中辊温度70℃～100℃，下辊温度60℃～115℃，辊距1mm，压延速度为35～50m/min。According to the present invention, the calendering process parameters in step (7) are: the temperature of the upper roll is 80°C to 120°C, the temperature of the middle roll is 70°C to 100°C, the temperature of the lower roll is 60°C to 115°C, the roll distance is 1mm, and the rolling speed is 35°C. ~50m/min.
作为优选的技术方案，本发明所述的一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法包括以下步骤：As a preferred technical solution, the preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection of the present invention comprises the following steps:
(1)配置1.5g/L-2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节PH至8-9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18-24h后过滤分离，再分别用去离子水和乙醇洗涤2-3次后烘干，得到W@PDA；(1) Prepare a dopamine salt solution with a concentration of 1.5g/L-2.5g/L, add tris buffer to adjust the pH to 8-9, then add tungsten powder cleaned with ethanol, stir with an electric stirrer for 18-24h, and then filter Separate, then wash with deionized water and ethanol for 2-3 times and dry to obtain W@PDA;
(2)将步骤(1)得到的W@PDA加入到0.3-0.5M/L浓度的硝酸钆溶液中，磁力搅拌一定时间后，过滤分离，烘干，再将制得的样品在800-1000℃下通氮气高温煅烧2-3h(升温速率2-4℃/min)，最后得到核壳结构W@Gd
2O
3粉末。
(2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution with a concentration of 0.3-0.5M/L, stirring magnetically for a certain period of time, filtering and separating, drying, and then the prepared sample was heated at 800-1000 The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2-3 h (heating rate of 2-4 °C/min).
(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，控制质量比为1:1～1:5，超声搅拌10-20min，制备成溶液粘度为1000～10000mPa.s的核壳结构钨/氧化钆溶液。(3) uniformly dispersing the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) into anhydrous ethanol, controlling the mass ratio to be 1:1-1:5, and ultrasonically stirring for 10-20min, to prepare a solution with a viscosity of 1000～10000mPa.s core-shell tungsten/gadolinium oxide solution.
(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，至于热压机上，先在250～270℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至285～300℃，在25MPa的机械压力下，恒温恒压压制10～20min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为50～200μm。(4) The core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film. As for the hot press, preheat at 250-270° C. and 0 pressure for 20 minutes to make the core-shell The structured tungsten/gadolinium oxide powder is uniformly heated; the temperature is raised to 285～300℃, under the mechanical pressure of 25MPa, pressed at constant temperature and constant pressure for 10～20min, the core-shell structured tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell Structural tungsten/gadolinium oxide thin skin layer with a thickness of 50-200μm.
(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理10-20min，滴加二甲基乙酰胺溶液，机械搅拌1-2h，加入PVC树脂继续搅拌均匀，升温至50-60℃脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌20-30min，得到功能PVC胶涂料，粘度为1000～5000mPa.s。(5) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 10-20 min, dimethylacetamide solution is added dropwise, and mechanical stirring is performed for 1- 2h, add PVC resin and continue to stir evenly, raise the temperature to 50-60°C to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for 20-30min to obtain functional PVC adhesive coating with a viscosity of 1000-5000mPa.s.
(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，喷涂的工艺参数为上液量为500ml/min～800ml/min，空气压力为0.3MPa～0.7MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为30次/min～120次/min；干燥后制得功能PVC涂层，厚度为0.1～0.3mm。(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 500ml/min～800ml/min, the air pressure is 0.3MPa～0.7MPa, the diameter of the spray nozzle is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 30 times/min～120 times/min; after drying The functional PVC coating is prepared, and the thickness is 0.1-0.3 mm.
(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，压延工艺参数为：上辊温度80℃～120℃，中辊温度70℃～100℃，下辊温度60℃～115℃，辊距1mm，压延速度为35～50m/min，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly attached to the surface of the polyimide film. The calendering process parameters are: the temperature of the upper roll is 80℃～120℃, the temperature of the middle roll is 70℃～100℃, the temperature of the lower roll is 60℃～115℃, and the roll distance is 1mm. , the rolling speed is 35-50 m/min, and the lead-free light-weight X and γ-ray protective materials are obtained by rolling.
采用上述优选的技术方案制得的核壳结构W@Gd
2O
3粉末，相比于钨和氧化钆共混粉末而言，核壳结构在辐射防护方面可以起到协同防护作用，消除防护弱区同时将辐射所产生的二次辐射进行有效吸收。
Compared with the tungsten and gadolinium oxide blend powder, the core-shell structure W@Gd 2 O 3 powder prepared by the above preferred technical solution has a core-shell structure that can play a synergistic protective role in radiation protection and eliminates weak protection. At the same time, the secondary radiation generated by the radiation is effectively absorbed.
