CN110317359B - Lead-free light X-ray and gamma-ray protection material and preparation method thereof - Google Patents
Lead-free light X-ray and gamma-ray protection material and preparation method thereof Download PDFInfo
- Publication number
- CN110317359B CN110317359B CN201910637020.2A CN201910637020A CN110317359B CN 110317359 B CN110317359 B CN 110317359B CN 201910637020 A CN201910637020 A CN 201910637020A CN 110317359 B CN110317359 B CN 110317359B
- Authority
- CN
- China
- Prior art keywords
- ray
- coating
- bismuth
- gamma
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
- G21F1/085—Heavy metals or alloys
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/12—Laminated shielding materials
- G21F1/125—Laminated shielding materials comprising metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention relates to a lead-free light X-ray and gamma-ray protective material and a preparation method thereof. Uniformly coating nano metal bismuth powder on a polyester imide film, melting the metal bismuth powder into a bismuth thin skin layer after high-temperature hot pressing, adding the modified nano metal bismuth powder into PU glue, uniformly mixing, spraying the mixture on the surface of the bismuth thin skin layer, drying, and carrying out calendering molding on a fabric through a roller of a calendering machine to obtain the lead-free light X-ray and gamma-ray protective material. The prepared X-ray and gamma-ray protective material greatly improves the protective efficiency due to the flaky bismuth thin skin layer, is high-temperature resistant, lead-free and light as a protective clothing material, and has simple preparation process, high production efficiency and good application prospect in the aspect of ray protection.
Description
Technical Field
The application relates to the field of radiation protection, in particular to a lead-free light X-ray and gamma-ray protection material and a preparation method thereof.
Background
In recent years, with the rapid development of national defense research, radiology and atomic energy industries, the use of various rays is increasingly widespread. X and gamma rays are one of the important types. X and gamma rays can enter the interior of a human body and are ionized with cells in the human body, and the ions generated by ionization can destroy genetic substances such as protein, nucleic acid and the like in living cells in the human body, so that the normal metabolic process in the human body is caused, and the death of the living cells in the human body can be seriously caused. The long-term exposure to X and gamma rays can cause damage to gonads, mammary glands, hematopoietic bone marrow and the like, and the exceeding dosage can even cause cancer, thereby bringing serious threat to human bodies. Therefore, according to the properties of X and gamma rays and the action mechanism of the X and gamma rays and substances, corresponding materials are selected and prepared for protection.
The first X-ray and gamma-ray protective materials are metal materials such as lead plates and iron plates, and then heavy metals are introduced to prepare protective glass and rubber lead products and are processed into various protective clothing, helmets, protective gloves and the like. The prepared traditional protective clothing is poor in protection efficiency, can only shield some low-energy X rays, is poor in air permeability, heavy and uncomfortable to wear, and meanwhile, lead has serious harm to human bodies and the environment.
At present, the lead-free lightweight protective clothing prepared by the prior art generally takes spherical or irregular-shaped ray absorption powder as a main ray absorption substance, the absorption powder is uniformly mixed with an organic base material by a physical blending method, and the radiation-proof material is prepared by processes such as coating or calendaring and the like. For example, the Chinese invention patent CN1075702308A discloses an epoxy resin-based radiation protection material, which is formed by blending and molding rare earth oxide powder and lead oxide powder which are modified by a coupling agent and epoxy resin; for example, chinese patent CN107316667A discloses a radiation protection material and a preparation method thereof, wherein the metal shielding powder: and mixing tungsten, antimony, tantalum, bismuth and the like with a high-molecular tough substrate, and pressing to form the protective material. For example, the invention patent CN104900282A discloses a method for preparing gamma radiation protective clothing, which comprises adding micro-nano gamma radiation protective functional powder prepared by ball milling into a rubber matrix, calendering and gluing with a fabric, and vulcanizing and molding to obtain the gamma radiation protective fabric. The ray protection material prepared by the prior art gets rid of the defect of heavy weight of the traditional protection material, and the protection function is improved. However, in the functional radiation absorbing powder used in these materials, since the particles have gaps due to the spherical shape or the irregular shape, photons are directly leaked through the gaps in the process of radiation protection. Generally, the action probability of the ray and the absorption powder is increased by the overlapping mode of the protective materials. This results in an increase in the weight of the resulting radiation protective garment and a waste of resources. .
