High radiation shielding particulate material and method of making same

Abstract

The application relates to a high-radiation shielding particle material and a preparation method thereof, and belongs to the technical field of shielding materials. The application aims to solve the problems that the existing radiation shielding materials cannot have the shielding performance of gamma rays, good flexibility and convenient construction performance and the like, and the particle material is composed of glass microspheres, a chemical nickel plating layer, an electroplated lead layer, an electroplated tungsten layer and an electroplated tantalum layer. The thickness of each layer is controlled to be 20 mu m. The method is that nickel is deposited on the surface of the glass microspheres by a chemical nickel plating method, and then an electroplated lead layer, an electroplated tungsten layer and an electroplated tantalum layer are sequentially deposited by an electroplating method. The glass microspheres are pretreated, and nickel is deposited on the surface of the glass microspheres by a chemical nickel plating method, so that other electroplated layers can be more easily deposited on the surface; the electroplated lead layer and the electroplated tungsten layer have the characteristics of good combined shielding performance of gamma rays and neutrons; and the metal tantalum layer has good gamma ray shielding performance and excellent mechanical performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of shielding materials, and relates to a high-radiation shielding particle material and a preparation method thereof. BACKGROUND

[0002] High-gamma-ray shielding composite materials play an important role in protection in specific places such as hospitals and power stations, and high-gamma-ray shielding particles are the basis of shielding composite materials, so it is of great significance to design new shielding particles. Traditional gamma-ray radiation shielding materials include glass and concrete, and the shielding performance of the current gamma-ray shielding materials is always limited, and in the actual ray penetration process, multiple rays often exist at the same time. The LBL (layer-by-layer self-assembly) method can be used to construct a nano shielding film on the surface of hollow glass microspheres, so as to reduce the density of the shielding material and the sedimentation of the filler powder in the preparation process, and realize the controllable preparation of a multi-layer gradient structure, and improve the ray shielding effect through multi-interface reflection / scattering. SUMMARY

[0003] The application aims to solve the problems that the existing radiation shielding materials cannot have the shielding performance of gamma rays, good flexibility and convenient construction, and provides a high-radiation shielding particle material and a preparation method thereof. The composite material has excellent high-energy ray shielding performance, good construction and versatility, simple preparation process, low cost, convenient operation and good performance.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the application is as follows:

[0005] A high-radiation shielding particle material, which is composed of glass microspheres, a chemical nickel plating layer, an electroplated lead layer, an electroplated tungsten layer and an electroplated tantalum layer.

[0006] Further, the thickness of each layer is controlled to be 20 μm.

[0007] A preparation method of the high-radiation shielding particle material, which comprises the following steps: depositing nickel on the surface of the glass microspheres by chemical nickel plating, and then sequentially depositing an electroplated lead layer, an electroplated tungsten layer and an electroplated tantalum layer by electroplating.

[0008] Further, the method comprises the following steps:

[0009] Step 1: After the glass microspheres are pretreated by acid washing, they are immersed in a nickel sulfate plating solution, nickel ions in the plating solution are reduced to metallic nickel on the surface of the glass microspheres, and a plating layer is formed on the glass microspheres, and then the glass microspheres are cleaned to remove residual impurities;

[0010] Step two: the lead plate is placed in the trough and connected with the electrode as the cathode, and the basic lead carbonate plating solution is prepared, then the glass microspheres with chemical nickel plating in step one are rolled down along the lead plate, so that the reduced lead ions are uniformly deposited on the surface, and the residual impurities are removed by cleaning;

[0011] Step three: the tungsten plate is placed in the trough and connected with the electrode as the cathode, and the sodium tungstate plating solution is prepared, then the glass microspheres with chemical nickel plating and lead plating in step two are rolled down along the lead plate, so that the reduced tungsten ions are uniformly deposited on the surface, and the residual impurities are removed by cleaning;

[0012] Step four: the tantalum plate is placed in the trough and connected with the electrode as the cathode, and the sodium tantalum fluoride plating solution is prepared, then the glass microspheres with chemical nickel plating, lead plating and tungsten plating in step three are rolled down along the lead plate, so that the reduced tantalum ions are uniformly deposited on the surface, and the residual impurities are removed by cleaning.

