Lead-free X-ray and gamma-ray protection hard material and preparation method thereof
阅读说明：本技术 一种无铅的X、γ射线防护硬质材料及制备方法 (Lead-free X-ray and gamma-ray protection hard material and preparation method thereof ) 是由 许凤奎 杜延修 王海 戚玮 于 2021-08-20 设计创作，主要内容包括：本发明公开了一种无铅的X、γ射线防护硬质材料及制备方法,主要涉及辐射防护材料领域。其原料包括树脂基材、功能性粒子和助剂,所述树脂基材与功能性粒子的重量配比为1：1.5-3.5；所述树脂基材包括聚氯乙烯、聚乙烯、聚丙烯、聚苯烯、工程塑料中的任一项或几项的组合；所述功能性粒子包括钨粉、氧化铋、氧化钆、氧化钽；所述助剂包括钙锌复合稳定剂、氯化聚乙烯、硬脂酸、聚乙烯蜡、偶联剂。本发明不含铅,绿色环保,对于X、γ射线的防护等级高。(The invention discloses a lead-free X-ray and gamma-ray protection hard material and a preparation method thereof, and mainly relates to the field of radiation protection materials. The raw materials comprise a resin base material, functional particles and an auxiliary agent, wherein the weight ratio of the resin base material to the functional particles is 1: 1.5-3.5; the resin substrate comprises any one or a combination of polyvinyl chloride, polyethylene, polypropylene, polyphenylene and engineering plastics; the functional particles comprise tungsten powder, bismuth oxide, gadolinium oxide and tantalum oxide; the auxiliary agent comprises a calcium-zinc composite stabilizer, chlorinated polyethylene, stearic acid, polyethylene wax and a coupling agent. The invention does not contain lead, is green and environment-friendly, and has high protection level for X and gamma rays.)
1. The lead-free X-ray and gamma-ray protection hard material is characterized by comprising a resin base material, functional particles and an auxiliary agent, wherein the weight ratio of the resin base material to the functional particles is 1: 1.5-3.5;
the resin substrate comprises any one or a combination of polyvinyl chloride, polyethylene, polypropylene, polyphenylene and engineering plastics;
the functional particles comprise tungsten powder, bismuth oxide, gadolinium oxide and tantalum oxide;
the auxiliary agent comprises a calcium-zinc composite stabilizer, chlorinated polyethylene, stearic acid, polyethylene wax and a coupling agent.
2. The lead-free X and gamma ray protective hard material as claimed in claim 1, wherein the resin substrate is polyvinyl chloride.
3. The lead-free hard X-ray and gamma-ray protective material as claimed in claim 1, wherein the weight ratio of the resin base material to the tungsten powder, the bismuth oxide, the gadolinium oxide and the tantalum oxide is 1:1 xX: 0.62 xX: 0.2 xX: 0.21 xX, wherein the value of X is 1-6.
4. The lead-free hard X-ray and gamma-ray protective material according to claim 1,
the purity of the tungsten powder is not less than 98%, the granularity is not less than 300 meshes, and the density is not less than 19g/cm3；
And/or the presence of a gas in the gas,
the bismuth oxide is alpha type or beta type, the purity of the bismuth oxide is not less than 99%, the granularity is not less than 300 meshes, and the density is not less than 8.5g/cm3；
And/or the presence of a gas in the gas,
the gadolinium oxide has the purity of not less than 95%, the granularity of not less than 300 meshes and the density of not less than 7.4g/cm3；
And/or the presence of a gas in the gas,
the purity of the tantalum oxide is not less than 98%, the granularity is not less than 300 meshes, and the density is not less than 8.7g/cm3。
5. The lead-free X-ray and gamma-ray protective hard material as claimed in claim 1, characterized by comprising the following raw materials in parts by weight:
100 parts of polyvinyl chloride, 350 parts of tungsten powder, 217 parts of bismuth oxide, 70 parts of gadolinium oxide, 73.5 parts of tantalum oxide, 7 parts of calcium-zinc composite heat stabilizer, 8 parts of chlorinated polyethylene, 1 part of stearic acid, 1.5 parts of polyethylene wax and 5 parts of coupling agent.
6. The lead-free X-ray and gamma-ray protective hard material as claimed in claim 1, which is prepared by the following method: the raw materials are evenly stirred and then are extruded and molded to obtain the composite material.
