Radiation resistant rubber glove with antibacterial properties and method of making

Abstract

The application provides an anti-radiation rubber glove with antibacterial properties and a preparation method thereof, and belongs to the technical field of radiation protection. The preparation method comprises the following steps: dispersing a silicon-based functional carrier, a core-shell heterogeneous gradient structure anti-ionizing radiation powder, a tungsten-based shielding agent, a bismuth-based shielding agent and a silver ion antibacterial agent in latex, and then performing dip forming to obtain the glove. The silicon-based functional carrier is silica loaded with gadolinium oxide and cerium oxide on the surface; the core-shell heterogeneous gradient structure anti-ionizing radiation powder has a core layer and at least one shell layer, and the atomic numbers of the core layer and the shell layer are in a gradient decreasing distribution. The application utilizes the synergistic effect of gadolinium oxide and cerium oxide, combines the hierarchical absorption and multiple scattering effect of the core-shell heterogeneous gradient structure, and is supplemented by the strong absorption capacity of the tungsten and bismuth-based shielding agents to high-energy rays, so that smooth and efficient protection in a wide energy spectrum range of 30-150 keV is realized.

Description

Technical Field

[0001] This application relates to the field of radiation protection technology, specifically to a radiation-resistant rubber glove with antibacterial properties and its preparation method. Background Technology

[0002] Most existing nuclear radiation protective materials and gloves are made of lead-containing rubber, posing certain health risks to wearers due to prolonged contact with lead. Furthermore, nuclear radiation protective gloves cannot provide long-term reliable protection in harsh environments such as strong acids, alkalis, greases, and strong radiation. Additionally, the excellent airtightness and impermeability of nuclear radiation protective gloves make them prone to the growth of various bacteria and viruses on the inner surface, posing additional health threats to users. Therefore, there is an urgent need to develop a lead-free radiation protective glove that combines high-efficiency protection, antibacterial properties, and wearing comfort.

[0003] Existing technology discloses a multi-layered radiation-proof glove with antiviral properties, using bismuth oxide, tungsten oxide, and lead compounds as shielding fillers, and adding GS5 antibacterial agent to achieve antiviral function. However, this technical solution has the following shortcomings: First, the use of a single shielding mechanism results in absorption troughs in the protective effect across a wide energy spectrum, making it difficult to achieve stable protection across the entire spectrum; second, the continued use of lead compounds poses a risk of heavy metal migration; third, silica is only used as a common filler, failing to fully utilize its potential as a functional carrier; and fourth, the antibacterial effect needs further improvement. Summary of the Invention

[0004] In view of the technical problems existing in the background art, this application provides a radiation-proof rubber glove with antibacterial properties and its preparation method. By introducing cerium oxide and gadolinium oxide to form a dual rare earth synergistic system, and using silicon dioxide as a functional carrier to load rare earth elements, a broad-spectrum and efficient protection is achieved, while giving the glove excellent antibacterial properties.

[0005] This application provides a method for preparing radiation-resistant rubber gloves with antibacterial properties, comprising the following steps: S1. Add 2-5 parts of silicone defoamer and 2-5 parts of OP-10 emulsifier to 100 parts of natural latex with a solid content of 30-60%, and stir and disperse thoroughly to obtain a mixture. S2, add 2-20 parts of silicon-based functional carrier to the mixture obtained in step S1; the silicon-based functional carrier is silicon dioxide with gadolinium oxide and cerium oxide loaded on its surface; S3, add 10-40 parts of core-shell heterogeneous gradient structure anti-ionizing radiation powder, 3-25 parts of tungsten-based shielding agent, and 3-25 parts of bismuth-based shielding agent to the mixture obtained in step S2, stir and disperse thoroughly, and set aside for later use; the core material of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is bismuth oxide, and the shell material of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is gadolinium oxide and titanium dioxide; S4. Add 0.5-5 parts of silver ion antibacterial agent and 1-3 parts of carbon black colorant to the mixture obtained in step S3, and stir to obtain the impregnation solution. S5, preparing gloves by impregnation: Immerse the hand mold in the impregnation solution prepared in step S4, then dry, vulcanize, and demold to obtain radiation-resistant rubber gloves with antibacterial properties.

[0006] Furthermore, the preparation method of the silicon-based functional carrier is as follows: nano-silica is dispersed in a solution containing gadolinium salt and cerium salt, and after precipitation and calcination, gadolinium oxide and cerium oxide nanoparticles are generated in situ on the surface of silica.

