CN109267333B - Anti-radiation composite material and preparation method thereof - Google Patents
Anti-radiation composite material and preparation method thereof Download PDFInfo
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- CN109267333B CN109267333B CN201810959442.7A CN201810959442A CN109267333B CN 109267333 B CN109267333 B CN 109267333B CN 201810959442 A CN201810959442 A CN 201810959442A CN 109267333 B CN109267333 B CN 109267333B
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- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000002861 polymer material Substances 0.000 claims abstract description 14
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/47—Oxides or hydroxides of elements of Groups 5 or 15 of the Periodic System; Vanadates; Niobates; Tantalates; Arsenates; Antimonates; Bismuthates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention discloses a radiation-resistant composite material and a preparation method thereof. The radiation resistant composite material comprises: the support layer is made of a high polymer material; the metal layer is arranged on the supporting layer in a stacked mode and comprises one or more of copper, nickel, iron and silver; the shielding layer is arranged on the metal layer in a lamination way, and comprises, by weight, 10-80 parts of a polymer matrix material, 10-70 parts of radiation-resistant composite powder and 0.5-8 parts of a bonding agent. The anti-radiation composite material provided by the invention has an efficient radiation protection function and simultaneously has light weight.
Description
Technical Field
The invention relates to the technical field of radiation protection, in particular to a radiation-resistant composite material and a preparation method thereof.
Background
With the rapid development of nuclear energy technology, nuclear radiation safety issues are becoming more and more important. Such as gamma rays in nuclear radiation, have high energy and extremely strong penetrating power, and can damage human tissues and organs, thereby causing various diseases and even death and causing extremely threatening to the life health of operators who are frequently contacted with nuclear radiation.
The radiation-resistant materials adopted at present are mainly lead uniform, lead plates, lead screens and the like, lead poisoning is easy to be caused by long-term contact of the radiation-resistant materials, and the radiation-resistant materials also have the problems of large weight, poor shielding performance and the like, so that the requirements of nuclear radiation safety are difficult to meet.
Disclosure of Invention
The embodiment of the invention provides a radiation-resistant composite material and a preparation method thereof, so that the radiation-resistant composite material has an efficient radiation protection function and is light in weight.
In a first aspect, embodiments of the present invention provide a radiation resistant composite material comprising: the support layer is made of a high polymer material; the metal layer is arranged on the supporting layer in a stacked manner and comprises one or more of copper, nickel, iron and silver; the shielding layer is laminated on the metal layer and comprises, by weight, 10-80 parts of a polymer matrix material, 10-70 parts of radiation-resistant composite powder and 0.5-8 parts of a bonding agent.
In a second aspect, an embodiment of the present invention provides a method for preparing a radiation resistant composite material, the method including the steps of:
providing a supporting layer, wherein the supporting layer is made of a high polymer material;
preparing a metal layer, wherein the metal layer is laminated on the supporting layer, and the metal layer comprises one or more of copper, nickel, iron and silver;
providing shielding slurry, wherein the shielding slurry comprises 30-80 parts by weight of aqueous resin, 10-70 parts by weight of anti-radiation composite powder and 0.5-8 parts by weight of bonding agent;
preparing a shielding layer, coating shielding slurry on the metal layer, and drying to obtain the shielding layer, thereby obtaining the radiation-resistant composite material.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the high polymer material is used as the supporting layer, the metal layer and the shielding layer are arranged on the supporting layer, and the composition of the metal layer and the shielding layer is optimized, so that the anti-radiation composite material has an efficient radiation protection function, and meanwhile, the high strength and the light weight are simultaneously considered; the radiation-resistant composite material has good flexibility, so that the universality and the use flexibility of the radiation-resistant composite material are improved, and various requirements of different application conditions are met. The radiation-resistant composite material can be used as a radiation protection layer for manufacturing protective clothing, protective tent, protective screen and the like, and is particularly suitable for radiation protection of nuclear workstation operators.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings that are needed to be used in the embodiments of the present invention will be briefly described, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a schematic structural diagram of a radiation resistant composite material according to an embodiment of the present invention.
Fig. 2 shows a schematic structural diagram of a radiation resistant composite material according to another embodiment of the present invention.