7. The lead-free X-ray and gamma-ray protective hard material as claimed in claim 1, which is prepared by the following method: the raw materials are uniformly stirred in a temperature-controlled stirring device, and after the mixture is cooled to below 30 ℃, the mixture is added into a plastic extruder for extrusion, and then the mixture is cooled and coated with a film, so that the composite material is obtained.
8. The lead-free X-ray and gamma-ray protective hard material as claimed in claim 1, which is prepared by the following method:
adding the resin base material into a temperature-controlled stirring device, stirring for 5 minutes at the temperature of 40-50 ℃, adding the functional particles and the auxiliary agent, and stirring at a high speed for 15 minutes at the temperature of 70-80 ℃ to obtain a raw material mixture;
cooling the raw material mixture to below 30 ℃;
feeding the cooled raw material mixture into a plastic extruder, heating the raw material mixture in a first zone to 125 ℃, heating the raw material mixture in a second zone to 165 ℃, heating the raw material mixture in a third zone to 165 ℃, heating the raw material mixture in a fourth zone to 150 ℃ and heating the raw material mixture in a fifth zone to 135 ℃, injecting the raw material mixture into a forming die, then forming the raw material mixture through the die, cooling and forming the raw material mixture, cooling the raw material mixture in a water tank, drawing the raw material mixture through a tractor, coating a film on a heating film coating machine, and cutting the raw material mixture through a fixed-length transverse cutting machine to prepare the hard protective material, wherein the forming die comprises two sets of front and back arranged devices and are provided with cooling circulating water devices;
and cooling the extruded protective material, laminating, and baking and heating the film and rolling by a plastic roller.
9. The lead-free hard X-ray and gamma-ray protective material as claimed in claim 1, wherein the lead-free hard X-ray and gamma-ray protective material is used for protecting against X-ray and gamma-ray radiation in specific applications.
10. A method for preparing lead-free X-ray and gamma-ray protective hard materials, which is characterized in that the lead-free X-ray and gamma-ray protective hard materials are prepared by mixing the raw materials according to claim 1 and performing extrusion molding.
Technical Field
The invention relates to the field of radiation protection materials, in particular to a lead-free X-ray and gamma-ray protection hard material and a preparation method thereof.
Background
With the development of science and technology, radiation technology brings great convenience to human beings, but also brings worry about the problem that ionizing radiation affects human or biological health, and because of the harm of radiation, a layer of shielding object or body is added or arranged between people and a radiation source in hospitals, nuclear power, military industry, industrial flaw detection, scientific research and other places to ensure the safety of human or biological.
Early protective materials generally adopt lead plates, but the lead plates have too large specific gravity per unit volume, are soft in texture and have no regular shape, and free lead atoms are dispersed in the air in the using process and are harmful to human bodies or organisms; the radiation impinging on the lead plate produces a compton effect that produces scattered radiation that can cause secondary damage to humans or living beings in the environment. The construction cost is high, the appearance is not beautiful, and the environment is polluted.
Disclosure of Invention
The invention aims to provide a lead-free hard X-ray and gamma-ray protection material and a preparation method thereof, which are lead-free, green and environment-friendly and have high protection level on X-ray and gamma-ray.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the lead-free X-ray and gamma-ray protection hard material comprises the following raw materials of a resin base material, functional particles and an auxiliary agent, wherein the weight ratio of the resin base material to the functional particles is 1: 1.5-3.5;
the resin substrate comprises any one or a combination of polyvinyl chloride, polyethylene, polypropylene, polyphenylene and engineering plastics;
the functional particles comprise tungsten powder, bismuth oxide, gadolinium oxide and tantalum oxide;
the auxiliary agent comprises a calcium-zinc composite stabilizer, chlorinated polyethylene, stearic acid, polyethylene wax and a coupling agent.
Further, the resin base material is polyvinyl chloride.
Furthermore, the weight ratio of the resin base material to the tungsten powder, the bismuth oxide, the gadolinium oxide and the tantalum oxide is 1:1 xX: 0.62 xX: 0.2 xX: 0.21 xX, wherein the value range of X is 1-6.