[0007] Furthermore, the mass ratio of gadolinium oxide to cerium oxide on the surface of the silicon-based functional carrier is 1:3 to 3:1.

[0008] Furthermore, the tungsten-based shielding agent is at least one of tungsten oxide and tungstate.

[0009] Furthermore, the bismuth-based shielding agent is at least one of bismuth oxide and bismuthate.

[0010] Furthermore, in steps S2, S3, and S4, the mixture is circulated and stirred through a U-shaped tube circulation system.

[0011] Furthermore, the circulation velocity of the U-shaped tube circulation system is 0.5-5 m / s, and the circulation time is 30-120 minutes.

[0012] This application also provides a radiation-proof rubber glove with antibacterial properties, which is prepared by the preparation method described in any of the foregoing technical solutions. The radiation-proof rubber glove with antibacterial properties can achieve stable and efficient protection in a wide energy spectrum range of 30-150 keV, and the antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans all reach more than 99%.

[0013] The beneficial effects of this application are as follows: 1. This application proposes a method for preparing radiation-proof rubber gloves with antibacterial properties. Utilizing the synergistic effect of gadolinium oxide and cerium oxide (two rare earth elements), combined with the hierarchical absorption and multiple scattering effects of core-shell heterogeneous gradient structure powders, and supplemented by the strong absorption capabilities of tungsten-based shielding agents (such as tungsten oxide and tungstate) and bismuth-based shielding agents (such as bismuth oxide and bismuthate) for high-energy radiation, stable and efficient protection is achieved within a broad energy spectrum range of 30-150 keV, significantly superior to single-shielding systems. Tungsten and bismuth, with their high atomic numbers and electron densities, exhibit excellent shielding performance against highly penetrating medium- and high-energy X / γ rays. Their complementary energy spectrum with the two rare earth elements further broadens the energy spectrum range for efficient protection and eliminates absorption troughs.

[0014] Specifically, this method fully utilizes the complementarity of gadolinium oxide (heavy rare earth) and cerium oxide (light rare earth) at the K absorption edge. Gadolinium oxide has a K absorption edge of approximately 50.2 keV, exhibiting high absorption efficiency for medium- and high-energy X / γ rays; cerium oxide has a K absorption edge of approximately 40.4 keV, demonstrating excellent absorption for low-energy rays. When the two are combined in a specific ratio, a continuous high absorption region can be formed over a broad energy spectrum range of 30-150 keV, overcoming the absorption trough near the K absorption edge of a single shielding agent and achieving stable protection across the entire spectrum.

[0015] The introduction of core-shell heterogeneous gradient structure powders, featuring a heterogeneous core and shell design, allows for a gradient distribution of core and shell materials in terms of atomic number, electron density, or X-ray absorption capacity. This enables graded absorption and multiple scattering of X-rays of varying energies, further enhancing shielding effectiveness. Simultaneously, the shell effectively prevents direct contact between highly reactive shielding elements and the rubber matrix, preventing adverse reactions such as catalytic degradation and extending glove lifespan.

[0016] 2. This application upgrades silica from a traditional "filler" to a "functional carrier." By in-situ generating gadolinium oxide and cerium oxide nanoparticles on the silica surface, a composite structure is formed with silica as the core and rare earth oxides as the shell. On the one hand, the high specific surface area and abundant surface hydroxyl groups of silica provide an ideal platform for the uniform loading of rare earth elements, effectively suppressing the self-agglomeration of powders under high filling amounts and achieving molecular-level dispersion of rare earth elements in the latex system. On the other hand, the gadolinium oxide and cerium oxide nanoparticles loaded on the silica surface serve as a functional interface in direct contact with the rubber matrix. Their abundant active sites can form physical entanglements, hydrogen bonds, or coordination bonds with rubber molecular chains, thereby significantly enhancing the interfacial bonding force between the functional powder and the rubber matrix. This structural design not only solves the industry problem of powder agglomeration but also significantly improves the mechanical properties of the composite material, enabling the gloves to possess both excellent shielding and mechanical properties.

[0017] 3. The radiation-proof rubber gloves prepared by the dip-molding process of this application have a dense and uniform rubber film, which gives the gloves excellent oil-proof, acid-proof, alkali-proof, impermeable and tear-proof properties, and can meet the long-term reliable use requirements in harsh environments such as strong acid, strong alkali, oil and strong radiation.

[0018] 4. The silver ion antibacterial agent added in this application can effectively inhibit the growth of bacteria and viruses, and the antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans all reach more than 99%, thus improving the hygiene performance of gloves.