[0013] Further, the method further comprises step five: selecting one or more times to repeat the step two, step three or step four to obtain one or more layers of nickel, tungsten or tantalum, and finally preparing the heterogeneous multi-layer core-shell structure microsphere radiation shielding composite material.

[0014] Further, in step one, the concentration of the nickel sulfate plating solution is 100-150g·L -1 , the PH is 5-5.5, and the cathode current density is 0.5-1A·dm -2 .

[0015] Further, in step two, the concentration of the basic lead carbonate plating solution is 130-150g·L -1 .

[0016] Further, in step three, the concentration of the sodium tungstate plating solution is 160-210g·L -1 .

[0017] Further, in step four, the concentration of the sodium tantalum fluoride plating solution is 180-220g·L -1 .

[0018] The beneficial effects of the present application relative to the prior art are: the heterogeneous multilayer core-shell structure type microsphere radiation shielding composite material in the present application is composed of glass microspheres, a chemical nickel plating layer, an electroplated lead layer, an electroplated tungsten layer, and an electroplated tantalum layer. Since the surface of the glass microspheres is smooth, it is difficult to directly deposit the shielding layer on the surface thereof, so the surface thereof needs to be pretreated, and the nickel is deposited on the surface thereof by chemical nickel plating, so that the other electroplated layers can be more easily deposited on the surface thereof; the electroplated lead layer and the electroplated tungsten layer have good combined shielding performance of gamma rays and neutrons; and the metal tantalum layer has good gamma ray shielding performance and excellent mechanical properties. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 Preparation schematic diagram of high irradiation shielding particle material

[0020] Figure 2 HVL schematic diagram of the shielding material of Example 1

[0021] Figure 3 TVL schematic diagram of the shielding material of Example 1

[0022] Figure 4 RPE schematic diagram of the shielding material of Example 1

[0023] Figure 5 HVL schematic diagram of the shielding material of Example 2

[0024] Figure 6 TVL schematic diagram of the shielding material of Example 2

[0025] Figure 7 RPE schematic diagram of the shielding material of Example 2. DETAILED DESCRIPTION

[0026] The technical solutions in the present application will be described clearly and completely in combination with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions suggested by the manufacturers. The reagents or instruments not mentioned by the manufacturers are all conventional products that can be obtained by market purchase.

[0027] Example 1

[0028] The functional layers of the multilayer structure glass microsphere shielding composite material are divided into four layers, the first layer is a metal nickel layer, the second layer is a metal lead layer, the third layer is a metal tungsten layer, and the fourth layer is a metal tantalum layer.

[0029] The glass microspheres are pretreated by acid washing and the like, and then immersed in a nickel sulfate plating solution. The nickel ions in the plating solution are reduced to metallic nickel on the surface of the glass microspheres, and are deposited on the sample to form a plating layer. The temperature is 50-70°C, and the glass microsphere@nickel structure is finally prepared. After the experiment is completed, the material is taken out of the plating tank and cleaned to remove residual impurities.

[0030] The lead plate is inclined in the electrolytic tank and connected to the electrode as a cathode. When the glass microsphere@nickel@lead small balls roll down the inclined plate, the lead ions in the plating solution will form a plating layer on the surface of the glass microsphere@nickel@lead small balls under the action of the electric field. The current density is 1-3 A / dm 2 , the plating temperature is 25-60°C, and the glass microsphere@nickel@lead structure is finally prepared. After the plating is completed, the material is taken out of the plating tank and cleaned to remove residual electrolyte and impurities.

[0031] The tungsten plate is inclined in the electrolytic tank and connected to the electrode as a cathode. When the glass microsphere@nickel@lead@tungsten small balls roll down the inclined plate, the tungsten ions in the plating solution will form a plating layer on the surface of the glass microsphere@nickel@lead@tungsten small balls under the action of the electric field. The current density is 1-2 A / dm 2 , the plating temperature is 25-60°C, and the glass microsphere@nickel@lead@tungsten structure is finally prepared. After the plating is completed, the material is taken out of the plating tank and cleaned to remove residual electrolyte and impurities.

