WO2022166142A1 - PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CALANDRÉ EN PVC D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ - Google Patents

PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CALANDRÉ EN PVC D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ Download PDF

Info

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
Application number
PCT/CN2021/111436
Other languages
English (en)
Chinese (zh)
Inventor
姚理荣
夏勇
杨涛
孙通
潘刚伟
徐思峻
季涛
高强
Original Assignee
南通大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南通大学 filed Critical 南通大学
Publication of WO2022166142A1 publication Critical patent/WO2022166142A1/fr

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Medicinal Preparation (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

Procédé de préparation d'un matériau calandré en PVC d'oxyde de tungstène/gadolinium à structure cœur-écorce pour la protection contre les rayons X et γ, le procédé comprenant : tout d'abord, la préparation d'une poudre d'oxyde de tungstène/gadolinium à structure cœur-écorce ; et la préparation d'un matériau calandré en PVC d'oxyde de tungstène/gadolinium à structure cœur-écorce à partir de la poudre. Un film mince de polyester-imine est uniformément déposé avec la poudre d'oxyde de tungstène/gadolinium à structure cœur-écorce ; la poudre d'oxyde de tungstène/gadolinium à structure cœur-écorce est fondue dans une couche de peau mince d'oxyde de tungstène/gadolinium à structure cœur-écorce lors d'un pressage à chaud à haute température ; la poudre d'oxyde de tungstène/gadolinium à structure cœur-écorce est ajoutée dans une résine de PVC et celle-ci est mélangée uniformément ; le mélange est ensuite pulvérisé sur la surface de la couche de peau mince d'oxyde de tungstène/gadolinium à structure cœur-écorce ; et après séchage, le tissu est soumis à un moulage de calandrage au moyen d'un rouleau d'une machine de calandrage pour préparer un matériau de protection contre les rayons X et γ, sans plomb et léger. Le matériau de protection contre les rayons X et γ peut avoir un effet de protection synergique pour la protection contre les rayonnements, et une zone de protection faible peut être éliminée tandis que le rayonnement secondaire généré par le rayonnement est efficacement absorbé. Le matériau fonctionnel a les caractéristiques d'être exempt de plomb et léger en poids, et présente de bonnes perspectives d'application dans la protection contre les rayons X et γ.
PCT/CN2021/111436 2021-02-08 2021-08-09 PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CALANDRÉ EN PVC D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ WO2022166142A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110178876.5 2021-02-08
CN202110178876.5A CN112831078B (zh) 2021-02-08 2021-02-08 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

Publications (1)

Publication Number Publication Date
WO2022166142A1 true WO2022166142A1 (fr) 2022-08-11

Family

ID=75933199

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/111436 WO2022166142A1 (fr) 2021-02-08 2021-08-09 PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CALANDRÉ EN PVC D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ

Country Status (2)

Country Link
CN (1) CN112831078B (fr)
WO (1) WO2022166142A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112846173A (zh) * 2021-02-08 2021-05-28 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆粉末的制备方法
CN112831855B (zh) * 2021-02-08 2022-05-31 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆功能纤维的制备方法
CN112831078B (zh) * 2021-02-08 2022-08-16 南通大学 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
CN113321877B (zh) * 2021-06-15 2023-04-07 天津天颐科苑科技有限公司 一种可循环利用的柔性防辐射片材及其制备方法
CN113845817B (zh) * 2021-09-27 2022-07-12 哈尔滨工业大学 用于空间高能质子辐射防护的双组份功能填料复合涂层的制备方法
CN113943531B (zh) * 2021-09-27 2022-08-19 哈尔滨工业大学 一种抗辐射封装加固的cmos器件及其制备方法
CN113881312B (zh) * 2021-09-30 2022-06-17 哈尔滨工业大学 用于宇航级芯片总剂量效应防护的稀土-高z-石墨烯-复合涂层及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004055833A1 (fr) * 2002-12-17 2004-07-01 Lanxess Deutschland Gmbh Melange sans plomb utilise en tant qu'additif de protection contre les rayonnements
US20070194256A1 (en) * 2005-05-10 2007-08-23 Space Micro, Inc. Multifunctional radiation shield for space and aerospace applications
CN110911025A (zh) * 2019-11-27 2020-03-24 中国人民解放军海军特色医学中心 一种多重射线屏蔽材料
CN110948918A (zh) * 2019-11-27 2020-04-03 中国人民解放军海军特色医学中心 复合式辐射防护材料制备方法
CN111849175A (zh) * 2020-07-16 2020-10-30 成都盛帮密封件股份有限公司 一种耐辐照无铅辐射屏蔽的柔性材料及制法和应用
CN112831855A (zh) * 2021-02-08 2021-05-25 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆功能纤维的制备方法
CN112831078A (zh) * 2021-02-08 2021-05-25 南通大学 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
CN112846173A (zh) * 2021-02-08 2021-05-28 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆粉末的制备方法
CN112900155A (zh) * 2021-02-08 2021-06-04 南通大学 一种X、γ射线防护用无纺布的制备方法
CN112900110A (zh) * 2021-02-08 2021-06-04 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103463648A (zh) * 2013-08-23 2013-12-25 南京大学 一种表面修饰的氧化铁核-氧化钆壳复合纳米粒子及其制法和用途
CN107052356B (zh) * 2017-01-18 2019-01-15 天津大学 一种核壳结构的钨-氧化钇超细复合前驱体粉末的制备方法
CN109181224B (zh) * 2018-08-08 2020-11-24 中国科学院合肥物质科学研究院 一种含mof衍生多孔氧化钆的复合屏蔽材料及制备方法
CN110057885B (zh) * 2019-04-15 2021-07-02 安徽师范大学 一种氧化钆纳米空心球修饰的电极及其制备方法和电化学传感器及应用
CN110038614B (zh) * 2019-05-20 2020-06-16 中国科学院长春应用化学研究所 一种氮化钴负载的氮掺杂碳材料及其制备方法
CN110372903B (zh) * 2019-07-15 2022-02-01 南通大学 一种无铅轻质X、γ、中子一体防护材料及其制备方法
CN111250697B (zh) * 2020-02-18 2022-03-29 太原理工大学 一种氧化钆/钨/铝中子和伽马射线核壳共屏蔽材料的制备方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004055833A1 (fr) * 2002-12-17 2004-07-01 Lanxess Deutschland Gmbh Melange sans plomb utilise en tant qu'additif de protection contre les rayonnements
US20070194256A1 (en) * 2005-05-10 2007-08-23 Space Micro, Inc. Multifunctional radiation shield for space and aerospace applications
CN110911025A (zh) * 2019-11-27 2020-03-24 中国人民解放军海军特色医学中心 一种多重射线屏蔽材料
CN110948918A (zh) * 2019-11-27 2020-04-03 中国人民解放军海军特色医学中心 复合式辐射防护材料制备方法
CN111849175A (zh) * 2020-07-16 2020-10-30 成都盛帮密封件股份有限公司 一种耐辐照无铅辐射屏蔽的柔性材料及制法和应用
CN112831855A (zh) * 2021-02-08 2021-05-25 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆功能纤维的制备方法
CN112831078A (zh) * 2021-02-08 2021-05-25 南通大学 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
CN112846173A (zh) * 2021-02-08 2021-05-28 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆粉末的制备方法
CN112900155A (zh) * 2021-02-08 2021-06-04 南通大学 一种X、γ射线防护用无纺布的制备方法
CN112900110A (zh) * 2021-02-08 2021-06-04 南通大学 一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法