[0019] 5. This application adopts a U-shaped tube circulating mixing system, which enables the material to form a continuous circulating flow in the tube, solving the problem of uneven sedimentation and dispersion of high-density functional fillers in latex, and ensuring the performance stability of the product.

[0020] 6. This application completely eliminates lead and its compounds, avoiding the risk of heavy metal migration, while also being soft to the touch and comfortable to wear.

[0021] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0023] Figure 1 This is a schematic diagram of the U-shaped tube circulating mixing system in this application.

[0024] Figure 2 SEM image of the surface of the antibacterial radiation-resistant rubber glove prepared in Example 1.

[0025] Figure 3 A photograph of the antibacterial radiation-resistant rubber gloves prepared in Example 1.

[0026] Figure 4 This is a TEM image of the silicon-based functional carrier prepared in Example 1. Detailed Implementation

[0027] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0029] Please see Figures 1 to 3 As shown in the figure, this application provides a method for preparing radiation-resistant rubber gloves with antibacterial properties, including the following steps: S1. Add 2-5 parts of silicone defoamer and 2-5 parts of OP-10 emulsifier to 100 parts of natural latex with a solid content of 30-60%, and stir and disperse thoroughly to obtain a mixture; S2, add 2-20 parts of silicon-based functional carrier to the mixture obtained in step S1; the silicon-based functional carrier is silicon dioxide with gadolinium oxide and cerium oxide loaded on its surface; The preparation method of the silicon-based functional carrier is as follows: nano-silica is dispersed in a solution containing gadolinium salt and cerium salt, and then precipitated and calcined to allow gadolinium oxide and cerium oxide nanoparticles to be generated in situ on the surface of the silica. The mass ratio of gadolinium oxide to cerium oxide on the surface of the silicon-based functional carrier is 1:3 to 3:1. Preferably, it is 1:2 to 2:1, and more preferably, it is 1:1.

[0030] S3, add 10-40 parts of core-shell heterogeneous gradient structure anti-ionizing radiation powder, 3-25 parts of tungsten-based shielding agent, and 3-25 parts of bismuth-based shielding agent to the mixture obtained in step S2, stir and disperse thoroughly, and set aside for later use; Among them, the tungsten-based shielding agent is at least one of tungsten oxide and tungstate.

[0031] Bismuth-based shielding agents are at least one of bismuth oxide and bismuth salts.

[0032] The core-shell heterogeneous gradient structure anti-ionizing radiation powder has a core layer and at least one shell layer covering the surface of the core layer. The atomic number of the core layer material and the shell layer material of the core-shell heterogeneous gradient structure anti-ionizing radiation powder are distributed in a gradient decreasing manner.

[0033] The core layer material of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is bismuth oxide.

[0034] The shell material of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is gadolinium oxide and titanium dioxide.

[0035] S4. Add 0.5-5 parts of silver ion antibacterial agent and 1-3 parts of carbon black colorant to the mixture obtained in step S3, and stir to obtain the impregnation solution. S5, preparing gloves by impregnation: Immerse the hand mold in the impregnation solution prepared in step S4, then dry, vulcanize, and demold to obtain radiation-resistant rubber gloves with antibacterial properties.

[0036] In steps S2, S3, and S4, the mixture is circulated and stirred through a U-shaped tube circulation system. The U-shaped tube circulation system causes the material to circulate within the tube, achieving uniform dispersion.

[0037] The circulation velocity of the U-tube circulation system is 0.5-5 m / s, and the circulation time is 30-120 minutes.

[0038] This application also provides an antibacterial radiation-proof rubber glove, prepared using the above-described method. The glove has a lead equivalent of 0.139-0.291 mmPb over a broad energy spectrum range of 30-150 keV; its antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans all exceed 99%; its tensile strength is 18.2-24.5 MPa, its elongation at break is 520%-980%, and its hardness is 65-76 Shore A. This glove is lead-free, environmentally friendly, lightweight, and soft, and can be widely used in medical, nuclear industry, and industrial testing fields.

[0039] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0040] The preparation process of silicon-based functional carriers is as follows: Twenty parts of nano-silica (30 nm particle size) were dispersed in a mixed solution containing gadolinium nitrate and cerium nitrate. The pH was adjusted to 8-9, and the precipitation reaction was carried out for 2 hours. After filtration and washing, the silica functional carrier with gadolinium oxide and cerium oxide loaded on its surface was obtained. Figure 4 This is a TEM image of the prepared silicon-based functional carrier.