[0032] The tantalum plate is inclined in the electrolytic tank and connected to the electrode as a cathode. When the glass microsphere@nickel@lead@tungsten small balls roll down the inclined plate, the tantalum ions in the plating solution will form a plating layer on the surface of the glass microsphere@nickel@lead@tungsten small balls under the action of the electric field. The current density is 1-2 A / dm 2 , the plating temperature is 450-500°C, and the glass microsphere@nickel@lead@tungsten@tantalum structure is finally prepared. After the plating is completed, the material is taken out of the plating tank and cleaned to remove residual electrolyte and impurities.

[0033] The important parameters of gamma ray shielding are half value layer (HVL), tenth value layer (TVL) and mean free path (MFP). HVL (cm) is a parameter of the thickness of the material required to reduce the initial radiation intensity to half value, TVL (cm) is a parameter of the thickness of the material required to reduce the initial radiation intensity to one tenth value, and MFP (%) is the radiation shielding efficiency. In order to verify the advantages of the shielding material for gamma ray shielding, the present application obtains some gamma ray shielding parameters of the shielding material and shielding parameters of a comparative group (lead ton, tantalum and tungsten) with the same thickness through experiments. It can be observed from the drawing of embodiment 1 that, whether it is HVL or TVL data, the shielding material is the lowest, indicating that the thickness of the shielding material required to reduce the initial radiation intensity to a certain value is the smallest. In addition, the RPE value of the shielding material is also the highest, indicating that its radiation shielding efficiency is the best. All the above indicates the advantages of the shielding performance of the shielding material.

[0034] Embodiment 2:

[0035] The functional layer of the multilayer structure glass microsphere shielding composite material is divided into four layers. The first layer is a metal nickel layer, the second layer is a metal lead layer, the third, fourth and fifth layers are metal tungsten layers, and the sixth, seventh and eighth layers are metal tantalum layers.

[0036] After the glass microspheres are pretreated by pickling and the like, they are immersed in a nickel sulfate plating solution. The nickel ions in the plating solution are reduced to metal nickel on the surface of the glass microspheres and deposited on the sample to form a plating layer. The temperature is 50-70℃, and finally a glass microsphere@nickel structure is prepared. After the electroplating is completed, the material is taken out of the plating tank and cleaned to remove residual impurities.

[0037] The lead plate is inclined in the electrolytic tank and connected to the electrode as a cathode. When the glass microsphere@nickel small balls slide down the inclined plate, the lead ions in the electroplating solution will form a plating layer on the surface of the glass microsphere@nickel small balls under the action of the electric field. The current density is 1-3 A / dm 2 , the electroplating temperature is 18-30℃, and finally a glass microsphere@nickel@lead structure is prepared. After the electroplating is completed, the material is taken out of the electroplating tank and cleaned to remove residual electrolyte and impurities.

[0038] The tungsten plate is inclined in the electrolytic tank and connected to the electrode as a cathode. When the glass microsphere@nickel@lead small balls slide down the inclined plate, the tungsten ions in the electroplating solution will form a plating layer on the surface of the glass microsphere@nickel@lead small balls under the action of the electric field. The current density is 1-2 A / dm 2 , the electroplating temperature is 25-60℃, and the step is repeated three times, and finally a glass microsphere@nickel@lead@tungsten 3 structure is prepared. After the electroplating is completed, the material is taken out of the electroplating tank and cleaned to remove residual electrolyte and impurities.

[0039] The tantalum plate is inclined in the electrolytic cell and connected with the electrode as a cathode. When the glass microspheres-nickel-lead-lead small balls roll down the inclined plate, the tantalum ions in the electroplating solution will form a plating layer on the surface of the glass microspheres-nickel-lead-lead small balls under the action of the electric field, wherein the current density is 1-2 A / dm 2 , the electroplating temperature is 400-450℃, the step is repeated three times, and finally the glass microspheres-nickel-lead-tungsten-3-tantalum-3 structure is prepared. After electroplating is completed, the material is taken out from the electroplating tank and cleaned to remove residual electrolyte and impurities.

