Lightweight lead-based alloy as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of anti-radiation articles, and particularly relates to a light lead-based alloy and a preparation method and application thereof.The light lead-based alloy comprises, by weight, 2.5%-2.7% of tin, 0.015%-0.017% of silver, 0.55%-0.6% of cerium-aluminum alloy, 0.7%-1.0% of copper and the balance lead, and the copper is a sheet copper material. The metal lead is used as an alloy main body, the basic anti-radiation characteristic is reserved, the density of auxiliary material elements is smaller than that of Pb, the alloy density is smaller, the finished product is lighter, meanwhile, the anti-radiation performance is better than that of pure lead, under the combination of the two aspects, the anti-radiation performance is guaranteed, meanwhile, the weight of the needed alloy is reduced by 30% or above, and the load burden of workers is effectively relieved; the wearing comfort and the working efficiency are greatly improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of radiation protection products, and particularly relates to a light lead-based alloy, a preparation method and application thereof. BACKGROUND

[0002] With the wide application of radioactive substances in the fields of medical treatment, industry and scientific research, the demand for radiation protection is increasing. Lead is a core material for protective equipment due to its excellent radiation shielding performance (can effectively absorb X-rays, gamma rays, etc.), especially for manufacturing radiation protection lead clothes. However, the density of pure lead is as high as 11.34 g / cm³, which leads to the excessive weight of lead clothes (such as traditional lead clothes weighing 5-15 kg), and long-term wearing easily causes muscle strain, joint damage and other problems of workers. In addition, in order to meet the protection requirements of high radiation places, the thickness of the lead layer needs to be increased, which further aggravates the wearing burden and reduces the work efficiency and wearing comfort. In order to reduce the weight of the lead clothes, lead and other metal components are currently used to achieve the radiation protection effect to some extent, but the hardness and casting performance of the prepared alloy are general, and the efficiency and safety of the preparation cannot be guaranteed.

[0003] In the prior art, there are researches on light lead-based alloys. For example, patent CN116536539A - a lead-based alloy and its preparation process and application, which reduces the density and improves the mechanical strength by adding aluminum (8-9%), silver, copper, silicon and other elements, although the hardness and casting performance of the alloy are enhanced, but due to the high content of aluminum and the density of aluminum (2.7 g / cm³) is higher than that of other light elements, the overall density of the alloy is reduced limitedly, and long time stirring (3-5h) at high temperature (1080-1100℃) is required in the preparation process, which is high in energy consumption and easy to cause component burning loss, and the flexible processing demand of thin plate is not solved, which is difficult to adapt to the flexible protective layer structure of lead clothes; a non-lead-based light alloy such as patent CN102690979A - a kind of alloy material for light metal handicraft and its preparation method, which takes magnesium as the main body (density 1.6-1.7 g / cm³) and adds aluminum and zinc to improve the strength, but such alloy does not contain lead at all, and the radiation shielding performance is insufficient, which is only suitable for handicraft manufacturing and cannot meet the technical requirements of radiation protection equipment.

[0004] In summary, the existing light lead-based alloy has contradictions in radiation protection efficiency, density optimization and process applicability: the density of aluminum-based alloy is insufficiently reduced and the processing energy consumption is high, and the non-lead-based alloy lacks radiation shielding ability and is difficult to adapt to the flexible thin plate processing technology of lead clothes. Therefore, a new technical solution is needed to solve the above technical problems. SUMMARY

[0005] The present application aims to provide a light lead-based alloy and a preparation method and application, so as to solve the problems of the light lead-based alloy in the prior art, i.e., the contradiction between the radiation protection efficiency, the density optimization and the process applicability, the insufficient reduction of the density of the aluminum-based alloy and the high processing energy consumption, the lack of the radiation shielding ability of the non-lead-based alloy, and the difficulty in adapting to the flexible sheet processing technology of the lead clothing.

[0006] To achieve the above object, the present application provides the following technical scheme: a light lead-based alloy, comprising the following components by weight percentage: tin 2.5-2.7%, silver 0.015-0.017%, cerium-aluminum alloy 0.55-0.6%, copper 0.7-1.0%, and the balance being lead, wherein the copper is sheet copper material, the tin is Sn99.90 with a purity of ≥99.9% and is refined tin, the silver is Ag99.90 with a purity of ≥99.9% and is industrial silver, the cerium-aluminum alloy is CeAl-10 with a cerium content of 9.0-11.0%, the sheet copper material is Cu-CATH-1 with a purity of ≥99.95% and is a powder, and the lead is 994Pb with a content of ≥99.994% and is electrolytic lead.