Detailed Description
Features and exemplary embodiments of various aspects of the present invention will be described in detail below, and in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely configured to illustrate the invention and are not configured to limit the invention. It will be apparent to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the invention by showing examples of the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above," below, "and" below "are inclusive of the present numbers, and the meaning of" multiple "in one or more" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
The radiation resistant composite material of the first aspect of the embodiment of the present invention is first described. The radiation-resistant composite material comprises a support layer, a metal layer and a shielding layer which are arranged in a laminated mode.
Wherein, the supporting layer adopts polymer material.
The metal layer is arranged on the supporting layer in a layer-by-layer mode, and the metal layer comprises one or more of copper, nickel, iron and silver.
The shielding layer is arranged on the metal layer, and comprises, by weight, 10-80 parts of a polymer matrix material, 10-70 parts of an anti-radiation composite powder and 0.5-8 parts of a bonding agent.
The radiation-resistant composite material provided by the embodiment of the invention adopts the high polymer material as the supporting layer, can meet the supporting and protecting effects on the metal layer and the shielding layer, and can also enable the radiation-resistant composite material to have flexibility in winding in the processing and using processes. Because the density of the high polymer material is lower than that of the metal and the radiation-resistant powder, the weight of the radiation-resistant composite material of the embodiment of the invention is obviously reduced compared with that of the traditional radiation-resistant composite material. The polymer material also has a certain degree of ray shielding effect.
Further, the metal layer and the shielding layer are arranged on the supporting layer, and the composition of the metal layer and the shielding layer is optimized, so that the metal layer can effectively weaken rays, has a good slowing effect on fast neutrons, enables the shielding layer to absorb rays with different energy respectively, improves the absorption of the shielding layer on the rays, and remarkably improves the radiation protection function of the radiation-resistant composite material through the double matching effect of the metal layer and the shielding layer. It will be appreciated that the dual-cooperation between the metal layer and the shielding layer may be that the metal layer attenuates the radiation and then the shielding layer fully absorbs the radiation, or that the shielding layer absorbs the radiation and then the metal layer fully absorbs the radiation, or a combination of the two.
The anti-radiation composite material has excellent radiation protection effects on alpha rays, beta rays, gamma rays, X rays, neutron rays and the like, can be used as a radiation protection layer for manufacturing protective clothing, protective tent, protective screen and the like, and is particularly suitable for radiation protection of nuclear workstation operators. The radiation-resistant composite material has higher universality and use flexibility, and can meet various requirements of different application conditions.
Preferably, the shielding layer is arranged on a surface of the metal layer facing away from the support layer.
As a specific example, fig. 1 shows a radiation resistant composite material 10 according to an embodiment of the present invention, where the support layer 11 has a first surface 121 and a second surface 122 opposite to each other along its thickness direction, the metal layer 12 is disposed on the first surface 121 of the support layer 11, and the shielding layer 13 is disposed on a surface of the metal layer 12 facing away from the support layer 11. The close bonding between the layers is beneficial to ensuring the long-term radiation protection effect of the radiation resistant composite material 10.
It will be appreciated that the metal layer 12 may also be disposed on the second surface 122 of the support layer 11.
As another specific example, fig. 2 shows a radiation resistant composite material 10 according to an embodiment of the present invention, where the support layer 11 has a first surface 121 and a second surface 122 opposite to each other along its thickness direction, the metal layer 12 is disposed on the first surface 121 and the second surface 122 of the support layer 11, and the shielding layer 13 is disposed on a surface of the metal layer 12 facing away from the support layer 11. The close bonding between the layers is beneficial to ensuring the long-term radiation protection effect of the radiation resistant composite material 10.
The radiation resistant composite material of the embodiment of the invention is exemplified by one or more of polyamide, poly (paraphenylene terephthalamide), polyimide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polystyrene, silicone rubber, epoxy resin, cellulose and protein.
In some embodiments, the support layer is woven from the polymeric fibers described above.
In other embodiments, the supporting layer is formed by weaving the polymer material fibers and the inorganic fibers in a compounding manner, so that the strength and the radiation-resistant effect of the supporting layer are improved, and the strength and the radiation protection effect of the radiation-resistant composite material are improved. As an example, the aforementioned inorganic fibers may be one or more of carbon fibers, glass fibers, metal fibers, and boron fibers.