与现有技术方案相比，本发明至少具有以下有益效果：Compared with the prior art solutions, the present invention at least has the following beneficial effects:
本发明首先利用多巴胺在在弱碱有氧的条件下可自聚合为聚多巴胺，并且聚多巴胺在不同物质表面均具有非凡的黏附性，能够成功包覆钨，得到W@PDA。The present invention firstly utilizes that dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions, and polydopamine has extraordinary adhesion on the surfaces of different substances, and can successfully coat tungsten to obtain W@PDA.
PDA表面含有大量的酚羟基、胺基等极性基团，为络合各种金属离子提供了丰富的活性位点，能够有效地和硝酸钆溶液中的Gd
+进行螯合。经过高温煅烧后PDA形成氮掺杂碳层附着在钨表面，而与Gd
+发生螯的W@PDA转变成W@Gd
2O
3。
The surface of PDA contains a large number of polar groups such as phenolic hydroxyl groups and amine groups, which provide abundant active sites for complexing various metal ions, which can effectively chelate Gd + in gadolinium nitrate solution. After high temperature calcination, PDA forms a nitrogen-doped carbon layer attached to the surface of tungsten, and the W@PDA chelated with Gd + transforms into W@Gd 2 O 3 .
图1为实施例1制得的一种X，γ射线防护功能粉体的扫描电镜图。Fig. 1 is the scanning electron microscope image of a kind of X, γ-ray protective function powder prepared in Example 1.
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, typical but non-limiting examples of the present invention are as follows:
实施例1Example 1
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，所述方法包括以下步骤为：The present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection, and the method includes the following steps:
(1)配置2g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为8.5，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌24h后过滤分离，再分别用去离子水和乙醇洗涤2次后，在80℃下烘干5h，得到W@PDA；(1) Prepare dopamine salt solution with a concentration of 2g/L, add tris buffer to adjust the pH value of the solution to 8.5, then add tungsten powder cleaned with ethanol, stir with an electric stirrer for 24 hours, filter and separate, and then use deionized water respectively. After washing twice with ethanol, drying at 80 °C for 5 h to obtain W@PDA;
(2)将步骤(1)得到的W@PDA加入到0.3M/L浓度的硝酸钆溶液中，磁力搅拌2h后，过滤分离，在80℃下烘干5h，再将制得的样品在800℃下通氮气高温煅烧2h(升温速率2℃/min)，最后得到核壳结构W@Gd
2O
3粉末。
(2) The W@PDA obtained in step (1) was added to a solution of gadolinium nitrate with a concentration of 0.3M/L, and after magnetic stirring for 2h, filtration and separation were performed, and dried at 80°C for 5h, and then the prepared sample was heated at 800°C. The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2 h (heating rate of 2 °C/min).
(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，控制质量比为1:2，超声搅拌10min，制备成溶液粘度为5000mPa.s的核壳结构钨/氧化钆溶液。(3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed in absolute ethanol, the mass ratio is controlled to be 1:2, and ultrasonically stirred for 10 minutes to prepare a core-shell with a solution viscosity of 5000 mPa.s Structural tungsten/gadolinium oxide solution.
(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，至于热压机上，先在250℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至285℃，在25MPa的机械压力下，恒温恒压压制10min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为50μm。(4) Apply the core-shell tungsten/gadolinium oxide solution obtained in step (3) evenly on the polyimide film. As for the hot press, preheat at 250° C. and 0 pressure for 20 minutes to make the core-shell structure tungsten /Gadolinium oxide powder is uniformly heated; raise the temperature to 285℃, press at a constant temperature and pressure for 10min under the mechanical pressure of 25MPa, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 50 μm.
(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理10min，滴加二甲基乙酰胺溶液，机械搅拌1h，加入PVC树脂继续搅拌均匀，升 温至50℃脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌20min，得到功能PVC胶涂料，粘度为2000mPa.s。(5) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed and then treated in an ultrasonic generator for 10 minutes, dimethylacetamide solution is added dropwise, mechanically stirred for 1 hour, and PVC is added The resin continued to be stirred evenly, the temperature was raised to 50° C. to remove part of the dimethylacetamide, the viscosity value was adjusted, and the stirring was continued for 20 minutes to obtain a functional PVC adhesive coating with a viscosity of 2000 mPa.s.
(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，喷涂的工艺参数为上液量为500ml/min，空气压力为0.3MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为30次/min；干燥后制得功能PVC涂层，厚度为0.1mm。(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 500ml/min, the air pressure is 0.3MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of round trips of the spray gun is 30 times/min; after drying, a functional PVC coating with a thickness of 0.1mm is obtained.
(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，压延工艺参数为：上辊温度80℃，中辊温度70℃℃，下辊温度60℃，辊距1mm，压延速度为35m/min，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly attached to the surface of the polyimide film. The calendering process parameters are: the temperature of the upper roll is 80°C, the temperature of the middle roll is 70°C, the temperature of the lower roll is 60°C, the roll distance is 1mm, and the calendering speed is 35m/min. A lead-free light-weight X and γ-ray protective material is obtained by rolling.