Also Published As

Publication number Publication date
CN112831078B (zh) 2022-08-16
CN112831078A (zh) 2021-05-25

Similar Documents

Publication Publication Date Title
WO2022166142A1 (fr) PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CALANDRÉ EN PVC D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ
WO2022166171A1 (fr) Procédé de préparation de tissu de revêtement de pu d'oxide de tungstène/gadolinium avec structure cœur-écorce pour la protection contre les rayons x et γ
WO2021174709A1 (fr) Séparateur de pulvérisation pour batterie lithium-ion et son procédé de préparation
WO2022166152A1 (fr) PROCÉDÉ DE PRÉPARATION DE POUDRE D'OXYDE DE TUNGSTÈNE/GADOLINIUM À STRUCTURE CŒUR-ÉCORCE POUR LA PROTECTION CONTRE LES RAYONS X ET γ
CN104282865B (zh) 一种凝胶聚合物涂层复合膜的制备方法及电池隔膜
US11987886B2 (en) Preparation method for tungsten/gadolinium oxide functional fiber having core-shell structure for x and gamma ray protection
CN112900155B (zh) 一种X、γ射线防护用无纺布的制备方法
Ran et al. Core–shell BiVO 4@ PDA composite photocatalysts on cotton fabrics for highly efficient photodegradation under visible light
CN110048057A (zh) 表面改性pmma/pvdf混合涂覆的锂电池复合隔膜及其制备方法
CN109560204A (zh) 一种钙钛矿薄膜及其制备方法和其应用
CN107523988A (zh) 一种w18o49包覆碳纤维复合材料及其制备方法
CN105428539B (zh) 一种控制退火时压强气氛提高其光电性能的钙钛矿太阳能电池吸收层的制备方法
CN110209013A (zh) 一种光敏材料用增效剂的制备方法
CN108239778A (zh) 一种钛合金基体表面高发射率陶瓷涂层的制备方法
CN112756617A (zh) 一种用于导电银胶的片状银粉的制备方法
CN112080943B (zh) 一种功能性环保无纺布及其制备方法
CN107604635A (zh) 一种w18o49包覆碳纤维复合材料及其制备方法
CN109913055A (zh) 一种改善聚合物绝缘沿面耐电纳米改性膜材料的制备方法
CN112259747B (zh) 一种生长晶须形成的燃料电池膜电极组件及制备方法
CN114592228A (zh) 一种可见光均匀高吸收的镁合金表面处理方法
DE2949349A1 (de) Durch belichten haertbare, elektrisch leitfaehige beschichtungsmasse und verfahren zur herstellung von silberaggregatteilchen fuer eine solche masse
CN108281591A (zh) 一种锂离子电池陶瓷涂层复合隔膜的制备方法
CN110372903B (zh) 一种无铅轻质X、γ、中子一体防护材料及其制备方法
CN110013824B (zh) 地膜状二维纳米薄层钛酸钠覆盖氧化银/氧化钛异质结光催化膜层材料及其制备方法
CN113046801B (zh) 一种高发射、高吸收镍-铈复合黑色薄膜及其制备方法

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