Disclosure of Invention
In order to solve the technical problems, the invention provides a lead-free light X-ray and gamma-ray protection material and a preparation method thereof, which can greatly improve the ray shielding effect under the condition of the same thickness and quality.
The invention provides a lead-free light X-ray and gamma-ray protective material which is composed of a three-layer structure, wherein a polyimide film (1), a bismuth film layer (2) and a functional PU coating (3) are respectively arranged from top to bottom; the thickness of the protective material is 0.3-0.7 mm.
As a further improvement of the invention, the thickness of the polyimide film (1) is 150-250 μm.
As a further improvement of the invention, the thickness of the bismuth thin skin layer (2) is 50-200 μm.
As a further improvement of the invention, the functional PU coating (3) is prepared from the following raw materials: metal bismuth powder, dimethyl acetamide, PU glue and a silane coupling agent.
As a further improvement of the invention, the mass ratio of the metal bismuth powder to the silane coupling agent is 2: 1-5: 1, the mass ratio of dimethylacetamide to PU glue is 2: 1-1: 2, the mass ratio of the metal bismuth powder to the PU is 0.5: 1-3: 1.
the invention further provides a method for preparing the lead-free light X-ray and gamma-ray protective material, which comprises the following steps:
s1, preparing a metal bismuth solution, namely uniformly dispersing nano metal bismuth powder into absolute ethyl alcohol, wherein the mass ratio is 1: 1-1: 5, ultrasonically stirring for 10min to form a metal bismuth solution with the viscosity of 1000-10000 mPa.s, and uniformly coating the solution on the high-temperature-resistant polyimide film (1); the diameter of the nano metal bismuth powder is 10-100 nm, and the diameter-thickness ratio is 1-500;
s2, hot-pressing to form a bismuth thin skin layer (2): uniformly coating the polyimide film of the metal bismuth in the step S1, placing the polyimide film on a hot press, and preheating for 20min at the temperature of 250-270 ℃ and under the pressure of 0 to uniformly heat the metal bismuth powder; the temperature is increased to 285-300 ℃, the bismuth powder is pressed for 10-20 min at constant temperature and constant pressure under the mechanical pressure of 25MPa, and the bismuth powder is melted at high temperature to form a bismuth thin skin layer (2) with the thickness of 50-200 mu m;
s3, preparing a functional PU coating: uniformly mixing nano metal bismuth powder and a silane coupling agent, treating the mixture in an ultrasonic generator for 10-20 min, then dropwise adding a dimethylacetamide solution, mechanically stirring the mixture for 1-2 hours, adding PU glue after the mixture is uniformly dispersed, continuously stirring the mixture uniformly, heating the mixture to 50-60 ℃, removing part of dimethylacetamide, adjusting the viscosity value, and continuously stirring the mixture for 20-30 min to obtain a functional PU coating (3) coating with the viscosity of 1000-5000 mPa.s;
s4, spraying the functional PU coating (3): adding the coating in the step S3 into a charging barrel of a spraying device, spraying the coating on the bismuth thin skin layer (2) in the step S2 through a spraying process, and drying to obtain a functional PU coating (3); the spraying process parameters are that the liquid feeding amount is 500 ml/min-800 ml/min, the air pressure is 0.3 MPa-0.7 MPa, the diameter of a nozzle of a spraying head is 10cm, the distance between the nozzle and a cloth cover is 15cm, and the number of times of the back and forth of a spray gun is 30-120 times/min; the thickness of the functional PU coating (3) is 0.1-0.3 mm;
s5, rolling and forming materials: and (4) rolling the three-layer material obtained in the step S4 through a roller of a rolling mill to enable the bismuth thin skin layer (2) and the functional PU coating (3) to be flatly and uniformly coated and adhered on the surface of the polyimide film (1), so as to obtain the rolling-formed lead-free light X-ray and gamma-ray protective material.
As a further improvement of the present invention, the calendering process parameters in the step S5 are: the temperature of the upper roller is 80-120 ℃, the temperature of the middle roller is 70-100 ℃, the temperature of the lower roller is 60-115 ℃, the roller distance is 1mm, and the rolling speed is 35-50 m/min.
The invention further protects the application of the lead-free light X-ray and gamma-ray protective material, and the protective material is used for X-ray and gamma-ray protective clothing materials.
The invention has the following beneficial effects:
(1) the metal bismuth has good capability of shielding X and gamma rays, replaces the traditional heavy metal and the existing composite material mixed with a plurality of metals, and meets the modern requirements of lead-free, light and environment-friendly protective clothing materials.
