CN110948918A - Preparation method of composite radiation protection material - Google Patents

Preparation method of composite radiation protection material Download PDF

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Publication number
CN110948918A
CN110948918A CN201911181865.1A CN201911181865A CN110948918A CN 110948918 A CN110948918 A CN 110948918A CN 201911181865 A CN201911181865 A CN 201911181865A CN 110948918 A CN110948918 A CN 110948918A
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rubber
agent
parts
tungsten
gadolinium
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Inventor
何颖
沈先荣
李珂娴
王庆蓉
蒋定文
侯登勇
刘玉明
陈伟
罗群
刘李娜
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Chinese Peoples Liberation Army Naval Characteristic Medical Center
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Chinese Peoples Liberation Army Naval Characteristic Medical Center
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/18Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K2003/026Phosphorus
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0887Tungsten
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention provides a preparation method of a composite radiation protection material, which comprises three processes of preparing an unvulcanized tungsten-containing film, preparing an unvulcanized gadolinium-containing film and integrally preparing the composite radiation protection material, wherein the unvulcanized tungsten-containing film and the unvulcanized gadolinium-containing film are prepared through the first two processes, the unvulcanized film after being placed for a certain time is placed on a flat vulcanizing machine from top to bottom according to a tungsten-containing layer, a gadolinium-containing layer and a tungsten-containing layer in a stacking manner to be vulcanized to obtain a composite shielding function layer, the surface of the composite shielding function layer is treated by a surface treating agent, then a cold adhesive is coated, the dried composite shielding function layer and a wear-resistant layer cloth coated with the cold adhesive on the surface are placed in an oven to be preheated, the wear-resistant layer cloth is bonded after being taken out, and the.

Description

Preparation method of composite radiation protection material
Technical Field
The invention belongs to the technical field of radiation protection, and particularly relates to a preparation method of a composite radiation protection material.
Background
The ray shielding materials on the market at present are various in types, materials for neutron shielding comprise boron-containing paraffin, boron-containing polyethylene, water, graphite and the like, and materials for X-ray and gamma-ray shielding comprise lead, cement, lead-boron polyethylene, cement, cast iron and the like. Some of the shielding materials are hard materials, have poor flexibility and poor subsequent processing performance, and are mainly used for manufacturing shielding equipment with a more regular structure.
In practical situations, the most of the occasions needing shielding need to use a special-shaped component, and the common shielding material is difficult to meet the requirement. The traditional lead as one of the main shielding materials has good ductility and shielding performance, but has certain toxicity, and causes harm to human bodies and the environment. In addition, most radiation protection materials are designed to shield only one kind of ray (neutron or gamma ray), and the radiation protection requirements cannot be met in some places.
In addition, with the development of the requirements of various nuclear reactors and emergency rescue, the comprehensive requirements and the matching requirements for the shielding materials are higher and higher, the materials are required to have mechanical properties, heat resistance, radiation resistance and the like, and the use requirements of the existing shielding materials are difficult to meet.
Disclosure of Invention
The invention is carried out to solve the technical problems, and provides a preparation method of a composite radiation protection material to solve the technical problems of single radiation-resistant type and insufficient mechanical property of a shielding material in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the composite radiation protection material provided by the invention comprises the following three steps:
A. preparation of unvulcanized tungsten-containing film
Pouring rubber raw rubber, tungsten powder and a rubber auxiliary agent into an internal mixer in sequence according to a certain proportion for banburying to obtain a co-mixed rubber, then uniformly mixing the co-mixed rubber in an open mill, adding a cross-linking agent for continuous mixing, performing triangular bag making to obtain a mixed rubber, and obtaining an unvulcanized tungsten-containing rubber sheet after calendering;
B. preparation of unvulcanized gadolinium-containing rubber sheet
Pouring rubber raw rubber, gadolinium methacrylate and a rubber auxiliary agent into an internal mixer in sequence according to a certain proportion for internal mixing to obtain blended rubber, then uniformly mixing the blended rubber in an open mill, adding a cross-linking agent for continuous mixing, performing triangular bag making to obtain mixed rubber, and obtaining an unvulcanized gadolinium-containing rubber sheet after calendering;
C. integral preparation of composite radiation protection material
Placing an unvulcanized rubber sheet on a flat vulcanizing machine from top to bottom after being placed for a certain time according to a tungsten-containing layer, a gadolinium-containing layer and a tungsten-containing layer in a laminated manner for vulcanization to obtain a composite shielding function layer, treating the surface of the composite shielding function layer by using a surface treatment agent, coating a cold adhesive, drying, placing the dried composite shielding function layer and a wear-resistant layer cloth coated with the cold adhesive on the surface into a drying oven for preheating, taking out, adhering the wear-resistant layer cloth, and calendering to obtain the composite radiation protection material.