[0007] The specific steps for preparing the light lead-based alloy according to the above components and formula are as follows: First, the formula amount of lead is weighed and added to a smelting furnace, and the furnace temperature is set to 780℃, and the sheet copper material is preheated beside the furnace; second, the smelting furnace is started to heat and melt the lead, and when the melt temperature reaches 550-600℃, the furnace temperature is set to 600℃, and slag removal is performed; after the slag removal is completed, the furnace temperature is restored to 780℃; when the melt temperature rises to 650℃, the formula amount of silver and tin is added, stirred for 20-40min, and carbon dioxide gas is introduced into the smelting furnace at the same time to reduce the oxygen content in the furnace and reduce the generation of metal oxides; when the melt temperature rises to 750℃, the formula amount of cerium-aluminum alloy is added, and stirred for 15-20min; third, the melt temperature is continuously raised to 1200-1220℃, and the preheated sheet copper is poured into the smelting furnace, and stirred at a medium speed of 20-40Hz; after the stirring is completed, the sample is detected for spectral data, and after the analysis result meets the alloy component requirements, the alloy liquid is obtained; then, the alloy liquid is discharged through the preheated lead conveying pipe, and injected into the mold through the cooling system with a cooling water temperature of 10-25℃ and the lead conveying pump; finally, the formed light lead-based alloy is stacked, weighed, labeled and packed into the warehouse.

[0008] In addition to the above technical scheme, the light lead-based alloy prepared above can also be applied to the radiation protection lead clothing.

[0009] Compared with the prior art, the present application has the following beneficial effects: 1. This invention utilizes the fact that auxiliary elements such as tin, silver, cerium-aluminum alloy, and copper all have lower densities than lead, resulting in a lightweight lead-based alloy with a lower density than pure lead. This significantly reduces the weight of the radiation-protective lead apron, by more than 30%, effectively reducing the burden on workers, greatly improving wearing comfort and work efficiency, while also effectively reducing the amount of precious metals used and lowering production costs. By adding silver and copper, which have excellent electrical conductivity, to the alloy, they act as a harmonizer between the elements and reduce grain boundary formation, thereby improving the alloy's radiation protection performance. Furthermore, by adding cerium to the alloy... Aluminum alloys are used to purify the lead matrix and refine the grains, effectively improving the fatigue strength and extending the service life of the alloy, thus enabling it to maintain stable radiation protection performance during long-term use. By adding tin to the alloy, the fluidity of the alloy is effectively improved, making it easier to fill the mold during die casting and processing, reducing cracks and defects in thin-walled structures, effectively solving the problem of flexible thin-plate processing, improving yield and production efficiency. Through reasonable formulation and process design, the alloy can be easily processed into radiation-proof lead apron components of various shapes and sizes, meeting the needs of flexible thin-plate processing technology. 2. This invention, by precisely controlling the composition of each component of the alloy, helps to optimize the microstructure of the alloy, thereby improving the overall performance of the alloy (such as strength, toughness, corrosion resistance, etc.), making it more suitable for use in radiation-proof lead aprons and extending the service life of the lead aprons. The use of CeAl-10 aluminum alloy with a cerium content of 9.0-11.0% and the synergistic effect of other elements improves the radiation protection performance of the alloy, providing more reliable protection for radiation-proof lead aprons. On this basis, the use of Cu-CATH-1 copper sheet with a purity of ≥99.95% powder improves the electrical and thermal conductivity of the alloy, and the interaction with other elements improves the processing performance of the alloy, making it easier to manufacture parts that meet the shape requirements of radiation-proof lead aprons, and ensuring the comfort and flexibility of the lead aprons during use. 3. The present application adopts staged temperature control (780℃→600℃→780℃→1200℃) and CO2 protective gas, effectively avoiding the problem of high energy consumption caused by long time melting in the existing preparation process. By introducing carbon dioxide gas into the smelting furnace while adding silver and tin, the oxygen content in the furnace is reduced, the generation of metal oxides is reduced, the impurity content in the alloy is effectively reduced, the safety of the preparation process and the purity of the alloy are improved, thereby improving the radiation resistance and mechanical properties of the alloy. At the same time, harmful waste gas emissions are also reduced, meeting environmental protection requirements. By adding preheated sheet copper material into a smelting furnace at 1200-1220℃, the high-temperature stirring time is shortened to minutes, the energy consumption is reduced by more than 40%, the element burning loss rate is 0.5 or less, and by reasonably controlling the stirring frequency, the uniform mixing of each component can be effectively promoted, avoiding the occurrence of local component unevenness, ensuring the performance consistency of the alloy, and being beneficial to produce quality stable radiation protection lead clothes. 4. The lightweight lead-based alloy prepared by the present application has the characteristics of lightweight, high shielding, low energy consumption and flexible processing, and is not only suitable for the production of radiation protection lead clothes, but also can be widely used in other fields requiring radiation protection (such as medical equipment, industrial detection devices, nuclear power facilities, etc.), thereby expanding the application range of lead-based alloys. The radiation protection lead clothes prepared by the lightweight lead-based alloy not only ensures its radiation protection performance, but also has lighter weight and better flexibility, making it more portable and comfortable, and facilitating the user to wear it in various scenes, thereby improving the practicality and market competitiveness of the radiation protection lead clothes. DETAILED DESCRIPTION