[0041] As can be seen, the Si element highlighted in red is mainly distributed in the core region of the particles, while the Gd element highlighted in yellow and the Ce element highlighted in green are mainly distributed in the surface region of the particles. Because the Gd and Ce elements distributed on the particle surface cover the Si elements in the core region, some Si signals are blocked; however, this precisely confirms the core-shell structure characteristics of rare earth oxides coating the surface of silicon dioxide.

[0042] Functional carriers with different Gd / Ce ratios can be obtained by adjusting the ratio of gadolinium nitrate to cerium nitrate.

[0043] The preparation process of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is as follows: (1) Core layer preparation: Dissolve 0.02 mol bismuth nitrate pentahydrate in 100 mL of deionized water, and add 1 mol / L dilute nitric acid dropwise until the solution is just clear. Then add 0.3 mol urea and stir until completely dissolved to obtain the precursor solution. Place the precursor solution in an 80°C constant temperature water bath and stir continuously for 2 hours to allow the urea to slowly hydrolyze and release OH-. - Bi 3+ A white precipitate was obtained by uniform precipitation; the white precipitate was washed three times each by centrifugation with deionized water and anhydrous ethanol, and dried at 80℃ for 12 hours; the dried powder was placed in a muffle furnace and heated to 500℃ at a heating rate of 5℃ / min, held at that temperature for 2 hours, and ground after natural cooling to obtain yellow Bi2O3 core particles.

[0044] (2) Shell covering: ① First shell layer gadolinium oxide coating: Take 0.01 mol of Bi2O3 powder obtained in step (1), add it to 150 mL of a mixed solvent of anhydrous ethanol / deionized water with a volume ratio of 1:1, and ultrasonically disperse for 30 minutes to form suspension A; dissolve 0.005 mol of gadolinium nitrate hexahydrate in 20 mL of deionized water to obtain solution B; under vigorous stirring, slowly add solution B to suspension A, and then add concentrated ammonia water with a mass concentration of 25%~28% dropwise to adjust the pH of the system to 9~10, and continue to stir the reaction at 60℃ for 3 hours; after centrifugation, water washing and alcohol washing, the product is dried at 80℃ and placed in a muffle furnace, heated to 600℃ at 5℃ / min, and calcined for 3 hours to obtain Bi2O3@Gd2O3 core-shell particles.

[0045] ② Second shell titanium dioxide coating: The Bi2O3@Gd2O3 powder prepared in ① was ultrasonically dispersed in 100 mL of anhydrous ethanol to obtain suspension C; 5 mL of tetrabutyl titanate was dissolved in 30 mL of anhydrous ethanol to obtain solution D; 10 mL of anhydrous ethanol, 0.5 mL of deionized water and 0.3 mL of concentrated ammonia were mixed evenly to obtain hydrolysis promoting solution E; under vigorous stirring at 40℃, solution D was added dropwise to suspension C, and stirred for 30 minutes to allow tetrabutyl titanate to be fully adsorbed, and then solution E was added dropwise. After the addition was completed, the temperature was raised to 60℃ and the reaction was continued for 3 hours; the product was centrifuged, washed three times with anhydrous ethanol, dried at 80℃, and placed in a muffle furnace, heated to 500℃ at 2℃ / min, and calcined for 2 hours to obtain Bi2O3@Gd2O3@TiO2 core-shell heterogeneous gradient anti-ionizing radiation powder. Among them, the atomic number of bismuth oxide, the core material, is higher than that of gadolinium oxide and titanium dioxide, the shell materials, forming a gradient decreasing distribution.

[0046] Example 1 This embodiment provides a method for preparing radiation-resistant rubber gloves with antibacterial properties, including the following steps: S1. Add 2 parts of silicone defoamer and 2 parts of OP-10 emulsifier to 100 parts of natural latex with a solid content of 30%, and stir and disperse at 6000 r / min for 0.5 h to obtain a mixture.

[0047] S2, take 10 parts of the silicon-based functional carrier prepared above and add them to the mixture obtained in step S1, and circulate and stir for 1 hour through a U-tube circulation system (circulation flow rate 2m / s); in the silicon-based functional carrier, Gd:Ce=1:1, and the mass fraction of rare earth in the silicon-based functional carrier is 67%.

[0048] S3, add 20 parts of the core-shell heterogeneous gradient structure anti-ionizing radiation powder, 5 parts of tungsten oxide, and 5 parts of bismuth oxide prepared above to the mixture obtained in step S2, and circulate and stir for 1 hour through a U-tube circulation system (circulation flow rate 2m / s).