Preferably, in the unvulcanized tungsten-containing film preparation step in step a:
the rubber raw rubber is silicon rubber, the rubber auxiliary agent comprises carbon black, coupling agents A-D, boron-containing substances, a peroxide crosslinking agent, an activating agent, a plasticizer, an anti-aging agent and a flame retardant,
in terms of component content, the silicon rubber is 70-90 parts by weight, the tungsten powder is 600-700 parts by weight, the carbon black is 30-40 parts by weight, the coupling agent A is 2-3 parts by weight, the coupling agent B is 1.5-2 parts by weight, the coupling agent C is 1.5-2 parts by weight, the coupling agent D is 1-1.3 parts by weight, the boron-containing substance is 40-60 parts by weight, the peroxide crosslinking agent is 2-2.5 parts by weight, the activating agent is 3-4.5 parts by weight, the plasticizer is 7-9 parts by weight, the anti-aging agent is 1.5-2 parts by weight, and the flame retardant is 7-9 parts by weight.
Preferably, the silicone rubber is any one of methyl silicone rubber, methyl phenyl vinyl silicone rubber, methyl vinyl silicone rubber, nitrile silicone rubber or fluorosilicone rubber; the carbon black is selected from one of gas phase carbon black and precipitation carbon black; the coupling agent A is selected from any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil and cyanogen-containing silicone oil; the coupling agent B is selected from any one of KH550, KH560, KH570, KH580 and KH 590; the coupling agent C is selected from any one of A-151, A-171, A-172, A-174, A-187, A-1120, A-2120 and A-1100; the coupling agent D is selected from any one of PN-130, PN-131, PN-133, PN-101, PN-102, PN-105, PN-201, PN-311, PN-401 and GZ-80; the peroxide crosslinking agent is dicumyl peroxide (DCP) or 2, 5-dimethyl-2, 5- (di-tert-butylperoxy) hexane; the boron-containing substance is boron carbide, the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
The specific process flow is as follows:
(1) reinforcing the silicon rubber, weighing the silicon rubber according to the weight part ratio, putting the silicon rubber into an open mill or an internal mixer, adding the carbon black, the coupling agent A and the coupling agent B which are weighed according to the weight part ratio at room temperature, carrying out open milling or internal mixing for 20-35 minutes, and uniformly dispersing the carbon black into the silicon rubber;
(2) banburying and adding tungsten powder and boron-containing substances: putting the silicon rubber obtained in the step (1) into an internal mixer, quantitatively adding the tungsten powder, the boron-containing substance, the activator, the plasticizer, the anti-aging agent, the flame retardant, the coupling agent C and the coupling agent D in parts by weight, and internally mixing for 40-70 minutes to uniformly disperse the tungsten powder and the boron-containing substance in the silicon rubber; heating the internal mixer to 80 ℃, vacuumizing and internally mixing for 60 minutes to fully combine the tungsten powder, the boron-containing substance and the silicon rubber to obtain a rubber compound with better mechanical property;
(3) performing crosslinking reaction, namely cooling the rubber compound obtained in the step (2) to room temperature, putting the rubber compound into an open mill, adding a peroxide crosslinking agent weighed according to the weight part ratio, thinly passing the rubber compound for 10-15 times, opening cooling water during the process, and turning the rubber compound left and right to uniformly disperse the crosslinking agent in the rubber compound; adding the mixed rubber after open mixing into a mould on a flat vulcanizing machine, vulcanizing and crosslinking for 9-10 minutes at the temperature of 160-170 ℃ and under the pressure of 15-25 MPa to obtain a functional layer of the silicon rubber-based flexible shielding material, and calendering and cutting to obtain an unvulcanized tungsten-containing rubber sheet with the thickness of 2 mm.
Preferably, in the step B of preparing an unvulcanized gadolinium-containing rubber sheet:
the rubber raw rubber is silicon rubber, and the rubber auxiliary agent comprises an activating agent, a plasticizer, an anti-aging agent and a flame retardant.
In terms of component content, 80-120 parts by weight of silicone rubber, 30-50 parts by weight of gadolinium methacrylate, 2-8 parts by weight of activator, 5-15 parts by weight of plasticizer, 1-3 parts by weight of anti-aging agent and 5-15 parts by weight of flame retardant.
