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, gamma rays and neutrons are one of their important types. X-ray, gamma-ray and neutron can enter the interior of human body and ionize 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. Due to long-term exposure to X, gamma rays and neutrons, the medicine can cause damage to gonads, mammary glands, hematopoietic bone marrow and the like, and even cause cancer when the dosage is over, thereby bringing serious threat to human bodies. Therefore, according to the properties of X, gamma rays and neutrons and the action mechanism of the neutrons and substances, corresponding materials are selected and prepared for protection.
The first X-ray, gamma-ray and neutron 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, gamma-ray and neutron protection material and a preparation method thereof, and the radiation shielding effect can be greatly improved under the condition of the same thickness and quality.
The invention provides a lead-free light X-ray, gamma-ray and neutron protection material which is composed of a three-layer structure, wherein a polyimide film (1), a bismuth film layer (2) and a functional polyurethane rubber resin coating (3) are respectively arranged from top to bottom; the thickness of the protective material is 0.3-2 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 50-800 μm.
As a further improvement of the invention, the functional polyurethane rubber resin coating (3) comprises the following raw materials: functional powder, a silane coupling agent, dimethylacetamide and polyurethane rubber resin.
As a further improvement of the invention, the functional powder comprises nano metal bismuth powder, metal tungsten powder and boron powder.
As a further improvement of the invention, the mass ratio of the functional powder to the silane coupling agent is 2: 1-5: 1, the mass ratio of dimethylacetamide to polyurethane rubber resin is 1: 1-1: 2, and the mass ratio of functional powder to polyurethane rubber resin is 0.5: 1-3: 1; the thickness of the coating is 0.1 mm-1 mm.
The invention further provides a method for preparing the lead-free light X-ray, gamma-ray and neutron protection 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 100 nm-1000 nm, and the diameter-thickness ratio is 1-500;
s2, hot pressing to form a bismuth thin skin layer: putting the polyimide film uniformly coated with the metal bismuth in the step S1 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 50-800 mu m;
s3, preparing a functional polyurethane rubber resin coating: uniformly mixing the functional 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 for 1-2 hours, uniformly dispersing, then adding polyurethane rubber resin, continuously stirring uniformly, heating to 50-60 ℃, removing part of dimethylacetamide, adjusting the viscosity value, and continuously stirring for 20-30 min to obtain a coating of the functional polyurethane rubber resin coating (3), wherein the viscosity is 1000-5000 mPa.s;
s4, spraying a functional polyurethane rubber resin coating: 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 polyurethane rubber resin 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 polyurethane rubber resin coating is 0.1-1 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 sheet layer (2) and the functional polyurethane rubber resin coating layer (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, gamma-ray and neutron protection 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, gamma-ray and neutron protection material, and the protection material is used for X-ray, gamma-ray and neutron protection clothing materials.
The invention has the following beneficial effects:
(1) the metal bismuth has good capability of shielding X, gamma rays and neutrons, 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.
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, gamma-ray and neutron protection material is composed of a three-layer structure, wherein a polyimide film 1, a bismuth thin skin layer 2 and a functional polyurethane rubber resin coating 3 are respectively arranged 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 substrate of X, gamma-ray and neutron protection materials; 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 polyurethane rubber resin coating 3 comprises the following raw materials: the functional powder comprises nano metal bismuth powder, metal tungsten powder and boron powder, the mass ratio of the functional powder to the silane coupling agent is 3:1, the mass ratio of the dimethylacetamide to the polyurethane rubber resin is 1:1, and the mass ratio of the functional powder to the polyurethane rubber resin is 2: 1; the thickness of the coating was 0.1 mm.
Referring to fig. 1, a lead-free light X-ray, gamma-ray and neutron shielding 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 polyurethane rubber resin coating.
Specifically, the functional powder and the silane coupling agent are uniformly mixed, after being treated in an ultrasonic generator for 20min, a dimethylacetamide solution is dripped, the mixture is mechanically stirred for 1 hour, polyurethane rubber resin is added after the mixture is uniformly dispersed, the mixture is continuously stirred uniformly, part of dimethylacetamide is removed when the temperature is raised to 50 ℃, the viscosity value is adjusted, and after the mixture is continuously stirred for 30min, the coating of the functional polyurethane rubber resin coating 3 is obtained, wherein the viscosity is 1000 mPa.s;
the mass ratio of the functional powder to the silane coupling agent is 3:1, the mass ratio of dimethylacetamide to polyurethane rubber resin is 1:1, and the mass ratio of functional powder to polyurethane rubber resin is 2: 1;
and step S04, spraying the functional polyurethane rubber resin 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 through a spraying process, and dried to obtain a functional polyurethane rubber resin 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 polyurethane rubber resin 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 sheet layer 2 and the functional polyurethane rubber resin layer 3 are flatly and uniformly coated on the surface of the polyimide film 1, and the roll-formed lead-free light X-ray, gamma-ray and neutron protection 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, gamma-ray and neutron protection material is composed of a three-layer structure, wherein the three-layer structure is a polyimide film 1, a bismuth film layer 2 and a functional polyurethane rubber resin 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 substrate of X, gamma-ray and neutron protection materials; 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 polyurethane rubber resin coating comprises the following raw materials: the functional powder comprises nano metal bismuth powder, metal tungsten powder and boron powder, the mass ratio of the functional powder to the silane coupling agent is 3:1, the mass ratio of the dimethylacetamide to the polyurethane rubber resin is 2:1, and the ratio of the functional powder to the polyurethane rubber resin is as follows: the mass ratio of the nano metal bismuth powder, the metal tungsten powder and the boron powder to the polyurethane rubber resin is 3: 1; the thickness of the coating was 0.2 mm.
Referring to fig. 1, a lead-free light X-ray, gamma-ray and neutron shielding 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 with the thickness of 150 mu m;
and step S03, preparing the functional polyurethane rubber resin coating.
Specifically, the functional powder and the silane coupling agent are uniformly mixed, after being treated in an ultrasonic generator for 20min, a dimethylacetamide solution is dripped, the mixture is mechanically stirred for 1 hour, polyurethane rubber resin is added after the mixture is uniformly dispersed, the mixture is continuously stirred uniformly, part of dimethylacetamide is removed when the temperature is raised to 50 ℃, the viscosity value is adjusted, and after the mixture is continuously stirred for 30min, the coating of the functional polyurethane rubber resin coating 3 is obtained, wherein the viscosity is 1500 mPa.s; the mass ratio of the functional powder to the silane coupling agent is 3:1, the mass ratio of dimethylacetamide to polyurethane rubber resin is 2:1, and the mass ratio of functional powder to polyurethane rubber resin is 3: 1;
and step S04, spraying the functional polyurethane rubber resin 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 through a spraying process, and dried to obtain a functional polyurethane rubber resin 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 polyurethane rubber resin 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 sheet layer 2 and the functional polyurethane rubber resin layer 3 are flatly and uniformly coated on the surface of the polyimide film 1, and the rolled and 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, and the protection efficiency on low-energy neutrons of 0.5eV reaches 80%.
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 polyurethane rubber resin 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, gamma rays and neutrons, 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.