Further, the purity of the tungsten powder is not less than 98%, the granularity is not less than 300 meshes, and the density is not less than 19g/cm3；
And/or the presence of a gas in the gas,
the bismuth oxide is alpha type or beta type, the purity of the bismuth oxide is not less than 99%, the granularity is not less than 300 meshes, and the density is not less than 8.5g/cm3；
And/or the presence of a gas in the gas,
the gadolinium oxide has the purity of not less than 95%, the granularity of not less than 300 meshes and the density of not less than 7.4g/cm3；
And/or the presence of a gas in the gas,
the purity of the tantalum oxide is not less than 98%, the granularity is not less than 300 meshes, and the density is not less than 8.7g/cm3。
Further, the raw materials comprise the following components in parts by weight:
100 parts of polyvinyl chloride, 350 parts of tungsten powder, 217 parts of bismuth oxide, 70 parts of gadolinium oxide, 73.5 parts of tantalum oxide, 7 parts of calcium-zinc composite heat stabilizer, 8 parts of chlorinated polyethylene, 1 part of stearic acid, 1.5 parts of polyethylene wax and 5 parts of coupling agent.
Further, the preparation method comprises the following steps: the raw materials are evenly stirred and then are extruded and molded to obtain the composite material.
Further, the preparation method comprises the following steps: the raw materials are uniformly stirred in a temperature-controlled stirring device, and after the mixture is cooled to below 30 ℃, the mixture is added into a plastic extruder for extrusion, and then the mixture is cooled and coated with a film, so that the composite material is obtained.
Further, the preparation method comprises the following steps:
adding the resin base material into a temperature-controlled stirring device, stirring for 5 minutes at the temperature of 40-50 ℃, adding the functional particles and the auxiliary agent, and stirring at a high speed for 15 minutes at the temperature of 70-80 ℃ to obtain a raw material mixture;
cooling the raw material mixture to below 30 ℃;
feeding the cooled raw material mixture into a plastic extruder, heating the raw material mixture in a first zone to 125 ℃, heating the raw material mixture in a second zone to 165 ℃, heating the raw material mixture in a third zone to 165 ℃, heating the raw material mixture in a fourth zone to 150 ℃ and heating the raw material mixture in a fifth zone to 135 ℃, injecting the raw material mixture into a forming die, then forming the raw material mixture through the die, cooling and forming the raw material mixture, cooling the raw material mixture in a water tank, drawing the raw material mixture through a tractor, coating a film on a heating film coating machine, and cutting the raw material mixture through a fixed-length transverse cutting machine to prepare the hard protective material, wherein the forming die comprises two sets of front and back arranged devices and are provided with cooling circulating water devices;
and cooling the extruded protective material, laminating, and baking and heating the film and rolling by a plastic roller.
Further, when in specific application, the material is used for protecting hard materials from X-ray and gamma-ray radiation.
The preparation method of the lead-free X-ray and gamma-ray protection hard material is used as another aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the technology adopts the resin base material, adds the functional particles and the auxiliary agent in combination, mixes and then extrudes and molds through a plastic extruder, and the obtained hard material has higher lead equivalent and can have good protection and shielding effects on X and gamma ray radiation. And lead is not contained, and green and environment-friendly processing and using processes can be realized.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the present application.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Example 1:
a lead-free X-ray and gamma-ray protective hard material comprises the following raw materials by weight:
100 parts of PVC (polyvinyl chloride), 150 parts of W (tungsten powder), 93 parts of Bi2O3 (bismuth oxide), 30 parts of Gd2O3 (gadolinium oxide), 31.5 parts of Ta2O5 (tantalum oxide), 7 parts of calcium-zinc composite heat stabilizer, 8 parts of CPE (chlorinated polyethylene), 1 part of SA (stearic acid), 1.5 parts of PE wax (polyethylene wax) and 5 parts of KH550 (coupling agent).
The materials are put into a speed-adjustable temperature-controlled stirring device, after the materials are uniformly stirred at a high speed, the mixture is cooled to below 30 ℃, the mixture is added into an injection molding machine for extrusion, and then the mixture is cooled and coated with a film to obtain the lead-free X-ray and gamma-ray protective hard material with the thickness of 8 mm.
Example 2:
a lead-free X-ray and gamma-ray protective hard material comprises the following raw materials by weight:
100 parts of PVC (polyvinyl chloride), 200 parts of W (tungsten powder), 124 parts of Bi2O3 (bismuth oxide), 40 parts of Gd2O3 (gadolinium oxide), 42 parts of Ta2O5 (tantalum oxide), 7 parts of calcium-zinc composite heat stabilizer, 8 parts of CPE (chlorinated polyethylene), 1 part of SA (stearic acid), 1.5 parts of PE wax (polyethylene wax) and 5 parts of KH550 (coupling agent).