Preferably, the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
The specific process flow is as follows:
(1) preparation of gadolinium methacrylate
Gadolinium oxide, methacrylic acid and water are stirred and react for 1-2h at the temperature of 90 ℃ until the system is clear and transparent, and a polymerizable active monomer Gd (MAA) is prepared3(ii) a Then carrying out reduced pressure distillation to evaporate water and methacrylic acid, stopping distillation when a small amount of solid appears in the system, filtering while hot, adding ethanol into the filtrate to generate a large amount of white solid, and then filtering, washing and drying to obtain gadolinium methacrylate;
(2) pouring rubber raw rubber, gadolinium methacrylate and a rubber auxiliary agent into an internal mixer in sequence according to the weight part ratio, and internally mixing for 20min at 80-160 ℃ in vacuum to obtain co-mixed rubber;
(3) transferring the co-mixed rubber to an open mill, mixing for 10min, fully mixing, opening cooling water during the mixing, uniformly mixing left and right rubber turns, adding a vulcanizing agent, an auxiliary vulcanizing agent and the like after the left and right rubber turns for 5 times after the roller is wrapped, continuously mixing, and wrapping in a triangular bag for 5 times to obtain a rubber compound;
(4) and extruding the film with the thickness of about 1mm on a calender, and cutting the film into the size required by mould pressing to obtain the unvulcanized gadolinium-containing film.
Preferably, in the step C, the overall preparation process of the composite radiation protection material includes the following steps:
(1) preparing a composite shielding functional layer: placing the unvulcanized rubber sheet placed for 8 hours on a flat vulcanizing machine in an overlapped mode according to the tungsten-containing layer, the gadolinium-containing layer and the tungsten-containing layer, and carrying out co-vulcanization according to the process that the temperature is 160 ℃, the pressure is 10MPa and the vulcanization time is 15min to obtain the composite shielding functional layer;
(2) surface treatment of the composite shielding functional layer: dissolving rubber surface treating agent B powder in the amount of 1.5-2.0 wt% in the solvent A, fully stirring to mix uniformly, coating a layer of A/B mixed rubber surface treating agent on the surface of the composite shielding functional layer, drying, coating cold adhesive PU glue on the surface of the composite shielding functional layer, and performing secondary drying;
wherein, the A/B mixed rubber surface treating agent is 1707A/B surface treating agent, and the preparation method comprises the following steps: and dissolving 1707B powder in 1707A according to the weight ratio of 1.5-2.0%, and fully stirring to mix uniformly.
(3) And (3) bonding the wear-resistant layer cloth, putting the composite shielding functional layer obtained in the step (2) and the wear-resistant layer cloth coated with the cold adhesive on the surface and dried into a 75-DEG C oven together for preheating for 5min, taking out the wear-resistant layer cloth, bonding the wear-resistant layer cloth, performing calendering by using a calendering roller, standing for 2h to form a composite product, and obtaining the corresponding composite radiation protection material after 24h when the practical strength reaches the highest.
The composite radiation protection material prepared by the method comprises wear-resistant layers respectively serving as the upper surface and the lower surface, tungsten-containing rubber protective layers respectively arranged on the inner surfaces of the two wear-resistant layers, and gadolinium-containing rubber protective layers arranged between the two tungsten-containing rubber protective layers. The two tungsten-containing rubber protective layers and the gadolinium-containing rubber protective layer form a sandwich structure and are connected together through vulcanization to form a composite shielding functional layer; the thickness of the tungsten-containing rubber protective layer is 2-3 mm, the thickness of the gadolinium-containing rubber protective layer is 1-1.5 mm, and the thickness of the wear-resistant layer is 0.08-1.0 mm.
The invention has the following beneficial guarantee and effects:
the composite radiation protection material prepared by the preparation method can prevent neutron rays and gamma rays, and has good shielding performance; the material has good flexibility, good ductility and excellent subsequent processing performance; the contained functional components are safe and nontoxic, the problem that the conventional radiation protection material has toxicity to human bodies is solved, and the radiation protection material has good thermal property, chemical property and mechanical property.
Drawings
FIG. 1 is a schematic structural diagram of a multiple-radiation shielding material according to an embodiment of the present invention;
FIG. 2 is a flow chart illustrating the preparation of an unvulcanized tungsten-containing film in accordance with an embodiment of the present invention;
FIG. 3 is a flow chart illustrating the preparation of an unvulcanized gadolinium-containing film in an embodiment of the present invention;
fig. 4 is a flowchart illustrating an overall process for preparing the multiple-radiation shielding material according to the embodiment of the present invention.
Detailed Description
The present invention will now be described in detail with reference to examples, but the practice of the present invention is not limited thereto.