According to the radiation-resistant composite material provided by the embodiment of the invention, the metal layer can be a foam metal layer so as to improve the radiation resistance of the metal layer.
In the radiation-resistant composite material provided by the embodiment of the invention, the radiation-resistant composite powder in the shielding layer is preferably two or more than three of tantalum, tantalum pentoxide, tantalum diboride, barium oxide, barium hydroxide, bismuth oxide and bismuth tungstate. The shielding layer has better radiation absorption effect on various different energies, so that the radiation protection effect of the shielding layer is better improved.
In order to further improve the radiation protection effect of the shielding layer, the radiation resistant composite powder is nano-sized particles, more preferably the particle size is 100nm or less, such as 5nm to 100nm, and the particle size of the radiation resistant composite powder may be 50nm to 100nm in consideration of material cost.
The radiation-resistant composite material of the embodiment of the invention is exemplified by a polymer matrix material of the shielding layer which adopts one or more of aqueous resin, such as aqueous polyurethane, aqueous polyacrylic acid, aqueous organic silicon resin, aqueous epoxy resin and aqueous alkyd resin. The radiation-resistant composite powder in the shielding layer is uniformly dispersed, and the combination between the shielding layer and the metal layer is firmer, so that the shielding layer has an efficient radiation protection effect.
It is understood that the polymer matrix material of the shielding layer is not limited to the above-mentioned aqueous resin, and may be, for example, one or more of polycarbonate, polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polystyrene, silicone rubber, cellulose, and protein, so long as the radiation-resistant composite powder can be uniformly dispersed in the shielding layer and stably attached to the metal layer.
According to the radiation-resistant composite material disclosed by the embodiment of the invention, the bonding agent in the shielding layer is preferably the coupling agent, and the coupling agent can improve the interface effect between the high polymer matrix material and the radiation-resistant composite powder particles, so that the radiation-resistant composite powder is more beneficial to uniformly distributing in the high polymer matrix material, the radiation-resistant composite powder in the shielding layer forms a uniform ray absorption network, and the radiation protection effect is improved.
Further, the coupling agent is preferably one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and an aluminum-titanium composite coupling agent.
The radiation-resistant composite material of the embodiment of the invention has the thickness D of the supporting layer 1 Preferably 70 μm to 150. Mu.m.
Thickness D of metal layer 2 Preferably 1 μm to 5. Mu.m.
Thickness D of shielding layer 3 Preferably 100 μm to 1000. Mu.m.
The radiation-resistant composite material has excellent radiation protection effect, high strength and low quality, and good flexibility.
Further, the weight of the supporting layer was 50g/m 2 ～200g/m 2 。
The weight of the metal layer was 20g/m 2 ～80g/m 2 。
The weight of the shielding layer was 200g/m 2 ～2000g/m 2 。
The radiation-resistant composite material of the embodiment of the invention can be that the supporting layer is provided with a first concave-convex surface, and the metal layer is arranged on the first concave-convex surface of the supporting layer. The method is beneficial to buffering the stress of the metal layer when the radiation-resistant composite material is folded and wound, and can enhance the binding force between the metal layer and the supporting layer, so that the radiation-resistant composite material is folded and wound to ensure the tight combination between the metal layer and the supporting layer, the problem of peeling of the metal layer is avoided, and the long-term use stability and the radiation resistance of the radiation-resistant composite material are improved.
The metal layer may have a second concave-convex surface, and the shielding layer may be disposed on the second concave-convex surface of the metal layer. The method is beneficial to buffering the stress of the metal layer when the radiation-resistant composite material is folded and wound, and can enhance the binding force between the metal layer and the shielding layer, so that the radiation-resistant composite material is folded and wound to ensure the tight combination between the metal layer and the shielding layer, the problem of peeling of the shielding layer can not occur, and the long-term use stability and the radiation resistance of the radiation-resistant composite material are improved.
The first concave-convex surface and/or the second concave-convex surface can be rough surfaces, so that the contact area of the surfaces can be remarkably increased, and the bonding force between layers can be improved. Of course, in other embodiments, the first concave-convex surface and/or the second concave-convex surface may be patterned concave-convex structures, such as wave structures, tooth structures, etc., which can enhance the bonding between layers.