(2) The probability of the interaction between one flaky powder particle with the same volume and photons is more than 100 times that of the spherical powder particle. The melting point of the metal bismuth is 271.3 ℃, the powder can be melted and pressed into a sheet shape after being uniformly sprayed on the high-temperature resistant base cloth and then pressed at high temperature, the arrangement is compact, the powder can be overlapped into a nearly seamless metal bismuth thin skin, the probability of photons penetrating through gaps is extremely reduced, and the ray shielding capability is greatly improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a lead-free lightweight X-ray and gamma-ray protective material according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a lead-free lightweight X-ray and gamma-ray protective material according to an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of the nano-bismuth powder used in the embodiment of the present invention;
FIG. 4 is a scanning electron micrograph of a bismuth thin skin layer prepared in step S02 of example 1 according to the present invention;
1, a polyimide film; 2. a thin bismuth skin layer; 3. and (4) a functional PU coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1
Referring to the attached figure 2, the lead-free light X-ray and gamma-ray protection material is composed of a three-layer structure, namely a polyimide film 1, a bismuth thin skin layer 2 and a functional PU coating 3 from top to bottom; the thickness is 0.3 mm. The thickness of the polyimide film 1 is 150 mu m, and the polyimide film is a base material of an X-ray and gamma-ray protective material; the thickness of the bismuth thin skin layer 2 is 50 μm, the powder is melted and pressed into a sheet shape to form a seamless metal bismuth thin skin, thereby extremely reducing the probability of photons penetrating through the gap and greatly improving the ray shielding capability; the functional PU coating 3 comprises the following raw materials: the adhesive comprises bismuth metal powder, dimethylacetamide, PU adhesive and a silane coupling agent, wherein the mass ratio of the bismuth metal powder to the silane coupling agent is 3:1, the mass ratio of the dimethylacetamide to the PU adhesive is 1:1, and the mass ratio of the bismuth metal powder to the PU adhesive is 2: 1; the thickness of the coating was 0.1 mm.
Referring to fig. 1, a lead-free light X-ray and gamma-ray protective material is prepared by the following steps:
step S01, a metal bismuth solution is prepared.
Specifically, the nano metal bismuth powder is uniformly dispersed into absolute ethyl alcohol, and the mass ratio is 1: 2, ultrasonically stirring for 10min to form a metal bismuth solution with the viscosity of 1000mPa.s, and uniformly coating the solution on the high-temperature-resistant polyimide film 1; the diameter of the nano metal bismuth powder is 100 nm;
step S02, forming the bismuth thin skin layer 2 by hot pressing.
Specifically, the polyimide film 1 coated with the metal bismuth uniformly in the step S01 is placed on a hot press, and is preheated for 20min at the temperature of 270 ℃ and under the pressure of 0, so that the metal bismuth powder is heated uniformly; the temperature is raised to 300 ℃, the bismuth powder is pressed for 10min at constant temperature and constant pressure under the mechanical pressure of 25MPa, and the bismuth powder is melted at high temperature to form a bismuth thin skin layer 2 with the thickness of 50 mu m;
and step S03, preparing the functional PU coating.
Specifically, uniformly mixing nano metal bismuth powder and a silane coupling agent, treating the mixture in an ultrasonic generator for 20min, then dropwise adding a dimethylacetamide solution, mechanically stirring the mixture for 1 hour, adding PU glue after the mixture is uniformly dispersed, continuously stirring the mixture uniformly, heating the mixture to 50 ℃ to remove part of dimethylacetamide, adjusting the viscosity value, and continuously stirring the mixture for 30min to obtain the coating of the functional PU coating 3, wherein the viscosity is 1000 mPa.s; the functional PU coating 3 comprises the following raw materials: the mass ratio of the metal bismuth powder to the silane coupling agent is 3:1, the mass ratio of the dimethylacetamide to the PU adhesive is 1:1, and the mass ratio of the metal bismuth powder to the PU adhesive is 2: 1;
and step S04, spraying the functional PU coating 3.
Specifically, the coating in the step S03 is added into a charging barrel of a spraying device, sprayed onto the bismuth thin skin layer 2 in the step S02 by a spraying process, and dried to obtain a functional PU coating 3; the spraying process parameters are that the liquid feeding amount is 6500ml/min, the air pressure is 0.5MPa, the diameter of a nozzle of a spraying head is 10cm, the distance between the nozzle and a cloth cover is 15cm, and the reciprocating times of a spray gun are 80 times/min; the thickness of the functional PU coating 3 is 0.1 mm;
and step S05, performing stretch-draw forming.