对本实施例制备得到的W@Gd
2O
3粉末进行了SEM扫描，所得照片如图1所示，由图中可以看出，在W粉的表面形成了PDA薄膜。
The W@Gd 2 O 3 powder prepared in this example was scanned by SEM, and the obtained photo is shown in Figure 1. It can be seen from the figure that a PDA film is formed on the surface of the W powder.
实施例2Example 2
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，所述方法包括以下步骤为：The present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection, and the method includes the following steps:
(1)配置1.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为8，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌20h后过滤分离，再分别用去离子水和乙醇洗涤3次后，在60℃下烘干8h，得到W@PDA；(1) Prepare dopamine salt solution with a concentration of 1.5g/L, add tris buffer to adjust the pH value of the solution to 8, then add tungsten powder cleaned with ethanol, stir with an electric stirrer for 20 hours, filter and separate, and then deionize the solution separately. After washing with water and ethanol 3 times, drying at 60 °C for 8 h to obtain W@PDA;
(2)将步骤(1)得到的W@PDA加入到0.35M/L浓度的硝酸钆溶液中，磁力搅拌3h后，过滤分离，在60℃下烘干8h，再将制得的样品在900℃下通氮气高温煅烧2.5h(升温速率3℃/min)，最后得到核壳结构W@Gd
2O
3粉末。
(2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.35M/L, and after magnetic stirring for 3h, filtration and separation were carried out, and dried at 60°C for 8h, and then the prepared sample was heated at 900 °C. The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2.5 h (heating rate of 3 °C/min).
(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，控制质量比为1:3，超声搅拌15min，制备成溶液粘度为7000mPa.s的核壳结构钨/氧化钆溶液。(3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, the mass ratio is controlled to be 1:3, and ultrasonically stirred for 15 minutes to prepare a core-shell with a solution viscosity of 7000 mPa.s Structural tungsten/gadolinium oxide solution.
(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，至于热压机上，先在260℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至290℃，在25MPa的机械压力下，恒温恒压压制15min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为100μm。(4) Apply the core-shell tungsten/gadolinium oxide solution obtained in step (3) evenly on the polyimide film. As for the hot press, preheat for 20 minutes at 260° C. and 0 pressure to make the core-shell structure tungsten /Gadolinium oxide powder is heated evenly; the temperature is raised to 290℃, under the mechanical pressure of 25MPa, press at constant temperature and pressure for 15min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 100 μm.
(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理15min，滴加二甲基乙酰胺溶液，机械搅拌1.5h，加入PVC树脂继续搅拌均匀，升温至55℃脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌25min，得到功能PVC胶涂料，粘度为3000mPa.s。(5) The core-shell structured tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 15 minutes, dimethylacetamide solution is added dropwise, mechanically stirred for 1.5 hours, and added The PVC resin continued to be stirred evenly, the temperature was raised to 55° C. to remove part of the dimethylacetamide, the viscosity value was adjusted, and the stirring was continued for 25 minutes to obtain a functional PVC adhesive coating with a viscosity of 3000 mPa.s.
(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，喷涂的工艺参数为上液量为700ml/min，空气压力为0.5MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为80次/min；干燥后制得功能PVC涂层，厚度为0.2mm。(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 700ml/min, the air pressure is 0.5MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 80 times/min; after drying, a functional PVC coating with a thickness of 0.2mm is obtained.
(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，压延工艺参数为：上辊温度100℃，中辊温度80℃，下辊温度80℃，辊距1mm，压延速度为40m/min，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly attached to the surface of the polyimide film. The calendering process parameters are: the temperature of the upper roll is 100 °C, the temperature of the middle roll is 80 °C, the temperature of the lower roll is 80 °C, the roll distance is 1 mm, and the rolling speed is 40 m/min. A lead-free light-weight X and γ-ray protective material formed by extrusion.
实施例3Example 3
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，所述方法包括以下步骤为：The present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection, and the method includes the following steps:
(1)配置2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18h后过滤分离，再分别用去离子水和乙醇洗涤2次后，在70℃下烘干6h，得到W@PDA；(1) Prepare dopamine salt solution with a concentration of 2.5g/L, add tris buffer to adjust the pH value of the solution to 9, then add tungsten powder cleaned with ethanol, stir with an electric stirrer for 18 hours, filter and separate, and then deionize the solution separately. After being washed twice with water and ethanol, dried at 70 °C for 6 h to obtain W@PDA;
(2)将步骤(1)得到的W@PDA加入到0.4M/L浓度的硝酸钆溶液中，磁力搅拌2.5h后，过滤分离，在70℃下烘干6h，再将制得的样品在1000℃下通氮气高温煅烧3h(升温速率4℃/min)，最后得到核壳结构W@Gd
2O
3粉末。
(2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.4M/L, magnetically stirred for 2.5h, filtered and separated, dried at 70°C for 6h, and then the prepared sample was placed in The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at 1000 °C under nitrogen for 3 h (the heating rate was 4 °C/min).