The radiation-resistant composite material provided by the embodiment of the invention can be provided with more than one metal layer, such as one, two, three and the like, the shielding layer can be provided with more than one metal layer, such as one, two, three and the like, and the more than one metal layer and the more than one shielding layer are mutually laminated, and the outermost layer far away from the supporting layer is the shielding layer. The radiation-resistant composite material can have a more efficient radiation protection effect.
When a plurality of metal layers and a plurality of shielding layers are mutually stacked, more than one shielding layer can be arranged between two adjacent metal layers, more than one metal layer can also be arranged between two adjacent shielding layers, wherein the innermost layer close to the supporting layer is the metal layer, and the outermost layer far away from the supporting layer is the shielding layer.
The embodiment of the invention further provides a preparation method of the radiation-resistant composite material, and the radiation-resistant composite material can be realized through the method. The method comprises the following steps:
s100, providing a supporting layer, wherein the supporting layer is made of a high polymer material.
The polymeric material in the support layer may be a polymeric material as described above.
In step S100, a commercially available polymer film or cloth may be used as the support layer, or a film or cloth may be prepared as the support layer by a method known in the art. As an example, the support layer is prepared by a braiding process using the polymer material fibers as described above. As another example, the support layer is prepared by a braiding process using the polymer material fibers and the inorganic fibers as described above.
S200, preparing a metal layer, and laminating the metal layer on the supporting layer, wherein the metal layer comprises one or more of copper, nickel, iron and silver.
In step S200, the metal layer may be formed on the support layer by at least one of mechanical rolling, bonding, vapor deposition, electroplating, and electroless plating, wherein the vapor deposition is at least one of vacuum evaporation (vacuum evaporating), thermal evaporation (Thermal Evaporation Deposition), electron beam evaporation (electron beam evaporation method, EBEM), and magnetron sputtering (Magnetron sputtering). Preferably at least one of vapor deposition, electroplating and electroless plating.
S300, providing shielding slurry, wherein the shielding slurry comprises, by weight, 30-80 parts of aqueous resin, 10-70 parts of radiation-resistant composite powder and 0.5-8 parts of binding agent.
In step S300, the solid content of the aqueous resin is preferably 30% -50%, such as 30% -40%, and further such as 35% -38%, which is beneficial to uniformly dispersing the radiation-resistant composite powder and enhancing the binding force between the shielding layer and the metal layer.
In some preferred embodiments, step S300 includes:
s310, the bonding agent adopts a coupling agent, and the radiation-resistant composite powder is subjected to surface pretreatment by the coupling agent to obtain pretreated radiation-resistant composite powder.
In step S310, the radiation-resistant composite powder and the coupling agent are mixed, for example, the radiation-resistant composite powder and the coupling agent are added into a high-speed mixer, and the mixture is stirred for 3 to 10 minutes, for example, 4 to 6 minutes, so that the coupling agent is fully coated on the surface of the radiation-resistant composite powder, and then the pre-treated radiation-resistant composite powder is obtained through drying treatment. Wherein the temperature of the drying treatment is preferably 70-90 ℃, such as 75-85 ℃, and the time is preferably 20-2 h, such as 30-60 min. The coupling agent is used for carrying out surface treatment on the anti-radiation composite powder to enhance the interface compatibility of the anti-radiation composite powder and the resin matrix material, thereby being beneficial to the dispersion uniformity and stability of the anti-radiation composite powder in the shielding layer and being beneficial to improving the mechanical property of the shielding layer.
S320, mixing the pretreated radiation-resistant composite powder and the aqueous resin to obtain shielding slurry.
In step S320, the pretreated anti-radiation composite powder and the aqueous resin may be added into a high-speed mixer and stirred for 3min to 10min, for example, for 4min to 6min, so as to obtain a shielding slurry. The pretreated radiation-resistant composite powder has good interface effect with the resin matrix material, so that the radiation-resistant composite powder is uniformly and stably dispersed in the shielding slurry.
In other preferred embodiments, the shield paste further includes an auxiliary agent. Step S300 includes:
s310' is the same as step S310 described above.