Specifically, the three-layer material obtained in the step S04 is rolled by a roller of a calender so that the bismuth thin skin layer 2 and the functional PU coating 3 are flatly and uniformly coated on the surface of the polyimide film 1, and the rolling-formed lead-free light X-ray and gamma-ray protective material is obtained, wherein the thickness of the material is 0.3 mm. Wherein the parameters of the calendering process are as follows: the temperature of the upper roller is 100 ℃, the temperature of the middle roller is 80 ℃, the temperature of the lower roller is 70 ℃, the roller spacing is 1mm, and the rolling speed is 35 m/min.
Example 2
Referring to the attached figure 2, the lead-free light X-ray and gamma-ray protection material is composed of a three-layer structure, namely a polyimide film 1, a bismuth thin skin layer 2 and a functional PU coating 3 from top to bottom; the thickness is 0.5 mm. The thickness of the polyimide film 1 is 150 mu m, and the polyimide film is a base material of an X-ray and gamma-ray protective material; the thickness of the bismuth thin skin layer 2 is 150 μm, the powder is melted and pressed into a sheet shape to form a seamless metal bismuth thin skin, thereby extremely reducing the probability of photons penetrating through the gap and greatly improving the ray shielding capability; the functional PU coating 3 comprises the following raw materials: the adhesive comprises bismuth metal powder, dimethylacetamide, PU adhesive and a silane coupling agent, wherein the mass ratio of the bismuth metal powder to the silane coupling agent is 3:1, the mass ratio of the dimethylacetamide to the PU adhesive is 2:1, and the mass ratio of the bismuth metal powder to the PU adhesive is 3: 1; the thickness of the coating was 0.2 mm.
Referring to fig. 1, a lead-free light X-ray and gamma-ray protective material is prepared by the following steps:
step S01, a metal bismuth solution is prepared.
Specifically, the nano metal bismuth powder is uniformly dispersed into absolute ethyl alcohol, and the mass ratio is 1:1, ultrasonically stirring for 10min to form a metal bismuth solution with the viscosity of 5000mPa.s, and uniformly coating the solution on a high-temperature-resistant polyimide film 1; the diameter of the nano metal bismuth powder is 100 nm;
step S02, forming the bismuth thin skin layer 2 by hot pressing.
Specifically, the polyimide film 1 coated with the metal bismuth uniformly in the step S01 is placed on a hot press, and is preheated for 20min at the temperature of 280 ℃ and under the pressure of 0, so that the metal bismuth powder is heated uniformly; the temperature is increased to 290 ℃, the bismuth powder is pressed for 10min at constant temperature and constant pressure under the mechanical pressure of 25MPa, and the bismuth powder is melted at high temperature to form a bismuth thin skin layer 2 with the thickness of 150 mu m;
and step S03, preparing the functional PU coating.
Specifically, uniformly mixing nano metal bismuth powder and a silane coupling agent, treating the mixture in an ultrasonic generator for 20min, then dropwise adding a dimethylacetamide solution, mechanically stirring the mixture for 2 hours, adding PU glue after the mixture is uniformly dispersed, continuously stirring the mixture uniformly, heating the mixture to 50 ℃ to remove part of dimethylacetamide, adjusting the viscosity value, and continuously stirring the mixture for 30min to obtain the coating of the functional PU coating 3, wherein the viscosity is 1500 mPa.s; the functional PU coating 3 comprises the following raw materials: the mass ratio of the metal bismuth powder to the silane coupling agent is 3:1, the mass ratio of dimethylacetamide to PU glue is 2:1, and the mass ratio of metal bismuth powder to PU glue is 3: 1;
and step S04, spraying the functional PU coating 3.
Specifically, the coating in the step S03 is added into a charging barrel of a spraying device, sprayed onto the bismuth thin skin layer 2 in the step S02 by a spraying process, and dried to obtain a functional PU coating 3; the spraying process parameters are that the liquid feeding amount is 6500ml/min, the air pressure is 0.5MPa, the diameter of a nozzle of a spraying head is 10cm, the distance between the nozzle and a cloth cover is 15cm, and the reciprocating times of a spray gun are 80 times/min; the thickness of the functional PU coating 3 is 0.2 mm;
and step S05, performing stretch-draw forming.