(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，控制质量比为1:4，超声搅拌20min，制备成溶液粘度为10000mPa.s的核壳结构钨/氧化钆溶液。(3) The core-shell tungsten/gadolinium oxide powder obtained in step (2) is uniformly dispersed into absolute ethanol, the mass ratio is controlled to be 1:4, and ultrasonically stirred for 20 minutes to prepare a core-shell with a solution viscosity of 10000 mPa.s Structural tungsten/gadolinium oxide solution.
(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，至于热压机上，先在270℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至300℃，在25MPa的机械压力下，恒温恒压压制20min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为200μm。(4) The core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film. As for the hot press, preheat for 20 minutes at 270°C and 0 pressure to make the core-shell structure tungsten /Gadolinium oxide powder is heated evenly; the temperature is raised to 300℃, under the mechanical pressure of 25MPa, press at constant temperature and pressure for 20min, the core-shell structure tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 200 μm.
(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理20min，滴加二甲基乙酰胺溶液，机械搅拌2h，加入PVC树脂继续搅拌均匀，升温至60℃脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌30min，得到功能PVC胶涂料，粘度为5000mPa.s。(5) The core-shell structured tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 20 minutes, dimethylacetamide solution is added dropwise, mechanically stirred for 2 hours, and PVC is added The resin continued to be stirred evenly, the temperature was raised to 60° C. to remove part of the dimethylacetamide, the viscosity value was adjusted, and the stirring was continued for 30 minutes to obtain a functional PVC adhesive coating with a viscosity of 5000 mPa.s.
(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，喷涂的工艺参数为上液量为800ml/min，空气压力为0.7MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为120次/min；干燥后制得功能PVC涂层，厚度为0.3mm。(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 800ml/min, the air pressure is 0.7MPa, the diameter of the nozzle of the spray head is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of round trips of the spray gun is 120 times/min; after drying, a functional PVC coating with a thickness of 0.3mm is obtained.
(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，压延工艺参数为：上辊温度120℃，中辊温度100℃，下辊温度115℃，辊距1mm，压延速度为50m/min，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly attached to the surface of the polyimide film. The calendering process parameters are: the temperature of the upper roll is 120 °C, the temperature of the middle roll is 100 °C, the temperature of the lower roll is 115 °C, the roll distance is 1 mm, and the rolling speed is 50 m/min. A lead-free light-weight X and γ-ray protective material formed by extrusion.
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is provided to facilitate understanding and use of the invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the above-mentioned embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.
Claims (20)
- 一种X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，所述方法包括以下步骤：A kind of preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection, it is characterized in that, described method comprises the following steps:(1)配置多巴胺盐溶液，加入缓冲液调节PH值，然后加入钨粉，搅拌，过滤，洗涤烘干后得到W@PDA：(1) Configure dopamine salt solution, add buffer to adjust pH value, then add tungsten powder, stir, filter, wash and dry to obtain W@PDA:(2)将步骤(1)得到的W@PDA加入到硝酸钆溶液中，搅拌，过滤，经过高温煅烧得到核壳结构W@Gd 2O 3粉末； (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution, stirring, filtering, and calcining at high temperature to obtain the core-shell structure W@Gd 2 O 3 powder;(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，搅拌均匀制备成核壳结构钨/氧化钆溶液；(3) uniformly dispersing the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) into absolute ethanol, and stirring to prepare a core-shell structure tungsten/gadolinium oxide solution;(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，热压形成核壳结构钨/氧化钆薄皮层；(4) evenly coating the core-shell structure tungsten/gadolinium oxide solution obtained in step (3) on the polyimide film, and hot pressing to form a core-shell structure tungsten/gadolinium oxide thin skin layer;(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理一段时间，滴加二甲基乙酰胺溶液继续搅拌至分散均匀，加入PVC树脂继续搅拌均匀，升温脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌一段时间，得到功能PVC胶涂料；(5) the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed and treated in an ultrasonic generator for a period of time, and the dimethylacetamide solution is added dropwise to continue stirring until the dispersion is uniform, Add PVC resin and continue to stir evenly, heat up to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for a period of time to obtain functional PVC adhesive coating;(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，干燥后制得功能PVC涂层；(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and drying to obtain a functional PVC coating;(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly covered on the surface of the polyimide film to obtain a lead-free light-weight X and γ-ray protective material formed by rolling.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(1)所述加入缓冲液调节PH值，所述缓冲液为tris，所述PH值为8-9。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection as claimed in claim 1, is characterized in that, in step (1) described adding buffer to adjust pH value, and described buffer is tris, the pH is 8-9.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(1)所述钨粉为用乙醇清洗过的钨粉。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, in step (1), the tungsten powder is tungsten powder cleaned with ethanol.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(1)所述搅拌为电动搅拌器搅拌18-24h。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, the stirring in step (1) is an electric stirrer stirring for 18-24h.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(1)所述洗涤为用去离子水和乙醇分别清洗2-3次。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, is characterized in that, in step (1) described washing is to wash with deionized water and ethanol respectively 2- 3 times.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(1)所述多巴胺盐溶液浓度为1.5g/L-2.5g/L。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X and γ-ray protection as claimed in claim 1, wherein the concentration of the dopamine salt solution in step (1) is 1.5g/L-2.5g /L.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(2)所述高温煅烧温度为800-1000℃，时间为2-3h，升温速率为2-4℃/min。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, characterized in that, in step (2), the high-temperature calcination temperature is 800-1000° C., and the time is 2 -3h, the heating rate is 2-4°C/min.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(2)所述煅烧在保护性气体中进行，所述保护性气体为氮气或惰性气体。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, wherein the calcination in step (2) is carried out in a protective gas, and the protective The gas is nitrogen or an inert gas.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(2)所述硝酸钆溶液浓度为0.3-0.5M/L以上。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, wherein the concentration of the gadolinium nitrate solution in step (2) is more than 0.3-0.5M/L .