[0010] The following examples are used to further illustrate the content of the present application, and do not limit the application of the present application (the following percentages are all weight percentages). Example 1:

[0011] First, tin 2.520%, silver 0.016%, cerium-aluminum alloy 0.502%, copper 0.701%, lead 96.261% are weighed, among which copper is sheet copper material, the grade of tin is Sn99.90 with a purity of ≥99.9% refined tin, the grade of silver is Ag99.90 with a purity of ≥99.9% industrial silver, the grade of cerium-aluminum alloy is CeAl-10 with a cerium content of 9.0-11.0%, the grade of sheet copper material is Cu-CATH-1 with a purity of ≥99.95% powder, and the grade of lead is 994Pb with a content of ≥99.994% electrolytic lead.

[0012] The light-weight lead-based alloy is prepared according to the above selected light-weight lead-based alloy components. The specific light-weight lead-based alloy preparation method is as follows: first, 96.261% lead is added to a smelting furnace, and the furnace temperature is set to 780°C, while 0.701% sheet copper material is preheated beside the furnace; then the smelting furnace is started to heat and melt the lead, when the melt temperature reaches 550-600°C, the furnace temperature is set to 600°C, and slag removal operation is performed; after the slag removal is completed, the furnace temperature is restored to 780°C; when the melt temperature rises to 650°C, 0.016% silver and 2.520% tin are added, stirred for 20-40 min, and carbon dioxide gas is blown into the smelting furnace to reduce the oxygen content in the furnace and reduce the generation of metal oxides; when the melt temperature rises to 750°C, 0.502% cerium-aluminum alloy is added, and stirred for 15-20 min; continue to raise the melt temperature to 1200-1220°C, and preheat the sheet copper and pour it into the smelting furnace, and stir at a medium speed of 20-40 Hz; after the stirring is completed, the sample is detected for spectral data, and after the analysis results meet the alloy component requirements, the alloy liquid is obtained; then, the alloy liquid is discharged through the preheated lead conveying pipe, and injected into the mold through the cooling system with a cooling water temperature of 10-25°C and the lead conveying pump; the formed light-weight lead-based alloy is stacked, weighed, labeled, and packed into the warehouse.

[0013] Then the light-weight lead-based alloy prepared above is used as a matrix in the radiation-proof lead clothes.

[0014] Before preparing the radiation-proof lead clothes, the light-weight lead-based alloy prepared above is pressure cast into a lead plate sample with a thickness of 1.0 mm, and then cut into 500 mm x 500 mm and 100 mm x 100 mm sizes, and the equivalent Pb value of the alloy plate is detected according to the test method of GB Z / T147-2002, and the measured equivalent value is 1.31 mm Pb. Example 2:

[0015] First, 2.610% tin, 0.015% silver, 0.564% cerium-aluminum alloy, 0.807% copper, and 96.004% lead are weighed, wherein the copper is sheet copper material, the tin is Sn99.90 with a purity of ≥99.9% refined tin, the silver is Ag99.90 with a purity of ≥99.9% industrial silver, the cerium-aluminum alloy is CeAl-10 with a cerium content of 9.0-11.0%, the sheet copper material is Cu-CATH-1 with a purity of ≥99.95% powder, and the lead is 994Pb with a content of ≥99.994% electrolytic lead.