As shown in fig. 1, the multiple-radiation shielding material 100 provided by the present invention is capable of shielding neutron radiation, X-ray radiation and gamma-ray radiation simultaneously, and includes two wear-resistant layers 1, two tungsten-containing rubber protective layers 2, and one gadolinium-containing rubber protective layer 3. The two layers of wear-resistant layers 1 are respectively used as the upper surface and the lower surface, the two layers of tungsten-containing rubber protective layers 2 are respectively arranged on the inner surfaces of the wear-resistant layers 1, the gadolinium-containing rubber protective layer 3 is arranged between the two layers of tungsten-containing rubber protective layers 2, a sandwich structure is formed by the gadolinium-containing rubber protective layer and the tungsten-containing rubber protective layers 2, and the gadolinium-containing rubber protective layers and the tungsten-containing rubber protective layers are.
The thickness of the gadolinium-containing rubber protective layer is 50-60% of that of the tungsten-containing rubber protective layer, and the thickness of the wear-resistant layer is 10-50% of that of the tungsten-containing rubber protective layer. Preferably, the thickness of the tungsten-containing rubber protective layer is 2mm, the thickness of the gadolinium-containing rubber protective layer is 1mm, and the thickness of the wear-resistant layer is 0.08-1.0 mm.
The wear-resistant layer 1 is made of Kevlar fiber fabric and is bonded with the tungsten-containing rubber protective layer 2 through a binder layer. The tungsten-containing rubber protective layer comprises 80-120 parts by weight of silicone rubber, 30-40 parts by weight of carbon black, 500-1800 parts by weight of tungsten powder, 40-60 parts by weight of boron-containing substances, 2-8 parts by weight of activators, 5-15 parts by weight of plasticizers, 1-3 parts by weight of anti-aging agents and 5-15 parts by weight of flame retardants; the gadolinium-containing rubber protective layer comprises 80-120 parts by weight of silicone rubber, 30-50 parts by weight of gadolinium methacrylate, 2-8 parts by weight of an activator, 5-15 parts by weight of a plasticizer, 1-3 parts by weight of an anti-aging agent and 5-15 parts by weight of a flame retardant. Wherein the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
In this embodiment, the preparation of the multiple-ray shielding material includes three steps of preparing an unvulcanized tungsten-containing film, preparing an unvulcanized gadolinium-containing film, and integrally preparing the composite radiation protection material, and the general preparation process of each step is as follows:
A. preparation of unvulcanized tungsten-containing film
Referring to the flow in fig. 2, rubber crude rubber, tungsten powder and a rubber auxiliary agent are sequentially poured into an internal mixer for internal mixing according to a proportion to obtain blended rubber, then the blended rubber is mixed in an open mill for full mixing, then a peroxide cross-linking agent is added for continuous mixing, a triangular bag is formed to obtain mixed rubber, and an unvulcanized tungsten-containing rubber sheet is obtained after calendering.
The rubber raw rubber is silicon rubber, and the rubber auxiliary agent comprises carbon black, coupling agents A-D, a boron-containing substance, a peroxide crosslinking agent, an activating agent, a plasticizer, an anti-aging agent and a flame retardant.
In terms of component content, preferably 70-90 parts by weight of silicone rubber, 600-700 parts by weight of tungsten powder, 30-40 parts by weight of carbon black, 2-3 parts by weight of coupling agent A, 1.5-2 parts by weight of coupling agent B, 1.5-2 parts by weight of coupling agent C, 1-1.3 parts by weight of coupling agent D, 40-60 parts by weight of boron-containing substance, 2-2.5 parts by weight of peroxide crosslinking agent, 3-4.5 parts by weight of activating agent, 7-9 parts by weight of plasticizer, 1.5-2 parts by weight of anti-aging agent and 7-9 parts by weight of flame retardant.
The optimized component matching comprises the following two schemes:
the first scheme is as follows: 70 parts of silicon rubber, 600 parts of tungsten powder, 30 parts of carbon black, 2 parts of coupling agent A, 1.5 parts of coupling agent B, 1.5 parts of coupling agent C, 1 part of coupling agent D, 60 parts of boron-containing substance, 2 parts of peroxide crosslinking agent, 3 parts of activating agent, 7 parts of plasticizer, 1.5 parts of anti-aging agent and 7 parts of flame retardant.
Scheme II: 90 parts of silicon rubber, 700 parts of tungsten powder, 40 parts of carbon black, 3 parts of coupling agent A, 2 parts of coupling agent B, 2 parts of coupling agent C, 1.3 parts of coupling agent D, 40 parts of boron-containing substance, 2.5 parts of peroxide crosslinking agent, 4.5 parts of activating agent, 9 parts of plasticizer, 2 parts of anti-aging agent and 9 parts of flame retardant.