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(3)所述粉末均匀分散到无水乙醇中，需控制质量比为1:1～1:5。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, characterized in that, in step (3), the powder is uniformly dispersed in absolute ethanol, and the quality needs to be controlled The ratio is 1:1 to 1:5.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法， 其特征在于，在步骤(3)所述搅拌为超声搅拌10-20min。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, the stirring in step (3) is ultrasonic stirring for 10-20 min.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(3)所述溶液粘度为1000～10000mPa.s。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, in step (3), the solution viscosity is 1000-10000 mPa.s.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(4)所述热压，先在250～270℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至285～300℃，在25MPa的机械压力下，恒温恒压压制10～20min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为50～200μm。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, characterized in that, in the hot pressing in step (4), firstly at 250-270° C., 0 pressure Preheat for 20 minutes, so that the core-shell structure tungsten/gadolinium oxide powder is uniformly heated; increase the temperature to 285-300 °C, under the mechanical pressure of 25MPa, press at constant temperature and pressure for 10-20 minutes, the core-shell structure tungsten/gadolinium oxide The powder is melted at high temperature to form a core-shell structure tungsten/gadolinium oxide thin skin layer with a thickness of 50-200 μm.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(5)所述超声波发生器，需处理10～20min。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, the ultrasonic generator in step (5) needs to be processed for 10-20 min.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(5)所述搅拌，第一次搅拌需机械搅拌1-2h，第二次搅拌需搅拌20～30min。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in claim 1, is characterized in that, in the stirring described in step (5), the first stirring requires mechanical stirring for 1-2h , the second stirring needs to be stirred for 20 to 30 minutes.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(5)所述升温需升温至50-60℃。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, the temperature in step (5) needs to be heated to 50-60°C.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(5)所述PVC胶涂料粘度为1000～5000mPa.s。The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection according to claim 1, characterized in that, in step (5), the viscosity of the PVC glue coating is 1000-5000 mPa.s.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(6)所述喷涂的工艺参数为上液量为500ml/min～800ml/min，空气压力为0.3MPa～0.7MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为30次/min～120次/min；所述功能PU涂层厚度为0.1～0.3mm。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection as claimed in claim 1, is characterized in that, the process parameter of spraying described in step (6) is that the amount of liquid is 500ml/min ～800ml/min, the air pressure is 0.3MPa～0.7MPa, the diameter of the spray nozzle is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 30 times/min～120 times/min; the functional PU coating The layer thickness is 0.1 to 0.3 mm.
- 如权利要求1所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，在步骤(7)所述压延工艺参数为：上辊温度80℃～120℃，中辊温度70℃～100℃，下辊温度60℃～115℃，辊距1mm，压延速度为35～50m/min。The preparation method of core-shell structure tungsten/gadolinium oxide PVC calendering material for X, gamma ray protection as claimed in claim 1, characterized in that, in step (7), the calendering process parameters are: the temperature of the upper roller is 80 ℃～120 ℃ ℃, the middle roll temperature is 70℃～100℃, the bottom roll temperature is 60℃～115℃, the roll distance is 1mm, and the rolling speed is 35～50m/min.