[0049] S4. Add 2 parts of DOW silver ion antibacterial agent and 2 parts of carbon black colorant to the mixture obtained in step S3, and circulate and stir for 0.5 hours through a U-tube circulation system (circulation flow rate 1m / s) to obtain the impregnation solution. S5, preparing gloves by impregnation: Immerse a clean hand mold in the impregnation solution prepared in step S4, leave it for 30 seconds, and slowly remove it; dry it in an oven at 65℃ for 1 hour; then vulcanize it at 130℃ for 45 minutes; after demolding, obtain radiation-resistant rubber gloves with antibacterial properties.

[0050] Please see Figure 1 As shown, the U-shaped tube circulating mixing system used in this application includes a U-shaped circulating tube 1, a material inlet 2, a material outlet 3 located at the bottom of the U-shaped circulating tube 1, and a circulating pump 4. The U-shaped circulating tube 1 is hollow inside, and this hollow area is the functional packing dispersion area.

[0051] During the stirring and dispersion processes in steps S2, S3, and S4, the mixture is uniformly dispersed in the following ways: First, the latex mixture containing functional fillers (including silicon-based functional carriers, core-shell heterogeneous gradient structure anti-ionizing radiation powders, tungsten-based shielding agents, bismuth-based shielding agents, etc.) is pumped from material inlet 2 into U-shaped circulation pipe 1. Circulation pump 4 is then started to create a continuous and stable circulation flow of the latex mixture within U-shaped circulation pipe 1.

[0052] During the circulation process, the latex mixture flows through the functional filler dispersion zone. This zone utilizes the special geometry of the U-shaped circulation pipe 1 to generate strong turbulence and shearing action in the fluid, thereby uniformly dispersing the high-density functional filler in the latex system.

[0053] Specifically, when the latex mixture circulates in the U-shaped circulation pipe 1, the high-density functional filler tends to settle under gravity. However, due to the continuous power provided by the circulation pump 4, the latex mixture always remains in a flowing state, and the filler particles are carried by the fluid, forming a suspended dispersion system in the pipe.

[0054] The bend in the U-shaped circulation pipe 1 alters the flow direction of the fluid, generating local vortices that further enhance the shearing and dispersing effect on the packing agglomerates.

[0055] By controlling the circulation flow rate to 0.5-5 m / s and the circulation time to 30-120 minutes, it can be ensured that all filler particles are fully dispersed and evenly distributed in the latex during the circulation process.

[0056] After being processed by the U-shaped tube circulating mixing system, the mixture is discharged from material outlet 3 and directly used in the subsequent impregnation molding process. This system effectively solves the technical problem of rapid sedimentation of high-density functional fillers (such as bismuth oxide, tungsten oxide, core-shell powders with densities as high as 7-9 g / cm³) in latex due to gravity, and avoids the problems of uneven filler distribution and large performance fluctuations between product batches in traditional mixing processes.

[0057] Figure 2 This is a SEM image of the glove surface prepared in this embodiment. As can be seen from the image, the glove surface is smooth and dense, with functional filler particles uniformly embedded in the film, and no obvious agglomerates.

[0058] Example 2 The difference from Example 1 is that 10 portions of a silicon-based functional carrier with a Gd:Ce ratio of 2:1 are used in step S2. The remaining steps are the same as in Example 1.

[0059] Example 3 The difference from Example 1 is that in step S2, 10 portions of a silicon-based functional carrier with a Gd:Ce ratio of 1:2 are used. The remaining steps are the same as in Example 1.

[0060] Example 4 The difference from Example 1 is that in step S2, 10 portions of a silicon-based functional carrier with a Gd:Ce ratio of 3:1 are used. The remaining steps are the same as in Example 1.

[0061] Example 5 The difference from Example 1 is that in step S2, 10 portions of a silicon-based functional carrier with a Gd:Ce ratio of 1:3 are used. The remaining steps are the same as in Example 1.

[0062] Example 6 The difference from Example 1 is that in step S2, 15 parts of a silicon-based functional carrier with a Gd:Ce ratio of 1:1 are used, and in step S3, 15 parts of the core-shell heterogeneous gradient structure anti-ionizing radiation powder are used. The remaining steps are the same as in Example 1.

[0063] Comparative Example 1 The difference from Example 1 is that in step S2, 10 parts of silica with gadolinium oxide and cerium oxide loaded on the surface are replaced with 10 parts of unloaded nano-silica. The remaining steps are the same as in Example 1.