[0016] A lightweight lead-based alloy was then prepared based on the selected lightweight lead-based alloy components. The specific preparation method for the lightweight lead-based alloy is as follows: First, 96.004% lead was added to the melting furnace and the furnace temperature was set to 780℃. Simultaneously, 0.807% copper sheet was placed near the furnace for preheating. Then, the melting furnace was started to heat and melt the lead. When the melt temperature reached 550–600℃, the furnace temperature was adjusted to 600℃ for slag removal. After slag removal, the furnace temperature was restored to 780℃. When the melt temperature reached 650℃, 0.015% silver and 2.610% tin were added, and the mixture was stirred for 20–40 minutes. Simultaneously, carbon dioxide gas was introduced into the melting furnace to reduce the oxygen content and decrease the metal oxygen content. The formation of the alloy; when the melt temperature rises to 750℃, add 0.564% cerium-aluminum alloy and stir for 15-20 minutes; continue to raise the melt temperature to 1200-1220℃, put the preheated copper sheet into the melting furnace, and stir at a medium speed of 20-40Hz; after stirring is completed, take a sample to detect the spectral data, and obtain the alloy liquid after the analysis results meet the requirements of the alloy composition; then, discharge the alloy liquid through a preheated lead conveying pipe, and inject it into the mold through a cooling system with a cooling water temperature of 10-25℃ and a lead conveying pump to form the alloy; stack, weigh, label, and pack the formed lightweight lead-based alloy into the warehouse.

[0017] The lightweight lead-based alloy obtained above is then used as a matrix in radiation-proof lead aprons.

[0018] Before preparing the radiation-proof lead apron, the prepared lightweight lead-based alloy needs to be die-cast into lead plate samples with a thickness of 1.0 mm, and then cut into 500 mm × 500 mm and 100 mm × 100 mm sizes. The equivalent Pb value of the alloy plate is tested according to the test method of GB Z / T147-2002, and the measured equivalent value is 1.38 mmPb. Example 3:

[0019] First, weigh out 2.690% tin, 0.017% silver, 0.598% cerium-aluminum alloy, 0.989% copper, and 95.706% lead. The copper is copper sheet, the tin is refined tin with a grade of Sn99.90 and a purity of ≥99.9%, the silver is industrial silver with a grade of Ag99.90 and a purity of ≥99.9%, the cerium-aluminum alloy is CeAl-10 with a cerium content of 9.0-11.0%, the copper sheet is copper powder with a grade of Cu-CATH-1 and a purity of ≥99.95%, and the lead is electrolytic lead with a grade of 994Pb and a content of ≥99.994%.

[0020] A lightweight lead-based alloy was then prepared based on the selected lightweight lead-based alloy components. The specific preparation method for the lightweight lead-based alloy is as follows: First, 95.706% lead was added to the melting furnace and the furnace temperature was set to 780℃. Simultaneously, 0.989% copper sheet was placed near the furnace for preheating. Then, the melting furnace was started to heat and melt the lead. When the melt temperature reached 550–600℃, the furnace temperature was adjusted to 600℃ for slag removal. After slag removal, the furnace temperature was restored to 780℃. When the melt temperature reached 650℃, 0.017% silver and 2.690% tin were added, and the mixture was stirred for 20–40 minutes. Simultaneously, carbon dioxide gas was introduced into the melting furnace to reduce the oxygen content and decrease the metal oxygen content. The formation of the alloy; when the melt temperature rises to 750℃, add 0.598% cerium-aluminum alloy and stir for 15-20 minutes; continue to raise the melt temperature to 1200-1220℃, put the preheated copper sheet into the melting furnace, and stir at a medium speed of 20-40Hz; after stirring is completed, take a sample to detect the spectral data, and obtain the alloy liquid after the analysis results meet the requirements of the alloy composition; then, discharge the alloy liquid through a preheated lead conveying pipe, and inject it into the mold through a cooling system with a cooling water temperature of 10-25℃ and a lead conveying pump to form the alloy; stack, weigh, label, and pack the formed lightweight lead-based alloy into the warehouse.