- 如权利要求1-19任一项所述的X，γ射线防护用核壳结构钨/氧化钆PVC压延材料的制备方法，其特征在于，所述方法包括以下步骤：The preparation method of the core-shell structure tungsten/gadolinium oxide PVC calendering material for X, γ-ray protection as claimed in any one of claims 1-19, wherein the method comprises the following steps:(1)配置1.5g/L-2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节PH至8-9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18-24h后过滤分离，再分别用去离子水和乙醇洗涤2-3次后烘干，得到W@PDA；(1) Prepare a dopamine salt solution with a concentration of 1.5g/L-2.5g/L, add tris buffer to adjust the pH to 8-9, then add tungsten powder cleaned with ethanol, stir with an electric stirrer for 18-24h, and then filter Separate, then wash with deionized water and ethanol for 2-3 times and dry to obtain W@PDA;(2)将步骤(1)得到的W@PDA加入到0.3-0.5M/L浓度的硝酸钆溶液中，磁力搅拌一定时间后，过滤分离，烘干，再将制得的样品在800-1000℃下通氮气高温煅烧2-3h(升温速率2-4℃/min)，最后得到核壳结构W@Gd 2O 3粉末； (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution with a concentration of 0.3-0.5M/L, stirring magnetically for a certain period of time, filtering and separating, drying, and then the prepared sample was heated at 800-1000 calcined at high temperature under nitrogen for 2-3h (heating rate of 2-4°C/min), and finally the core-shell structure W@Gd 2 O 3 powder was obtained;(3)将步骤(2)得到的核壳结构钨/氧化钆粉体均匀分散到无水乙醇中，控制质量比为1:1～1:5，超声搅拌10-20min，制备成溶液粘度为1000～10000mPa.s的核壳结构钨/氧化钆溶液；(3) uniformly dispersing the core-shell structure tungsten/gadolinium oxide powder obtained in step (2) into anhydrous ethanol, controlling the mass ratio to be 1:1-1:5, and ultrasonically stirring for 10-20min, to prepare a solution with a viscosity of 1000～10000mPa.s core-shell tungsten/gadolinium oxide solution;(4)将步骤(3)得到的核壳结构钨/氧化钆溶液均匀涂抹在聚酰亚胺薄膜上，至于热压机上，先在250～270℃、0压力下预热20min，使得核壳结构钨/氧化钆粉体均匀受热；将温度升高至285～300℃，在25MPa的机械压力下，恒温恒压压制10～20min，核壳结构钨/氧化钆粉体高温熔融，形成核壳结构钨/氧化钆薄皮层，厚度为50～200μm；(4) The core-shell structure tungsten/gadolinium oxide solution obtained in step (3) is evenly spread on the polyimide film. As for the hot press, preheat at 250-270° C. and 0 pressure for 20 minutes to make the core-shell The structured tungsten/gadolinium oxide powder is uniformly heated; the temperature is raised to 285～300℃, under the mechanical pressure of 25MPa, pressed at constant temperature and constant pressure for 10～20min, the core-shell structured tungsten/gadolinium oxide powder is melted at high temperature to form a core-shell Structural tungsten/gadolinium oxide thin skin layer with a thickness of 50-200μm;(5)将步骤(2)得到的核壳结构钨/氧化钆粉体和硅烷偶联剂均匀混合后在超声波发生器内处理10-20min，滴加二甲基乙酰胺溶液，机械搅拌1-2h，加入PVC树脂继续搅拌均匀，升温至50-60℃脱除部分二甲基乙酰胺，调节粘度值，再继续搅拌20-30min，得到功能PVC胶涂料，粘度为1000～5000mPa.s；(5) The core-shell structure tungsten/gadolinium oxide powder obtained in step (2) and the silane coupling agent are uniformly mixed, and then treated in an ultrasonic generator for 10-20 min, dimethylacetamide solution is added dropwise, and mechanical stirring is performed for 1- 2h, add PVC resin and continue to stir evenly, raise the temperature to 50-60°C to remove part of dimethylacetamide, adjust the viscosity value, and continue stirring for 20-30min to obtain functional PVC adhesive coating with a viscosity of 1000-5000mPa.s;(6)将步骤(5)得到的PVC胶涂料加入喷涂装置料筒，通过喷涂工艺喷涂到步骤(4)得到的核壳结构钨/氧化钆薄皮层上，喷涂的工艺参数为上液量为500ml/min～800ml/min，空气压力为0.3MPa～0.7MPa，喷涂头喷嘴的直径为10cm，喷嘴距布面距离为15cm，喷枪往返的次数为30次/min～120次/min；干燥后制得功能PVC涂层，厚度为0.1～0.3mm；(6) adding the PVC glue coating obtained in step (5) to the barrel of the spraying device, and spraying onto the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) by a spraying process, and the process parameter of spraying is that the amount of liquid applied is 500ml/min～800ml/min, the air pressure is 0.3MPa～0.7MPa, the diameter of the spray nozzle is 10cm, the distance between the nozzle and the cloth surface is 15cm, and the number of times the spray gun goes back and forth is 30 times/min～120 times/min; after drying A functional PVC coating is prepared with a thickness of 0.1 to 0.3 mm;(7)将步骤(4)得到的核壳结构钨/氧化钆薄皮层和步骤(6)得到的PVC涂层通过压延机辊筒延压，使得核壳结构钨/氧化钆薄片层和功能PVC层平整、均匀地覆贴于聚酰亚胺薄膜表面，压延工艺参数为：上辊温度80℃～120℃，中辊温度70℃～100℃，下辊温度60℃～115℃，辊距1mm，压延速度为35～50m/min，得到延压成型的无铅轻质X、γ射线防护材料。(7) rolling the core-shell structure tungsten/gadolinium oxide thin skin layer obtained in step (4) and the PVC coating obtained in step (6) through a calender roll, so that the core-shell structure tungsten/gadolinium oxide thin layer and functional PVC The layer is flat and evenly attached to the surface of the polyimide film. The calendering process parameters are: the temperature of the upper roll is 80℃～120℃, the temperature of the middle roll is 70℃～100℃, the temperature of the lower roll is 60℃～115℃, and the roll distance is 1mm. , the rolling speed is 35-50 m/min, and the lead-free light-weight X and γ-ray protective materials are obtained by rolling.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110178876.5A CN112831078B (en) | 2021-02-08 | 2021-02-08 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| CN202110178876.5 | 2021-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022166142A1 true WO2022166142A1 (en) | 2022-08-11 |