The silicon rubber is selected from any one of methyl silicon rubber, methyl phenyl vinyl silicon rubber, methyl vinyl silicon rubber, nitrile silicon rubber or fluorine silicon rubber; the carbon black is selected from one of gas phase carbon black and precipitation carbon black; the coupling agent A is selected from any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil and cyanogen-containing silicone oil; the coupling agent B is selected from any one of KH550, KH560, KH570, KH580 and KH 590; the coupling agent C is selected from any one of A-151, A-171, A-172, A-174, A-187, A-1120, A-2120 and A-1100; the coupling agent D is selected from any one of PN-130, PN-131, PN-133, PN-101, PN-102, PN-105, PN-201, PN-311, PN-401 and GZ-80; the peroxide crosslinking agent is dicumyl peroxide (DCP) or 2, 5-dimethyl-2, 5- (di-tert-butylperoxy) hexane.
The specific process flow is as follows:
(1) reinforcing the silicon rubber, weighing the silicon rubber according to the weight part ratio, putting the silicon rubber into an open mill or an internal mixer, adding the carbon black, the coupling agent A and the coupling agent B which are weighed according to the weight part ratio at room temperature, carrying out open milling or internal mixing for 20-35 minutes, and uniformly dispersing the carbon black into the silicon rubber;
(2) banburying and adding tungsten powder and boron-containing substances: putting the silicon rubber obtained in the step (1) into an internal mixer, quantitatively adding the tungsten powder, the boron-containing substance, the activator, the plasticizer, the anti-aging agent, the flame retardant, the coupling agent C and the coupling agent D in parts by weight, and internally mixing for 40-70 minutes to uniformly disperse the tungsten powder and the boron-containing substance in the silicon rubber; heating the internal mixer to 80 ℃, vacuumizing and internally mixing for 60 minutes to fully combine the tungsten powder, the boron-containing substance and the silicon rubber to obtain a rubber compound with better mechanical property;
(3) performing crosslinking reaction, namely cooling the rubber compound obtained in the step (2) to room temperature, putting the rubber compound into an open mill, adding a peroxide crosslinking agent weighed according to the weight part ratio, thinly passing the rubber compound for 10-15 times, opening cooling water during the process, and turning the rubber compound left and right to uniformly disperse the crosslinking agent in the rubber compound; adding the mixed rubber after open mixing into a mould on a flat vulcanizing machine, vulcanizing and crosslinking for 9-10 minutes at the temperature of 160-170 ℃ and under the pressure of 15-25 MPa to obtain a functional layer of the silicon rubber-based flexible shielding material, and calendering and cutting to obtain an unvulcanized tungsten-containing rubber sheet with the thickness of 2 mm.
B. Preparation of unvulcanized gadolinium-containing rubber sheet
Referring to the flow in fig. 3, firstly, gadolinium methacrylate is prepared, then rubber virgin rubber, gadolinium methacrylate and rubber auxiliaries are poured into an internal mixer in sequence according to a certain proportion for internal mixing to obtain blended rubber, then the blended rubber is mixed and mixed uniformly in an open mill, then a vulcanizing agent and an auxiliary vulcanizing agent are added for continuous mixing, a triangular bag is formed to obtain mixed rubber, and unvulcanized gadolinium-containing rubber sheets are obtained after calendering.
The rubber raw rubber is silicon rubber, and the rubber auxiliary agent comprises an activating agent, a plasticizer, an anti-aging agent and a flame retardant.
The gadolinium-containing rubber protective layer comprises, by weight, 80-120 parts of silicone rubber, 30-50 parts of gadolinium methacrylate, 2-8 parts of an activator, 5-15 parts of a plasticizer, 1-3 parts of an anti-aging agent and 5-15 parts of a flame retardant. Wherein the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
The specific process flow is as follows:
(1) preparation of gadolinium methacrylate
Mixing gadolinium oxide and methylStirring and reacting acrylic acid and water at 90 ℃ for 1-2h until the system is clear and transparent, and preparing the polymerizable active monomer Gd (MAA)3(ii) a Then carrying out reduced pressure distillation to evaporate water and methacrylic acid, stopping distillation when a small amount of solid appears in the system, filtering while hot, adding ethanol into the filtrate to generate a large amount of white solid, and then filtering, washing and drying to obtain gadolinium methacrylate;
(2) pouring rubber raw rubber, gadolinium methacrylate and a rubber auxiliary agent into an internal mixer in sequence according to the weight part ratio, and internally mixing for 20min at 80-160 ℃ in vacuum to obtain co-mixed rubber;
(3) transferring the co-mixed rubber to an open mill, mixing for 10min, fully mixing, opening cooling water during the mixing, uniformly mixing left and right rubber turns, adding a vulcanizing agent, an auxiliary vulcanizing agent and the like after the left and right rubber turns for 5 times after the roller is wrapped, continuously mixing, and wrapping in a triangular bag for 5 times to obtain a rubber compound;
(4) and extruding the film with the thickness of about 1mm on a calender, and cutting the film into the size required by mould pressing to obtain the unvulcanized gadolinium-containing film.