Specifically, the three-layer material obtained in the step S04 is rolled by a roller of a calender so that the bismuth thin skin layer 2 and the functional PU coating 3 are flatly and uniformly coated on the surface of the polyimide film 1, and the rolling-formed lead-free light X-ray and gamma-ray protective material is obtained, wherein the thickness of the material is 0.5 mm. Wherein the parameters of the calendering process are as follows: the temperature of the upper roller is 100 ℃, the temperature of the middle roller is 80 ℃, the temperature of the lower roller is 70 ℃, the roller spacing is 1mm, and the rolling speed is 35 m/min.
The lead-free light X-ray and gamma-ray protective material with the thickness of 0.3mm prepared in the embodiment 1 of the invention is tested for the protective effect, and the results are shown in the following table 1:
TABLE 1
As can be seen from the table, the radiation protection effect of the lead-free light X-ray and gamma-ray protection material with the thickness of only 0.3mm meets the protection requirement.
Fig. 3 is a scanning electron microscope image of the nano bismuth powder used in the embodiment of the present invention. It can be seen that the metal bismuth powder has different sizes, forms irregular spherical shapes, is distributed in an agglomeration way, and is easy to form gaps among particles.
Fig. 4 is a scanning electron micrograph of the bismuth thin skin layer 2 prepared in step S02 of example 1 of the present invention, and it can be seen that the bismuth thin skin layer results in a compact and seamless structure. The metal bismuth powder is melted at high temperature by utilizing the characteristic of low melting point of the metal bismuth powder and is pressed into a sheet, when the metal bismuth powder contacts rays, the probability of photons penetrating through gaps is greatly reduced by the seamless bismuth thin skin layer, the radiation is more effectively absorbed and shielded, the resource is saved, and the defects of powder particles in the ray protection process are greatly improved. And the brittleness of the protective material is improved by the outer PU coating, and the radiation-proof performance is further improved. The prepared radiation-proof material can be compounded with different fabrics according to requirements to prepare ray-protection clothes.
Compared with the prior art, the metal bismuth has good capability of shielding X and gamma rays, replaces the traditional heavy metal and the existing composite material mixed with a plurality of metals, and meets the modern requirements of lead-free, light and environment-friendly protective clothing materials. The probability of the interaction between one flaky powder particle with the same volume and photons is more than 100 times that of the spherical powder particle. The melting point of the metal bismuth is 271.3 ℃, the powder can be melted and pressed into a sheet shape after being uniformly sprayed on the high-temperature resistant base cloth and then pressed at high temperature, the arrangement is compact, the powder can be overlapped into a nearly seamless metal bismuth thin skin, the probability of photons penetrating through gaps is extremely reduced, and the ray shielding capability is greatly improved.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (6)
1. A lead-free light X-ray and gamma-ray protective material is characterized by consisting of three layers of structures, namely a polyimide film (1), a bismuth film layer (2) and a functional PU coating (3) from top to bottom; the thickness of the protective material is 0.3-0.7 mm;
the thickness of the bismuth thin skin layer (2) is 50-200 mu m;
the functional PU coating (3) is prepared from the following raw materials: metal bismuth powder, dimethyl acetamide, PU glue and a silane coupling agent.
2. The lead-free light X-ray and gamma-ray protective material as claimed in claim 1, wherein the thickness of the polyimide film (1) is 150-250 μm.
3. The lead-free light X-ray and gamma-ray protective material as claimed in claim 1, wherein the mass ratio of the metal bismuth powder to the silane coupling agent is 2: 1-5: 1, the mass ratio of dimethylacetamide to PU glue is 2: 1-1: 2, the mass ratio of the metal bismuth powder to the PU is 0.5: 1-3: 1.