[0064] Comparative Example 2 The difference from Example 1 is that in step S2, 10 parts of a silica functional carrier loaded only with gadolinium oxide (total rare earth content of about 6.7 parts) are used, and cerium oxide is not added. The remaining steps are the same as in Example 1.

[0065] Comparative Example 3 The difference from Example 1 is that in step S2, 10 parts of a silica functional carrier loaded only with cerium oxide (total rare earth content of about 6.7 parts) are used, and gadolinium oxide is not added. The remaining steps are the same as in Example 1.

[0066] Comparative Example 4 The difference from Example 1 is that in step S3, the amount of the core-shell heterogeneous gradient structure anti-ionizing radiation powder is 30 parts, and tungsten oxide and bismuth oxide are not added. The remaining steps are the same as in Example 1.

[0067] Comparative Example 5 The difference from Example 1 is that in step S3, the core-shell heterogeneous gradient structure anti-ionizing radiation powder is not added, and the amounts of tungsten oxide and bismuth oxide are increased to 15 parts and 15 parts respectively (total 30 parts). The remaining steps are the same as in Example 1.

[0068] Comparative Example 6 The difference from Example 1 is that the U-tube circulation system is not used in steps S2, S3, and S4; instead, stirring is carried out in a regular stirred tank at 6000 r / min. The remaining steps are the same as in Example 1.

[0069] Comparative Example 7 The difference from Example 1 is that the silicon-based functional carrier, core-shell heterogeneous gradient structure anti-ionizing radiation powder, tungsten oxide, bismuth oxide, antibacterial agent, and carbon black colorant are added to the latex all at once, and only ordinary high-speed stirring is used for 60 minutes, without U-tube circulation treatment. The amount of other raw materials is the same as in Example 1.

[0070] Comparative Example 8 The difference from Example 1 is that in steps S2 and S3, equal masses of 300-mesh lead powder are used to replace all rare earth elements, the core-shell heterogeneous gradient structure anti-ionizing radiation powder (hereinafter referred to as core-shell powder), tungsten shielding agent, and bismuth shielding agent. The remaining steps are the same as in Example 1.

[0071] The gloves prepared in the above embodiments and comparative examples were subjected to performance tests.

[0072] 1. Shielding performance test The prepared radiation-proof rubber gloves were tested for ionizing radiation according to the method disclosed in YY / T 0292.1-2020 "Medical Diagnostic X-ray Radiation Protection Apparatus Part 1: Determination of Material Attenuation Performance". The X-ray tube voltage was 50kV and 100kV. Lead equivalent refers to the lead layer thickness corresponding to the shielding effect of a lead plate of a certain thickness at a specific X-ray energy. Radiation protection tests were conducted according to the method disclosed in GBZ / T 147-2002 "Determination of Attenuation Performance of X-ray Protective Materials". The X-ray energy was set to 50 keV and 100 keV to examine the shielding performance of the gloves at different energy levels. The test results are shown in Table 1.

[0073] Table 1 As can be seen from the data in Table 1, the lead equivalent of the dual rare earth composite sample at the energy points of 50 keV and 100 keV is significantly higher than that of the single rare earth sample. This indicates that gadolinium oxide has high absorption efficiency for medium and high energy rays, while cerium oxide has excellent absorption for low energy rays. The combination of the two can achieve stable and efficient protection over a wide energy spectrum. Among them, Example 2, with a gadolinium oxide to cerium oxide mass ratio of 2:1, has lead equivalents of 0.214 mmPb and 0.217 mmPb at 50 keV and 100 keV, respectively, while Example 3, with a mass ratio of 1:2, has lead equivalents of 0.242 mmPb and 0.237 mmPb, respectively. The values ​​at the two energy points are the closest and represent the preferred ratio. Comparing Example 1 with added core-shell powder to Comparative Example 5 without added core-shell powder, Example 1 showed lead equivalents of 0.262 mmPb and 0.291 mmPb at 50 keV and 100 keV, respectively, representing increases of 20.2% and 41.3% compared to Comparative Example 5. This demonstrates that the core-shell heterogeneous gradient structure significantly enhances shielding effectiveness. The mechanism lies in the atomic number gradient distribution between the core and shell layers, which enables graded absorption and multiple scattering of rays of different energies. Example 1, employing a U-tube circulating mixing system and a stepwise feeding process, exhibited a lead equivalent value far exceeding that of Comparative Examples 6 and 7 without this process. This indicates that uniform dispersion is crucial for ensuring shielding performance. This is because the U-tube circulating system generates strong turbulence and shearing through forced circulation, effectively solving the technical challenge of rapid sedimentation of high-density fillers in latex.