C. Integral preparation of composite radiation protection material
Referring to the flow in fig. 4, after being placed for a certain time, an unvulcanized rubber sheet is stacked and placed on a flat vulcanizing machine from top to bottom according to a tungsten-containing layer, a gadolinium-containing layer and a tungsten-containing layer for vulcanization to obtain a composite shielding functional layer, after the surface of the composite shielding functional layer is subjected to surface treatment by an A/B mixed treating agent, a cold adhesive is coated, after drying, the composite shielding functional layer and a wear-resistant layer cloth coated with the cold adhesive and dried are placed in a drying oven together for preheating, the wear-resistant layer cloth is bonded after being taken out, and the composite radiation protection material is obtained after being rolled.
The specific process flow is as follows:
(1) preparing a composite shielding functional layer: placing the unvulcanized rubber sheet placed for 8 hours on a flat vulcanizing machine in an overlapped mode according to the tungsten-containing layer, the gadolinium-containing layer and the tungsten-containing layer, and carrying out co-vulcanization according to the process that the temperature is 160 ℃, the pressure is 10MPa and the vulcanization time is 15min to obtain the composite shielding functional layer;
(2) surface treatment of the composite shielding functional layer: dissolving rubber surface treating agent B powder in the amount of 1.5-2.0 wt% in the solvent A, fully stirring to mix uniformly, coating a layer of A/B mixed rubber surface treating agent on the surface of the composite shielding functional layer, drying, coating cold adhesive PU glue on the surface of the composite shielding functional layer, and performing secondary drying;
(3) and (3) bonding the wear-resistant layer cloth, putting the composite shielding functional layer obtained in the step (2) and the wear-resistant layer cloth coated with the cold adhesive on the surface and dried into a 75-DEG C oven together for preheating for 5min, taking out the wear-resistant layer cloth, bonding the wear-resistant layer cloth, performing calendering by using a calendering roller, standing for 2h to form a composite product, and obtaining the corresponding composite radiation protection material after 24h when the practical strength reaches the highest.
The A/B mixed rubber surface treating agent is 1707A/B surface treating agent, and the preparation method comprises the following steps: and dissolving 1707B powder in 1707A according to the weight ratio of 1.5-2.0%, and fully stirring to mix uniformly.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.

Claims (8)

1. A preparation method of a composite radiation protection material is characterized by comprising the following steps:
A. preparation of unvulcanized tungsten-containing film
Pouring rubber raw rubber, tungsten powder and a rubber auxiliary agent into an internal mixer in sequence according to a certain proportion for banburying to obtain a co-mixed rubber, then uniformly mixing the co-mixed rubber in an open mill, adding a cross-linking agent for continuous mixing, performing triangular bag making to obtain a mixed rubber, and performing calendering to obtain the unvulcanized tungsten-containing rubber sheet;
B. preparation of unvulcanized gadolinium-containing rubber sheet
Pouring rubber raw rubber, gadolinium methacrylate and a rubber auxiliary agent into an internal mixer in sequence according to a certain proportion for internal mixing to obtain blended rubber, then uniformly mixing the blended rubber in an open mill, adding a cross-linking agent for continuous mixing, performing triangular bag making to obtain mixed rubber, and obtaining the unvulcanized gadolinium-containing rubber sheet after calendering;
C. integral preparation of composite radiation protection material
Placing an unvulcanized rubber sheet on a flat vulcanizing machine from top to bottom after being placed for a certain time according to a tungsten-containing layer, a gadolinium-containing layer and a tungsten-containing layer in a laminated manner for vulcanization to obtain a composite shielding function layer, treating the surface of the composite shielding function layer by using a surface treatment agent, coating a cold adhesive, drying, placing the dried composite shielding function layer and a wear-resistant layer cloth coated with the cold adhesive on the surface into a drying oven for preheating, taking out, adhering the wear-resistant layer cloth, and calendering to obtain the composite radiation protection material.