S320', mixing the pretreated anti-radiation composite powder, the aqueous resin and the auxiliary agent to obtain shielding slurry.
The auxiliary agent can comprise a defoaming agent, so that the generation of foam is inhibited, the generated foam is eliminated, the shielding slurry is promoted to form a uniform system, the uniformity and the stability of the shielding layer are improved, and the shielding layer is beneficial to playing a shielding function. The defoamer can be organic silicon, polyether, etc., such as higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, etc.
The auxiliary agent can also comprise a thickening agent to adjust the viscosity of the shielding slurry, and can promote the dispersion and dispersion stability of the radiation-resistant composite powder in the shielding slurry, thereby being beneficial to improving the uniformity of the radiation-resistant composite powder in the shielding layer and further being beneficial to improving the radiation protection effect of the shielding layer. As an example, the thickener may be one or more of silicone gel, hydroxymethyl cellulose, starch, sodium alginate, polyvinyl alcohol, and styrene butadiene rubber.
In some embodiments, the shielding paste includes 0.5 to 5 parts by weight of the auxiliary agent.
Further, the weight ratio of the defoamer to the thickener in the shielding slurry is 1:1-5:1, so that the respective effects can be better exerted.
In step S320', the pretreated anti-radiation composite powder, the aqueous resin and the auxiliary agent are added into a high-speed stirrer and stirred for 3 to 10 minutes, such as 4 to 6 minutes, so as to obtain shielding slurry. The pretreated radiation-resistant composite powder has good interface effect with the resin matrix material, so that the radiation-resistant composite powder is uniformly and stably dispersed in the shielding slurry.
S400, preparing a shielding layer, coating shielding slurry on the metal layer, and drying to obtain the shielding layer, thereby obtaining the radiation-resistant composite material.
In step S400, the shielding paste may be coated on the metal layer using a known coating process, such as at least one of a blade coating process, a spray coating process, and a spin coating process.
In step S400, the temperature of the drying treatment is preferably 100-130 ℃ and the time is preferably 3-15 min.
The binding force between the obtained shielding layer and the metal layer is strong, and the radiation-resistant composite powder in the shielding layer is uniformly distributed.
According to the preparation method, the radiation-resistant composite material can be obtained, so that the radiation-resistant composite material has an efficient radiation protection function, high strength and light weight are simultaneously considered, and the radiation-resistant composite material has good flexibility.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
S100, selecting the material with the thickness of 80 mu m and the weight of 50g/m 2 The polyester fiber (commonly called polyester) fabric is used as a supporting layer.
S200, plating a copper metal layer on the surface of the supporting layer by adopting a magnetron sputtering plating process, and plating a nickel metal layer on the surface of the copper metal layer by adopting an electroplating process, wherein the thickness of the copper metal layer is 1 mu m, the thickness of the nickel metal layer is 0.8 mu m, and the total weight G of the metal layer 1 Is 30g/m 2 。
S300, weighing 20 parts by weight of radiation-resistant composite powder which is a mixture of tantalum and bismuth oxide in a weight ratio of 1:1, and carrying out surface treatment on the radiation-resistant composite powder by using 1 part by weight of silane coupling agent KH550 to obtain pretreated radiation-resistant composite powder; then drying the pretreated anti-radiation composite powder for 1h at 80 ℃; adding the dried pretreated radiation-resistant composite powder into 75 parts of waterborne polyurethane (the solid content is 36%), stirring at a high speed to uniformly disperse the pretreated radiation-resistant composite powder in the waterborne polyurethane, adding 4 parts by weight of auxiliary agents, wherein the auxiliary agents comprise defoamer and thickener, the weight ratio of the defoamer to the thickener is 3:1, and continuously stirring to form a uniform system to obtain shielding slurry.
S400, coating shielding slurry on the metal layer by adopting a knife coating process, and drying for 10min at 100 ℃ to obtain the anti-radiation composite material, wherein the thickness of the shielding layer is 150 mu m, and the weight G of the shielding layer 2 300g/m 2 。
Example 2
S100, the thickness is 102 mu m, and the weight is 85g/m 2 The polyester fiber (commonly called polyester) fabric is used as a supporting layer.