[0074] 2. Mechanical property testing The mechanical properties of the radiation-proof gloves were tested using a universal testing machine, and the results are shown in Table 2.

[0075] Table 2 As shown in Table 2, Example 1 with added core-shell powder achieved a tensile strength of 24.5 MPa and an elongation at break of 980%, representing increases of 40.0% and 104.2% respectively compared to Comparative Example 5 without added core-shell powder. This indicates that the core-shell structure not only enhances shielding effectiveness but also significantly improves the mechanical properties of the material. The mechanism lies in the good compatibility between the shell material and the rubber matrix, enabling physical entanglement or chemical cross-linking with the rubber molecular chains. This allows stress to be effectively transferred from the shell to the core layer, while the core-shell interface hinders crack propagation. The addition of rare earth fillers also plays a reinforcing role. The tensile strength of Comparative Example 1 without rare earth fillers was 17.2 MPa, while the tensile strengths of Examples 1 to 3 ranged from 18.2 to 24.5 MPa. This is because gadolinium oxide and cerium oxide nanoparticles have high surface activity, enabling them to form physical adsorption or chemical bonds with the rubber molecular chains, acting as physical cross-linking points in the rubber matrix. Example 1, which uses a U-tube circulating mixing system and a step-by-step feeding process, showed significantly better tensile strength and elongation at break than Comparative Examples 6 and 7, which did not use the process. This demonstrates that uniform dispersion of the filler is a necessary condition for obtaining excellent mechanical properties, because uneven distribution of the filler can lead to local stress concentration, which becomes a crack initiation point.

[0076] 3. Hardness test The hardness of the radiation protection gloves was tested using a Shore hardness tester (HA), and the results are shown in Table 3.

[0077] Table 3 As shown in Table 3, the hardness of Examples 1 to 3 of this application is 65 to 76 Shore A, which is much lower than the 90 Shore A of Comparative Example 8 containing lead. This indicates that after completely eliminating lead and its compounds, the softness and wearing comfort of the gloves are significantly improved. This is because rare earth oxides and core-shell structured powders have small particle sizes and good dispersibility, and good compatibility with the rubber matrix, without excessively restricting the movement of rubber molecular chains. The hardness of Example 1, which added core-shell powder, is 65 Shore A, which is lower than the 77 Shore A of Comparative Example 5 without core-shell powder. This shows that the core-shell structure helps to reduce the hardness of the material and improve its softness. The mechanism is that the shell material of the core-shell structure can form a flexible transition layer between the filler and the matrix, reducing the restriction of the filler on the movement of molecular chains. The hardness of Example 1, which uses a U-tube circulating mixing system and a step-by-step feeding process, is 65 Shore A, which is significantly lower than 88 Shore A in Comparative Example 6 and 83 Shore A in Comparative Example 7, which did not use the process. This demonstrates that uniform dispersion of the filler can prevent the formation of local hard agglomerates, thereby maintaining the soft feel of the material.

[0078] 4. Antibacterial performance test The antibacterial properties were tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method", and the results are shown in Table 4.

[0079] Table 4 As can be seen from Table 4, the examples with added silver ion antibacterial agents all showed excellent antibacterial effects, with antibacterial rates of over 99.6% against the three typical bacterial species.

[0080] 5. Verification of process effects To verify the effectiveness of the U-tube circulating mixing system, sedimentation experiments were conducted on the impregnation solutions of Example 1 and Comparative Example 6: the impregnation solutions were allowed to stand for 24 hours, and the height of the supernatant was measured. The results showed that the supernatant height in Example 1 was 1.5 mm, and in Comparative Example 6 it was 18 mm. This result fully demonstrates that the U-tube circulating mixing system, through forced circulation, keeps the high-density packing material in a suspended and dispersed state, effectively solving the technical problem of rapid sedimentation of packing material in latex, and providing process assurance for the stability and consistency of product performance.

[0081] Comprehensive analysis of examples and comparative examples: Based on the above test results, this application achieves stable and efficient protection across a wide energy spectrum by using a dual rare earth compound of gadolinium oxide and cerium oxide. Under the optimized ratio, the lead equivalent values ​​at the two energy points are quite close. The introduction of the core-shell heterogeneous gradient structure anti-ionizing radiation powder not only improves the shielding effectiveness through hierarchical absorption and multiple scattering effects at the core-shell interface, but also significantly enhances the mechanical properties of the material through the good compatibility between the core-shell structure and the rubber matrix. Compared with Example 1 and Comparative Example 5, the lead equivalent is increased by 20.2% to 41.3%, the tensile strength is increased by 40.0%, and the elongation at break is more than doubled.