2. The method of claim 1, wherein the step of preparing the composite radiation protection material comprises:
wherein in the step A, the rubber raw rubber is silicon rubber, the rubber auxiliary agent comprises carbon black, coupling agents A-D, boron-containing substances, a peroxide crosslinking agent, an activating agent, a plasticizer, an anti-aging agent and a flame retardant,
70-90 parts of silicone rubber, 600-700 parts of tungsten powder, 30-40 parts of carbon black, 2-3 parts of coupling agent A, 1.5-2 parts of coupling agent B, 1.5-2 parts of coupling agent C, 1-1.3 parts of coupling agent D, 40-60 parts of boron-containing substance, 2-2.5 parts of peroxide crosslinking agent, 3-4.5 parts of activating agent, 7-9 parts of plasticizer, 1.5-2 parts of anti-aging agent and 7-9 parts of flame retardant.
3. The method of claim 2, wherein the step of preparing the composite radiation protection material comprises:
the preparation method of the unvulcanized tungsten-containing film comprises the following steps of:
(1) reinforcing the silicon rubber, weighing the silicon rubber according to the weight part ratio, putting the silicon rubber into an open mill or an internal mixer, adding the carbon black, the coupling agent A and the coupling agent B which are weighed according to the weight part ratio at room temperature, carrying out open milling or internal mixing for 20-35 minutes, and uniformly dispersing the carbon black into the silicon rubber;
(2) banburying and adding tungsten powder and boron-containing substances: b, putting the silicon rubber obtained in the step a into an internal mixer, quantitatively adding the tungsten powder, the boron-containing substance, the activator, the plasticizer, the anti-aging agent, the flame retardant, the coupling agent C and the coupling agent D which are weighed according to the weight part ratio in a fractional manner, and internally mixing for 40-70 minutes to uniformly disperse the tungsten powder and the boron-containing substance in the silicon rubber; heating the internal mixer to 80 ℃, vacuumizing and internally mixing for 60 minutes to fully combine the tungsten powder, the boron-containing substance and the silicon rubber to obtain a rubber compound with better mechanical property;
(3) performing crosslinking reaction, namely cooling the rubber compound obtained in the step (2) to room temperature, putting the rubber compound into an open mill, adding the peroxide crosslinking agent weighed according to the weight part ratio, thinly passing the rubber compound for at least 8 times, opening cooling water during the passing, and turning the rubber compound left and right to uniformly disperse the crosslinking agent in the rubber compound; adding the mixed rubber after open mixing into a mould on a flat vulcanizing machine, vulcanizing and crosslinking for 9-10 minutes at the temperature of 160-170 ℃ and under the pressure of 15-25 MPa to obtain a functional layer of the silicon rubber-based flexible shielding material, and calendering and cutting to obtain an unvulcanized tungsten-containing rubber sheet with the thickness of 2 mm.
4. The method of claim 2, wherein the step of preparing the composite radiation protection material comprises:
wherein, the silicon rubber is selected from any one of methyl silicon rubber, methyl phenyl vinyl silicon rubber, methyl vinyl silicon rubber, nitrile silicon rubber or fluorine silicon rubber;
the carbon black is taken from any one of gas-phase carbon black or precipitation-process carbon black;
the coupling agent A is selected from any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil and cyanogen-containing silicone oil;
the coupling agent B is selected from any one of KH550, KH560, KH570, KH580 and KH 590;
the coupling agent C is selected from any one of A-151, A-171, A-172, A-174, A-187, A-1120, A-2120 and A-1100;
the coupling agent D is selected from any one of PN-130, PN-131, PN-133, PN-101, PN-102, PN-105, PN-201, PN-311, PN-401 and GZ-80;
the peroxide crosslinking agent is dicumyl peroxide (DCP) or 2, 5-dimethyl-2, 5- (di-tert-butylperoxy) hexane;
the boron-containing substance is boron carbide, the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
5. The method of claim 1, wherein the step of preparing the composite radiation protection material comprises:
wherein in the step B, the rubber raw rubber is silicon rubber, the rubber auxiliary agent comprises an activating agent, a plasticizer, an anti-aging agent and a flame retardant,
80-120 parts of silicone rubber, 30-50 parts of gadolinium methacrylate, 2-8 parts of an activator, 5-15 parts of a plasticizer, 1-3 parts of an anti-aging agent and 5-15 parts of a flame retardant,
the activating agent is zinc oxide, the plasticizer is TP-95, the anti-aging agent is anti-aging agent 4010NA, and the flame retardant is inorganic phosphorus.