S200, plating an iron metal layer on the surface of the supporting layer by adopting an electroless plating process, and then plating a nickel metal layer on the surface of the iron metal layer by adopting an electroplating process, wherein the thickness of the iron metal layer is 1.5 mu m, the thickness of the nickel metal layer is 1.5 mu m, and the total weight G of the metal layer 1 55g/m 2 。
S300, weighing 34 parts by weight of radiation-resistant composite powder which is a mixture of barium hydroxide and tantalum pentoxide in a weight ratio of 1:2, and carrying out surface treatment on the radiation-resistant composite powder by using 1.5 parts by weight of monoalkoxy type titanium tricarboxylic acid coupling agent to obtain pretreated radiation-resistant composite powder; then drying the pretreated anti-radiation composite powder for 1h at 80 ℃; adding the dried pretreated radiation-resistant composite powder into 60 parts of aqueous polyurethane (the solid content is 36%), stirring at a high speed to uniformly disperse the pretreated radiation-resistant composite powder in the aqueous polyurethane, adding 4.5 parts by weight of auxiliary agent, wherein the auxiliary agent comprises a defoaming agent and a thickening agent, the weight ratio of the defoaming agent to the thickening agent is 3:1, and continuously stirring to form a uniform system to obtain shielding slurry.
S400, coating shielding slurry on the metal layer by adopting a knife coating process, and drying for 10min at 110 ℃ to obtain the anti-radiation composite material, wherein the thickness of the shielding layer is 200 mu m, and the weight G of the shielding layer 2 400g/m 2 。
Example 3
S100, selecting a material with the thickness of 115 mu m and the weight of 120g/m 2 The polyester fiber (commonly called polyester) fabric is used as a supporting layer.
S200, plating a nickel metal layer on the surface of the supporting layer by adopting an electroless plating process, and plating a nickel metal layer on the surface of the iron metal layer by adopting an electroplating process, wherein the thickness of the nickel metal layer is 2 mu m, the thickness of the nickel metal layer is 2.5 mu m, and the total weight G of the metal layer 1 70g/m 2 。
S300, weighing 45 parts by weight of radiation-resistant composite powder, and performing surface treatment on the radiation-resistant composite powder by using 2.5 parts by weight of aluminum triacetate and silane coupling agent KH550 composite coupling agent to obtain pretreated radiation-resistant composite powder, wherein the weight ratio of the aluminum triacetate to the silane coupling agent KH550 is 1:1; then drying the pretreated anti-radiation composite powder for 1h at 80 ℃; adding the dried pretreated radiation-resistant composite powder into 50 parts of waterborne polyurethane (the solid content is 36%), stirring at a high speed to uniformly disperse the pretreated radiation-resistant composite powder in the waterborne polyurethane, adding 2.5 parts by weight of auxiliary agent, wherein the auxiliary agent comprises defoamer and thickener, and the weight ratio of the defoamer to the thickener is 3:1, and continuously stirring to form a uniform system to obtain shielding slurry.
S400, coating shielding slurry on the metal layer by adopting a knife coating process, and drying for 8min at 130 ℃ to obtain the anti-radiation composite material, wherein the thickness of the shielding layer is 400 mu m, and the weight G of the shielding layer 2 800g/m 2 。
Comparative example 1
S100, selecting the material with the thickness of 80 mu m and the weight of 50g/m 2 The polyester fiber (commonly called polyester) fabric is used as a supporting layer.
S200, plating a radiation shielding layer on the surface of the supporting layer by adopting a magnetron sputtering plating process, wherein the radiation shielding layer is a composition of copper, nickel, tantalum and bismuth oxide, the weight ratio of the copper, the nickel, the tantalum and the bismuth oxide is the same as that of the embodiment 1, and the total weight G of the radiation shielding layer is 330G/m 2 。
The radiation protection effect test was performed on the radiation resistant composite materials prepared in examples 1 to 3 and comparative example 1 under the irradiation of gamma rays of 35.38keV, and the test results are shown in Table 1.
TABLE 1
As can be seen from comparative analysis example 1 and comparative example 1, the shielding rate of the radiation resistant composite material of the present invention against the gamma rays of 35.38keV is improved by 31% compared with comparative example 1, and the radiation protection effect of the radiation resistant composite material of the present invention is significantly improved.