[0082] This application utilizes silica as a functional carrier to load rare earth elements, leveraging silica's high specific surface area and surface hydroxyl groups to achieve uniform dispersion of rare earth elements at the molecular level, thus solving the industry problem of powder agglomeration under high filler content. Simultaneously, gadolinium oxide and cerium oxide nanoparticles loaded on the silica surface serve as functional interfaces that directly contact the rubber matrix. Their abundant active sites can form physical entanglements, hydrogen bonds, or coordination bonds with rubber molecular chains, thereby significantly enhancing the interfacial bonding force between the functional powder and the rubber matrix.

[0083] This application solves the problem of high-density filler sedimentation through a U-shaped tube circulating mixing system, ensuring the stability and consistency of product performance. This application completely eliminates lead and its compounds; the gloves have a hardness of 65 to 76 Shore A, far lower than lead-containing gloves, resulting in better wearing comfort. This application adds silver ion antibacterial agents, achieving an antibacterial rate of over 99.5%, exhibiting excellent killing effects against Staphylococcus aureus, Escherichia coli, and Candida albicans, significantly improving the hygiene performance of the gloves.

[0084] The preparation method provided in this application has a clear process route, and the equipment used is all general equipment used in the chemical and rubber industries. The conditions are easy to control and it has good feasibility for large-scale production.

[0085] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for preparing a radiation-resistant rubber glove with antibacterial properties, characterized in that, Includes the following steps: S1. Add 2-5 parts of silicone defoamer and 2-5 parts of OP-10 emulsifier to 100 parts of natural latex with a solid content of 30-60%, and stir and disperse thoroughly to obtain a mixture. S2, add 2-20 parts of silicon-based functional carrier to the mixture obtained in step S1; the silicon-based functional carrier is silicon dioxide with gadolinium oxide and cerium oxide loaded on its surface; S3, add 10-40 parts of core-shell heterogeneous gradient structure anti-ionizing radiation powder, 3-25 parts of tungsten-based shielding agent, and 3-25 parts of bismuth-based shielding agent to the mixture obtained in step S2, stir and disperse thoroughly, and set aside for later use; the core-shell heterogeneous gradient structure anti-ionizing radiation powder is Bi2O3@Gd2O3@TiO2 core-shell heterogeneous gradient anti-ionizing radiation powder; wherein, the core material is bismuth oxide, and the shell material is gadolinium oxide and titanium dioxide; S4. Add 0.5-5 parts of silver ion antibacterial agent and 1-3 parts of carbon black colorant to the mixture obtained in step S3, and stir to obtain the impregnation solution. S5, preparing gloves by impregnation: Immerse the hand mold in the impregnation solution prepared in step S4, then dry, vulcanize, and demold to obtain radiation-resistant rubber gloves with antibacterial properties.

2. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 1, characterized in that, The method for preparing the silicon-based functional carrier is as follows: nano-silica is dispersed in a solution containing gadolinium salt and cerium salt, and after precipitation and calcination, gadolinium oxide and cerium oxide nanoparticles are generated in situ on the surface of silica.

3. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 1, characterized in that, The mass ratio of gadolinium oxide to cerium oxide on the surface of the silicon-based functional carrier is 1:3 to 3:

1.

4. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 1, characterized in that, The tungsten-based shielding agent is at least one of tungsten oxide and tungstate.

5. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 1, characterized in that, The bismuth-based shielding agent is at least one of bismuth oxide and bismuthate.

6. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 1, characterized in that, In steps S2, S3, and S4, the mixture is circulated and stirred through a U-shaped tube circulation system.

7. The method for preparing the antibacterial radiation-resistant rubber gloves according to claim 6, characterized in that, During the process of dispersing the components in the latex, a U-shaped tube circulation system is used for circulation and stirring, with a circulation flow rate of 0.5-5 m / s and a circulation time of 30-120 minutes.

8. A radiation-resistant rubber glove with antibacterial properties, characterized in that, The antibacterial radiation-proof rubber gloves, prepared by the preparation method described in any one of claims 1-7, can achieve stable and efficient protection in a wide energy spectrum range of 30-150 keV, and the antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans all reach more than 99%.

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