6. The method of claim 5, wherein the step of preparing the composite radiation protection material comprises:
the preparation method of the unvulcanized gadolinium-containing rubber sheet comprises the following steps:
(1) preparation of gadolinium methacrylate
Gadolinium oxide, methacrylic acid and water are stirred and react for 1-2h at the temperature of 90 ℃ until the system is clear and transparent, and a polymerizable active monomer Gd (MAA) is prepared3(ii) a Then carrying out reduced pressure distillation to evaporate water and methacrylic acid, stopping distillation when a small amount of solid appears in the system, filtering while hot, adding ethanol into the filtrate to generate a large amount of white solid, and then filtering, washing and drying to obtain gadolinium methacrylate;
(2) pouring rubber raw rubber, gadolinium methacrylate and a rubber auxiliary agent into an internal mixer in sequence according to the weight part ratio, and internally mixing for 20min under the conditions of vacuum and 80-160 ℃ to obtain the co-mixing rubber;
(3) transferring the co-mixed rubber to an open mill, mixing for 10min, fully mixing, opening cooling water during the mixing, uniformly mixing left and right rubber turns, adding a vulcanizing agent, an auxiliary vulcanizing agent and the like after the left and right rubber turns for 5 times after the roller is wrapped, continuously mixing, and wrapping in a triangular bag for 5 times to obtain a rubber compound;
(4) and extruding the film with the thickness of about 1mm on a calender, and cutting the film into the size required by mould pressing to obtain the unvulcanized gadolinium-containing film.
7. The method of claim 1, wherein the step of preparing the composite radiation protection material comprises:
the method for integrally preparing the composite radiation protection material in the step C comprises the following steps:
(1) preparing a composite shielding functional layer: placing the unvulcanized rubber sheet placed for 8 hours on a flat vulcanizing machine in an overlapped mode according to the tungsten-containing layer, the gadolinium-containing layer and the tungsten-containing layer, and carrying out co-vulcanization according to the process that the temperature is 160 ℃, the pressure is 10MPa and the vulcanization time is 15min to obtain the composite shielding functional layer;
(2) surface treatment of the composite shielding functional layer: dissolving rubber surface treating agent B powder in the amount of 1.5-2.0 wt% in the solvent A, fully stirring to mix uniformly, coating a layer of A/B mixed rubber surface treating agent on the surface of the composite shielding functional layer, drying, coating cold adhesive PU glue on the surface of the composite shielding functional layer, and performing secondary drying;
(3) and (3) bonding the wear-resistant layer cloth, putting the composite shielding functional layer obtained in the step (2) and the wear-resistant layer cloth coated with the cold adhesive on the surface and dried into a 75-DEG C oven together for preheating for 5min, taking out the wear-resistant layer cloth, bonding the wear-resistant layer cloth, performing calendering by using a calendering roller, standing for 2h to form a composite product, and obtaining the corresponding composite radiation protection material after 24h when the practical strength reaches the highest.
8. The method of claim 7, wherein the step of preparing the composite radiation protection material comprises:
wherein, the A/B mixed rubber surface treating agent is 1707A/B surface treating agent, and the preparation method comprises the following steps: and dissolving 1707B powder in 1707A according to the weight ratio of 1.5-2.0%, and fully stirring to mix uniformly.
CN201911181865.1A 2019-11-27 2019-11-27 Preparation method of composite radiation protection material Pending CN110948918A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022166142A1 (en) * 2021-02-08 2022-08-11 南通大学 PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION
CN115232893A (en) * 2022-08-18 2022-10-25 四川大学 Flexible neutron shielding material based on collagen fibers and preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558426A (en) * 2011-10-16 2012-07-11 浙江吉利汽车研究院有限公司 Leadless radiation-proof organic glass and preparation method thereof
CN104979031A (en) * 2014-04-02 2015-10-14 美国陶瓷技术公司 Radiation Shield With Magnetic Properties
CN105150636A (en) * 2015-06-19 2015-12-16 中科华核电技术研究院有限公司 Flexible shielding material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558426A (en) * 2011-10-16 2012-07-11 浙江吉利汽车研究院有限公司 Leadless radiation-proof organic glass and preparation method thereof
CN104979031A (en) * 2014-04-02 2015-10-14 美国陶瓷技术公司 Radiation Shield With Magnetic Properties
CN105150636A (en) * 2015-06-19 2015-12-16 中科华核电技术研究院有限公司 Flexible shielding material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
董志华: "甲基丙烯酸钆/丁睛橡胶复合材料的制备及性能", 《合成橡胶工业》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022166142A1 (en) * 2021-02-08 2022-08-11 南通大学 PREPARATION METHOD FOR CORE-SHELL STRUCTURE TUNGSTEN/GADOLINIUM OXIDE PVC CALENDERED MATERIAL FOR X-RAY AND γ-RAY PROTECTION
CN115232893A (en) * 2022-08-18 2022-10-25 四川大学 Flexible neutron shielding material based on collagen fibers and preparation method
CN115232893B (en) * 2022-08-18 2023-05-12 四川大学 Flexible neutron shielding material based on collagen fibers and preparation method thereof

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