[0040] Important parameters of gamma ray shielding include half value layer (HVL), tenth value layer (TVL) and mean free path (MFP). HVL (cm) is a parameter of the thickness of the material required to reduce the initial radiation intensity to half, TVL (cm) is a parameter of the thickness of the material required to reduce the initial radiation intensity to one tenth, and MFP (%) is the radiation shielding efficiency. In order to verify the advantages of the shielding material for gamma ray shielding, the present application obtains some gamma ray shielding parameters of the shielding material and shielding parameters of a comparative group (lead ton, tantalum and tungsten) with the same thickness through experiments. It can be observed from the drawing of Example 1 that, whether it is HVL or TVL data, the shielding material is the lowest, indicating that the thickness of the shielding material required to reduce the initial radiation intensity to a certain value is the smallest. In addition, the RPE value of the shielding material is also the highest, indicating that its radiation shielding efficiency is the best. All the above indicates the advantages of the shielding performance of the shielding material.

Claims

1. A method for preparing a high-irradiation shielding particulate material, characterized in that: The particulate material is composed of glass microspheres, a chemically plated nickel layer, an electroplated lead layer, an electroplated tungsten layer, and an electroplated tantalum layer; the method specifically includes: Step 1: After pretreatment such as acid washing, the glass microspheres are immersed in nickel sulfate plating solution. The nickel ions in the plating solution are reduced to metallic nickel on the surface of the glass microspheres and deposited on the glass microspheres to form a coating. The microspheres are then cleaned to remove any residual impurities. Step 2: Place the lead plate at an angle in the trough and connect it to the electrode as the cathode. Prepare the basic lead carbonate electroplating solution. Then roll the glass microspheres that have been electroless nickel plated in Step 1 down the lead plate to make the reduced lead ions uniformly deposited on its surface. Then clean it to remove residual impurities. Step 3: Place the tungsten plate at an angle in the trough and connect it to the electrode as the cathode. Prepare the sodium tungstate electroplating solution. Then, roll the glass microspheres that have been electrolessly plated with nickel and electroplated with lead in Step 2 down the lead plate to make the reduced tungsten ions uniformly deposited on its surface. Then clean it to remove residual impurities. Step 4: Place the tantalum plate at an angle in the trough and connect it to the electrode as the cathode. Prepare the sodium tantalum fluoride electroplating solution. Then, roll the glass microspheres that have been electrolessly plated with nickel, lead, and tungsten in Step 3 down the lead plate to allow the reduced tantalum ions to be uniformly deposited on its surface. Clean the surface to remove any remaining impurities.

2. The method for preparing a high-irradiation shielding particulate material according to claim 1, characterized in that: The thickness of each layer is controlled at 20μm.

3. The method for preparing a high-irradiation shielding particulate material according to claim 1, characterized in that: The method further includes step five: repeating this step once or multiple times during step two, step three or step four to obtain one or more layers of nickel, tungsten or tantalum, and finally preparing a heterogeneous multilayer core-shell structured microsphere radiation shielding composite material.

4. A method for preparing a high-irradiation shielding particulate material according to claim 1 or 3, characterized in that: In step one, the concentration of the nickel sulfate plating solution is 100~150 g·L. -1 pH 5~5.5, cathode current density 0.5~1 A·dm³ -2 .

5. A method for preparing a high-irradiation shielding particulate material according to claim 1 or 3, characterized in that: In step two, the concentration of the basic lead carbonate electroplating solution is 130~150 g·L. -1 .

6. A method for preparing a high-irradiation shielding particulate material according to claim 1 or 3, characterized in that: In step three, the concentration of the sodium tungstate electroplating solution is 160~210 g·L. -1 .

7. A method for preparing a high-irradiation shielding particulate material according to claim 1 or 3, characterized in that: In step four, the concentration of the sodium tantalum fluoride electroplating solution is 180~220 g·L. -1 .

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