Family
ID=75933199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/111436 WO2022166142A1 (en) | 2021-02-08 | 2021-08-09 | PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112831078B (en) |
| WO (1) | WO2022166142A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112831855B (en) * | 2021-02-08 | 2022-05-31 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection |
| CN112831078B (en) * | 2021-02-08 | 2022-08-16 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| CN112846173A (en) * | 2021-02-08 | 2021-05-28 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide powder for X, gamma ray protection |
| CN113321877B (en) * | 2021-06-15 | 2023-04-07 | 天津天颐科苑科技有限公司 | Recyclable flexible radiation-proof sheet and preparation method thereof |
| CN113845817B (en) * | 2021-09-27 | 2022-07-12 | 哈尔滨工业大学 | Preparation method of double-component functional filler composite coating for space high-energy proton radiation protection |
| CN113943531B (en) * | 2021-09-27 | 2022-08-19 | 哈尔滨工业大学 | Radiation-resistant packaging reinforced CMOS device and preparation method thereof |
| CN113881312B (en) * | 2021-09-30 | 2022-06-17 | 哈尔滨工业大学 | Rare earth-high Z-graphene-composite coating for aerospace-grade chip total dose effect protection and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004055833A1 (en) * | 2002-12-17 | 2004-07-01 | Lanxess Deutschland Gmbh | Lead-free mixture used as an additive for shielding radiation |
| US20070194256A1 (en) * | 2005-05-10 | 2007-08-23 | Space Micro, Inc. | Multifunctional radiation shield for space and aerospace applications |
| CN110911025A (en) * | 2019-11-27 | 2020-03-24 | 中国人民解放军海军特色医学中心 | Multiple ray shielding material |
| CN110948918A (en) * | 2019-11-27 | 2020-04-03 | 中国人民解放军海军特色医学中心 | Preparation method of composite radiation protection material |
| CN111849175A (en) * | 2020-07-16 | 2020-10-30 | 成都盛帮密封件股份有限公司 | Irradiation-resistant lead-free radiation shielding flexible material, and preparation method and application thereof |
| CN112831078A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| CN112831855A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection |
| CN112846173A (en) * | 2021-02-08 | 2021-05-28 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide powder for X, gamma ray protection |
| CN112900110A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PU coating fabric for X, gamma ray protection |
| CN112900155A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of non-woven fabric for X and gamma ray protection |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103463648A (en) * | 2013-08-23 | 2013-12-25 | 南京大学 | Surface modified ferric oxide nucleus-gadolinium oxide shell composite nano particle, as well as preparation method and application of particle |
| CN107052356B (en) * | 2017-01-18 | 2019-01-15 | 天津大学 | A kind of preparation method of the tungsten of core-shell structure-yttrium oxide superfine composite precursor powder |
| CN109181224B (en) * | 2018-08-08 | 2020-11-24 | 中国科学院合肥物质科学研究院 | Composite shielding material containing MOF-derived porous gadolinium oxide and preparation method thereof |
| CN110057885B (en) * | 2019-04-15 | 2021-07-02 | 安徽师范大学 | Gadolinium oxide nano hollow sphere modified electrode, preparation method thereof, electrochemical sensor and application |
| CN110038614B (en) * | 2019-05-20 | 2020-06-16 | 中国科学院长春应用化学研究所 | Cobalt nitride loaded nitrogen-doped carbon material and preparation method thereof |
| CN110372903B (en) * | 2019-07-15 | 2022-02-01 | 南通大学 | Lead-free light X, gamma and neutron integrated protection material and preparation method thereof |
| CN111250697B (en) * | 2020-02-18 | 2022-03-29 | 太原理工大学 | Preparation method of gadolinium oxide/tungsten/aluminum neutron and gamma ray core-shell co-shielding material |
-
2021
- 2021-02-08 CN CN202110178876.5A patent/CN112831078B/en active Active
- 2021-08-09 WO PCT/CN2021/111436 patent/WO2022166142A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004055833A1 (en) * | 2002-12-17 | 2004-07-01 | Lanxess Deutschland Gmbh | Lead-free mixture used as an additive for shielding radiation |