[0021] The lightweight lead-based alloy obtained above is then used as a matrix in radiation-proof lead aprons.

[0022] Before preparing the radiation-proof lead apron, the prepared lightweight lead-based alloy needs to be die-cast into lead plate samples with a thickness of 1.0 mm, and then cut into 500 mm × 500 mm and 100 mm × 100 mm sizes. The equivalent Pb value of the alloy plate is tested according to the test method of GB Z / T147-2002, and the measured equivalent value is 1.47 mmPb.

[0023] The following is a statistical table of the component ratios and equivalent Pb values ​​of lead plate samples tested in Examples 1-3: ; As shown in the table above, the radiation protection performance of this invention is superior to that of pure lead. Furthermore, since silver and copper have excellent electrical conductivity, and radiation protection performance is directly proportional to the conductivity of the alloy, the higher the proportion of silver and copper, the better the radiation protection performance. Therefore, this invention uses metallic lead as the main alloy, retaining the basic characteristics of radiation protection. The density of the auxiliary elements is lower than that of Pb, resulting in a lower alloy density and a lighter finished product. At the same time, the radiation protection performance is superior to that of pure lead. By combining these two aspects, the required alloy weight is reduced by more than 30% while ensuring radiation protection performance, effectively reducing the burden on workers and greatly improving wearing comfort and work efficiency.

Claims

1. A lightweight lead-based alloy, characterized in that, It comprises the following components by weight percentage: tin 2.5-2.7%, silver 0.015-0.017%, cerium-aluminum alloy 0.55-0.6%, copper 0.7-1.0%, and the balance being lead, wherein the copper is sheet copper.

2. The lightweight lead-based alloy according to claim 1, characterized in that, The tin is of grade Sn99.90 and has a purity of ≥99.9%.

3. The lightweight lead-based alloy according to claim 1, characterized in that, The silver is industrial silver with the grade Ag99.90 and a purity of ≥99.9%.

4. A lightweight lead-based alloy according to claim 1, characterized in that, The grade of the cerium-aluminum alloy is CeAl-10, wherein the cerium content is 9.0 to 11.0%.

5. A lightweight lead-based alloy according to claim 1, characterized in that, The copper sheet material is of grade Cu-CATH-1 and is a powder with a purity of ≥99.95%.

6. A lightweight lead-based alloy according to claim 1, characterized in that, The lead is electrolytic lead with a grade of 994Pb and a content of ≥99.994%.

7. A method for preparing a lightweight lead-based alloy according to any one of claims 1-6, characterized in that, The specific steps are as follows: First, weigh the required amount of lead, add it to the smelting furnace and set the furnace temperature to 780℃, while simultaneously preheating the copper sheet next to the furnace; second, The smelting furnace is started to heat and melt the lead. When the melt temperature reaches 550-600℃, the furnace temperature is set to 600℃ for slag removal. After slag removal, the furnace temperature is restored to 780℃. When the melt temperature rises to 650℃, the prescribed amounts of silver and tin are added and stirred for 20-40 minutes. When the melt temperature rises to 750℃, the prescribed amounts of cerium-aluminum alloy are added and stirred for 15-20 minutes. Next, the melt temperature is raised to 1200-1220℃, and the preheated copper sheets are added to the smelting furnace and stirred at a medium speed. After stirring, the spectral data is sampled and analyzed. Once the analysis results meet the alloy composition requirements, the alloy liquid is obtained. Then, the alloy liquid is discharged through a preheated lead conveying pipe and injected into a mold through a cooling system with a cooling water temperature of 10-25℃ and a lead pump to form the alloy. Finally, the formed lightweight lead-based alloy is stacked, weighed, labeled, and packaged for storage.

8. The method for preparing a lightweight lead-based alloy according to claim 7, characterized in that, While the silver and tin are being added to the smelting furnace, carbon dioxide gas is introduced into the furnace to reduce the oxygen content and decrease the formation of metal oxides.

9. The method for preparing a lightweight lead-based alloy according to claim 7, characterized in that, The stirring frequency for the medium speed is 20–40 Hz.

10. The application of a lightweight lead-based alloy as described in any one of claims 1-6 in a radiation-proof lead apron.