As shown in the data of table 1, the shielding rate of the radiation-resistant composite material of the embodiment of the invention to the gamma rays of 35.38keV is more than 50%, and the radiation-resistant composite material of the embodiment of the invention has excellent radiation protection effect and can meet the shielding protection under the nuclear radiation condition.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (11)
1. A radiation resistant composite material comprising:
the support layer is made of a high polymer material;
the metal layer is arranged on the supporting layer in a stacked mode and comprises one or more of copper, nickel, iron and silver;
the shielding layer is arranged on the metal layer in a lamination manner and comprises, by weight, 10-80 parts of a polymer matrix material, 10-70 parts of an anti-radiation composite powder and 0.5-8 parts of a bonding agent; the radiation-resistant composite powder is two or more than three of tantalum, tantalum pentoxide, tantalum diboride, barium oxide, barium hydroxide, bismuth oxide and bismuth tungstate.
2. The radiation resistant composite of claim 1 wherein said shielding layer is disposed on a surface of said metal layer facing away from said support layer.
3. The radiation resistant composite material according to claim 1, wherein the polymer matrix material adopts an aqueous resin, and the aqueous resin is one or more of aqueous polyurethane, aqueous polyacrylic acid, aqueous organic silicon resin, aqueous epoxy resin and aqueous alkyd resin;
the bonding agent adopts a coupling agent, and the coupling agent is one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and an aluminum-titanium composite coupling agent.
4. A radiation resistant composite material according to any one of claims 1 to 3, wherein the thickness of the support layer is 70 μm to 150 μm; and/or the number of the groups of groups,
the thickness of the metal layer is 1-5 mu m; and/or the number of the groups of groups,
the thickness of the shielding layer is 100-1000 mu m.
5. The radiation resistant composite of claim 1 wherein said support layer has a first concave-convex surface, said metal layer being disposed on said first concave-convex surface of said support layer; and/or the number of the groups of groups,
the metal layer is provided with a second concave-convex surface, and the shielding layer is arranged on the second concave-convex surface of the metal layer.
6. The radiation resistant composite material of claim 1 wherein said metal layer is one or more, said shielding layer is one or more, one or more of said metal layers and one or more of said shielding layers are stacked upon each other, and an outermost layer remote from said support layer is said shielding layer.
7. A method of preparing a radiation resistant composite material according to any one of claims 1 to 6, comprising the steps of:
providing a supporting layer, wherein the supporting layer is made of a high polymer material;
preparing a metal layer, wherein the metal layer is laminated on the supporting layer, and the metal layer comprises one or more of copper, nickel, iron and silver;
providing shielding slurry, wherein the shielding slurry comprises, by weight, 30-80 parts of aqueous resin, 10-70 parts of radiation-resistant composite powder and 0.5-8 parts of bonding agent;
preparing a shielding layer, coating the shielding slurry on the metal layer, and drying to obtain the shielding layer, thereby obtaining the radiation-resistant composite material.
8. The method of claim 7, wherein the step of providing a shielding paste comprises:
the bonding agent adopts a coupling agent, and the surface of the radiation-resistant composite powder is pretreated by the coupling agent to obtain pretreated radiation-resistant composite powder;
and mixing the pretreated radiation-resistant composite powder with water-based resin to obtain the shielding slurry.
9. The method of claim 7, wherein the step of providing a shielding paste comprises:
the bonding agent adopts a coupling agent, and the surface of the radiation-resistant composite powder is pretreated by the coupling agent to obtain pretreated radiation-resistant composite powder;
mixing the pretreated anti-radiation composite powder, the aqueous resin and the auxiliary agent to obtain the shielding slurry, wherein the auxiliary agent comprises a defoaming agent and a thickening agent, and the shielding slurry comprises 0.5-5 parts of the auxiliary agent in parts by weight.
10. The method of claim 9, wherein the weight ratio of the defoamer to the thickener is 1:1 to 5:1.
11. The method according to claim 7, wherein in the step of preparing the shielding layer, the temperature of the drying treatment is 100 ℃ to 130 ℃ and the time is 3min to 15min.
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