| US20070194256A1 (en) * | 2005-05-10 | 2007-08-23 | Space Micro, Inc. | Multifunctional radiation shield for space and aerospace applications |
| CN110911025A (en) * | 2019-11-27 | 2020-03-24 | 中国人民解放军海军特色医学中心 | Multiple ray shielding material |
| CN110948918A (en) * | 2019-11-27 | 2020-04-03 | 中国人民解放军海军特色医学中心 | Preparation method of composite radiation protection material |
| CN111849175A (en) * | 2020-07-16 | 2020-10-30 | 成都盛帮密封件股份有限公司 | Irradiation-resistant lead-free radiation shielding flexible material, and preparation method and application thereof |
| CN112831078A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection |
| CN112831855A (en) * | 2021-02-08 | 2021-05-25 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide functional fiber for X, gamma ray protection |
| CN112846173A (en) * | 2021-02-08 | 2021-05-28 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide powder for X, gamma ray protection |
| CN112900110A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of core-shell structure tungsten/gadolinium oxide PU coating fabric for X, gamma ray protection |
| CN112900155A (en) * | 2021-02-08 | 2021-06-04 | 南通大学 | Preparation method of non-woven fabric for X and gamma ray protection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112831078A (en) | 2021-05-25 |
| CN112831078B (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022166142A1 (en) | PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION | |
| WO2022166171A1 (en) | Preparation method for tungsten/gadolinium oxide pu coating fabric with core-shell structure for x and γ rays protection | |
| WO2021174709A1 (en) | Spray separator for lithium ion battery and preparation method therefor | |
| WO2022166152A1 (en) | PREPARATION METHOD FOR CORE-SHELL STRUCTURED TUNGSTEN/GADOLINIUM OXIDE POWDER FOR X AND γ RAY PROTECTION | |
| CN104282865B (en) | Preparation method of gel polymer coating composite membrane, and battery diaphragm | |
| CN112900155B (en) | Preparation method of non-woven fabric for X and gamma ray protection | |
| US20240093374A1 (en) | Preparation method for tungsten/gadolinium oxide functional fiber having core-shell structure for x and gamma ray protection | |
| Ran et al. | Core–shell BiVO 4@ PDA composite photocatalysts on cotton fabrics for highly efficient photodegradation under visible light | |
| CN110048057A (en) | Surface modified PMMA/PVDF mixing coating composite diaphragm for lithium battery and preparation method thereof | |
| CN111082147B (en) | Preparation method of photonic crystal lithium sulfur battery based on large-area thick film controllable texture | |
| CN109560204A (en) | A kind of perovskite thin film and preparation method thereof and its application | |
| CN107523988A (en) | A kind of W18O49Coat carbon fibre composite and preparation method thereof | |
| CN105428539B (en) | Pressure atmosphere improves the preparation method of the perovskite solar battery obsorbing layer of its photoelectric properties during a kind of control annealing | |
| CN114759167A (en) | Manufacturing process of lithium battery positive plate | |
| CN108239778B (en) | A kind of preparation method of titanium alloy substrate surface high emissivity ceramic coating | |
| CN103832021A (en) | Method for preparing organic molecule hybridized TiO2 nanometer composite film on titanium substrate | |
| CN112756617A (en) | Preparation method of flake silver powder for conductive silver adhesive | |
| CN110209013A (en) | A kind of preparation method of light-sensitive material synergist | |
| CN112080943B (en) | Functional environment-friendly non-woven fabric and preparation method thereof | |
| CN107604635A (en) | A kind of W18O49Coat carbon fibre composite and preparation method thereof | |
| CN112259747B (en) | Fuel cell membrane electrode assembly formed by growing whiskers and preparation method | |
| DE2949349A1 (en) | BY EXPOSURE CURABLE, ELECTRICALLY CONDUCTIVE COATING MEASUREMENT AND METHOD FOR PRODUCING SILVER AGGREGATE PARTICLES FOR SUCH A MEASUREMENT | |
| CN108281591A (en) | A kind of preparation method of lithium ion battery ceramic coating composite diaphragm | |
| CN110372903B (en) | Lead-free light X, gamma and neutron integrated protection material and preparation method thereof | |
| CN113046801B (en) | High-emission and high-absorption nickel-cerium composite black film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21924142 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21924142 Country of ref document: EP Kind code of ref document: A1 |