4. a method for preparing the lead-free light X-ray and gamma-ray protective material according to any one of claims 1 to 3, comprising the steps of:
s1, preparing a metal bismuth solution, namely uniformly dispersing nano metal bismuth powder into absolute ethyl alcohol, wherein the mass ratio is 1: 1-1: 5, ultrasonically stirring for 10min to form a metal bismuth solution with the viscosity of 1000-10000 mPa.s, and uniformly coating the solution on the high-temperature-resistant polyimide film (1); the diameter of the nano metal bismuth powder is 10-100 nm, and the diameter-thickness ratio is 1-500;
s2, hot-pressing to form a bismuth thin skin layer (2): uniformly coating the polyimide film of the metal bismuth in the step S1, placing the polyimide film on a hot press, and preheating for 20min at the temperature of 250-270 ℃ and under the pressure of 0 to uniformly heat the metal bismuth powder; the temperature is increased to 285-300 ℃, the bismuth powder is pressed for 10-20 min at constant temperature and constant pressure under the mechanical pressure of 25MPa, and the bismuth powder is melted at high temperature to form a bismuth thin skin layer (2) with the thickness of 50-200 mu m;
s3, preparing a functional PU coating: uniformly mixing nano metal bismuth powder and a silane coupling agent, treating the mixture in an ultrasonic generator for 10-20 min, then dropwise adding a dimethylacetamide solution, mechanically stirring the mixture for 1-2 hours, adding PU glue after the mixture is uniformly dispersed, continuously stirring the mixture uniformly, heating the mixture to 50-60 ℃, removing part of dimethylacetamide, adjusting the viscosity value, and continuously stirring the mixture for 20-30 min to obtain a functional PU coating (3) coating with the viscosity of 1000-5000 mPa.s;
s4, spraying the functional PU coating (3): adding the coating in the step S3 into a charging barrel of a spraying device, spraying the coating on the bismuth thin skin layer (2) in the step S2 through a spraying process, and drying to obtain a functional PU coating (3); the spraying process parameters are that the liquid feeding amount is 500 ml/min-800 ml/min, the air pressure is 0.3 MPa-0.7 MPa, the diameter of a nozzle of a spraying head is 10cm, the distance between the nozzle and a cloth cover is 15cm, and the number of times of the back and forth of a spray gun is 30-120 times/min; the thickness of the functional PU coating (3) is 0.1-0.3 mm;
s5, rolling and forming materials: and (4) rolling the three-layer material obtained in the step S4 through a roller of a rolling mill to enable the bismuth thin skin layer (2) and the functional PU coating (3) to be flatly and uniformly coated and adhered on the surface of the polyimide film (1), so as to obtain the rolling-formed lead-free light X-ray and gamma-ray protective material.
5. The method for preparing the lead-free light X-ray and gamma-ray protective material according to claim 4, wherein the calendering process parameters in the step S5 are as follows: the temperature of the upper roller is 80-120 ℃, the temperature of the middle roller is 70-100 ℃, the temperature of the lower roller is 60-115 ℃, the roller distance is 1mm, and the rolling speed is 35-50 m/min.
6. Use of the lead-free lightweight X, gamma ray protective material according to any of claims 1 to 3 for X, gamma ray protective clothing materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910637020.2A CN110317359B (en) | 2019-07-15 | 2019-07-15 | Lead-free light X-ray and gamma-ray protection material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910637020.2A CN110317359B (en) | 2019-07-15 | 2019-07-15 | Lead-free light X-ray and gamma-ray protection material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110317359A CN110317359A (en) | 2019-10-11 |
| CN110317359B true CN110317359B (en) | 2022-01-04 |
Family
ID=68123434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910637020.2A Active CN110317359B (en) | 2019-07-15 | 2019-07-15 | Lead-free light X-ray and gamma-ray protection material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110317359B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110861319B (en) * | 2019-11-20 | 2022-04-05 | 中广核高新核材科技（苏州）有限公司 | Radiation-resistant high-temperature-resistant fiber composite material and preparation method thereof |
| CN111009332A (en) * | 2019-12-20 | 2020-04-14 | 北航（四川）西部国际创新港科技有限公司 | Nuclear radiation shielding structure and manufacturing method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005049713A1 (en) * | 2003-11-18 | 2005-06-02 | Arntz Beteiligungs Gmbh & Co. Kg | Radiation shielding material for protective clothing, such as aprons or the like |
| CN1706005A (en) * | 2003-09-03 | 2005-12-07 | 马威格股份有限公司 | Light radiation protection material for a large energy application field |