The materials are put into a speed-adjustable temperature-controlled stirring device, after the materials are uniformly stirred at a high speed, the mixture is cooled to below 30 ℃, and the mixture is added into a plastic extruder to be extruded, cooled and coated with a film, so that the lead-free X-ray and gamma-ray protective hard material with the thickness of 8mm is obtained.
Example 3:
a lead-free X-ray and gamma-ray protective hard material comprises the following raw materials by weight:
100 parts of PVC (polyvinyl chloride), 250 parts of W (tungsten powder), 155 parts of Bi2O3 (bismuth oxide), 50 parts of Gd2O3 (gadolinium oxide), 52.5 parts of Ta2O5 (tantalum oxide), 7 parts of calcium-zinc composite heat stabilizer, 8 parts of CPE (chlorinated polyethylene), 1 part of SA (stearic acid), 1.5 parts of PE wax (polyethylene wax) and 5 parts of KH550 (coupling agent).
The materials are put into a speed-adjustable temperature-controlled stirring device, after the materials are uniformly stirred at a high speed, the mixture is cooled to below 30 ℃, and the mixture is added into a plastic extruder to be extruded, cooled and coated with a film, so that the lead-free X-ray and gamma-ray protective hard material with the thickness of 8mm is obtained.
Example 4:
a lead-free X-ray and gamma-ray protective hard material comprises the following raw materials by weight:
100 parts of PVC (polyvinyl chloride), 300 parts of W (tungsten powder), 186 parts of Bi2O3 (bismuth oxide), 60 parts of Gd2O3 (gadolinium oxide), 63 parts of Ta2O5 (tantalum oxide), 7 parts of calcium-zinc composite heat stabilizer, 8 parts of CPE (chlorinated polyethylene), 1 part of SA (stearic acid), 1.5 parts of PE wax (polyethylene wax) and 5 parts of KH550 (coupling agent).
The materials are put into a speed-adjustable temperature-controlled stirring device, after the materials are uniformly stirred at a high speed, the mixture is cooled to below 30 ℃, and the mixture is added into a plastic extruder to be extruded, cooled and coated with a film, so that the lead-free X-ray and gamma-ray protective hard material with the thickness of 8mm is obtained.
Example 5:
a lead-free X-ray and gamma-ray protective hard material comprises the following raw materials by weight:
100 parts of PVC (polyvinyl chloride), 350 parts of W (tungsten powder), 217 parts of Bi2O3 (bismuth oxide), 70 parts of Gd2O3 (gadolinium oxide), 73.5 parts of Ta2O5 (tantalum oxide), 7 parts of calcium-zinc composite heat stabilizer, 8 parts of CPE (chlorinated polyethylene), 1 part of SA (stearic acid), 1.5 parts of PE wax (polyethylene wax) and 5 parts of KH550 (coupling agent).
The materials are put into a speed-adjustable temperature-controlled stirring device, after uniform stirring, the mixture is cooled to below 30 ℃, and the mixture is added into a plastic extruder for extrusion, and then is cooled and coated with a film to obtain the lead-free X and gamma ray protection hard material with the thickness of 8 mm.
Table one: example ratio statistics Table
Practice ofExample (b)
1
2
3
4
5
PVC (polyvinyl chloride)
100
100
100
100
100
PE (polyethylene)
PP (Polypropylene)
PS (polyphenylene)
ABS (engineering plastic)
W (tungsten powder)
150
200
250
300
350
Bi2O3(bismuth oxide)
93
124
155
186
217
Gd2O3(gadolinium oxide)
30
40
50
60
70
Ta2O5(tantalum oxide)
31.5
42
52.5
63
73.5
Calcium-zinc composite stabilizer
7
7
7
7
7
CPE (chlorinated polyethylene)
8
8
8
8
8
SA (stearic acid)
1
1
1
1
1
PE wax (polyethylene wax)
1.5
1.5
1.5
1.5
1.5
KH550 (coupling agent)
5
5
5
5
5
The components of one of the tables are calculated in parts by weight.
Table two: radiation protection effect data table of embodiment
The lead equivalent in the second table is measured by lead-free X-ray and gamma-ray protection hard materials under the voltage of a 120KV tube.
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