| CN105161150A (en) * | 2015-08-06 | 2015-12-16 | 安徽贵谷电子商务有限公司 | Neutron irradiation protective clothing material and preparation method for same |
| CN106659460A (en) * | 2014-06-02 | 2017-05-10 | 特纳创新有限责任公司 | Radiation shielding and processes for producing and using the same |
| CN108411618A (en) * | 2018-03-08 | 2018-08-17 | 南通大学 | A kind of preparation method of X, gamma-rays protective fabric |
| CN108766607A (en) * | 2018-07-26 | 2018-11-06 | 上海珑原精密材料有限公司 | Lightweight lead composite material and preparation method thereof for preventing X-ray back scattering |
| CN109712735A (en) * | 2018-12-11 | 2019-05-03 | 中广核核电运营有限公司 | Anti- ionising radiation container and preparation method thereof |
-
2019
- 2019-07-15 CN CN201910637020.2A patent/CN110317359B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706005A (en) * | 2003-09-03 | 2005-12-07 | 马威格股份有限公司 | Light radiation protection material for a large energy application field |
| WO2005049713A1 (en) * | 2003-11-18 | 2005-06-02 | Arntz Beteiligungs Gmbh & Co. Kg | Radiation shielding material for protective clothing, such as aprons or the like |
| CN106659460A (en) * | 2014-06-02 | 2017-05-10 | 特纳创新有限责任公司 | Radiation shielding and processes for producing and using the same |
| CN105161150A (en) * | 2015-08-06 | 2015-12-16 | 安徽贵谷电子商务有限公司 | Neutron irradiation protective clothing material and preparation method for same |
| CN108411618A (en) * | 2018-03-08 | 2018-08-17 | 南通大学 | A kind of preparation method of X, gamma-rays protective fabric |
| CN108766607A (en) * | 2018-07-26 | 2018-11-06 | 上海珑原精密材料有限公司 | Lightweight lead composite material and preparation method thereof for preventing X-ray back scattering |
| CN109712735A (en) * | 2018-12-11 | 2019-05-03 | 中广核核电运营有限公司 | Anti- ionising radiation container and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110317359A (en) | 2019-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110317359B (en) | Lead-free light X-ray and gamma-ray protection material and preparation method thereof | |
| CN112831078B (en) | Preparation method of core-shell structure tungsten/gadolinium oxide PVC (polyvinyl chloride) calendered material for X and gamma ray protection | |
| CN106566226B (en) | A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application | |
| CN107910088A (en) | A kind of rare-earth-based flexible core radiation protection material and its preparation method and application | |
| CN110372903B (en) | Lead-free light X, gamma and neutron integrated protection material and preparation method thereof | |
| CN101085842A (en) | Method for preparing electromagnetic shielding plastic master batch and composite plastic | |
| CN111228142A (en) | Radiation protection material, preparation method thereof and skin care product | |
| CN109825743A (en) | A kind of application method of structure-function integration neutron absorber material | |
| KR102318127B1 (en) | Hybrid lead-free radiation shielding material and radiation shielding suit using the same | |
| CN104558703B (en) | A kind of tungsten-based composite material and preparation method thereof applied to alpha ray shield | |
| CN109267333B (en) | Anti-radiation composite material and preparation method thereof | |
| CN105014075B (en) | A kind of lead aluminum boron complex nucleus shielding material and preparation method thereof | |
| CN107778508B (en) | Gradient type flexible n-gamma mixed field radiation shielding material and preparation method thereof | |
| CN110527887A (en) | A kind of shielding neutron and the boron tungsten aluminium composite material of gamma ray and preparation method thereof | |
| KR101591965B1 (en) | Radiation shielding thin-film composite materials made by non-leaded bismuth-tin alloy particles dispersed in the polymer | |
| CN113881312A (en) | Rare earth-high Z-graphene-composite coating for aerospace-grade chip total dose effect protection and preparation method thereof | |
| CN108118523B (en) | Lead-free radiation protection cloth and preparation method thereof | |
| CN109354826B (en) | Nuclear shielding material and method for producing same | |
| CN115602348A (en) | Gamma-ray protection composition, film, fabric, preparation method of gamma-ray protection composition, film, fabric and protective clothing | |
| CN109306628A (en) | A kind of duplex coating basalt fibre fabrics and preparation method thereof for electromagnetic protection field | |
| CN112802619B (en) | High-strength titanium-based boron-tungsten composite shielding material and preparation method thereof | |
| TWI804800B (en) | Neutron moderator material and method for producing the same | |
| CN104924731A (en) | Composite production process for rolled flexible lead-free gamma shielding material | |
| CN110197734B (en) | Preparation method of X-ray shielding material based on natural leather | |
| CN109868467B (en) | Preparation method of anti-radiation reinforced composite coating on surface of aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |