Preparation and melting method of anti-radiation neutral borosilicate medical special glass container material

Abstract

The invention relates to the technical field of special glass manufacturing, and discloses a preparation method and a melting method of an anti-radiation neutral borosilicate medical special glass container material, and the preparation method comprises the following steps and components: a boron source: boron carbonate and boric acid, which are mixed according to a mass ratio of 1: 1, and the total mass of the boron source accounts for 50% of the total mass of the boron element; a silicon source: silica sand, the addition amount of which accounts for 25% of the total mass; the nano zinc oxide nano particles are nano oxidized nano particles subjected to surface modification by a silane coupling agent, and the adding amount of the nano zinc oxide nano particles accounts for 1.5% of the total mass; the rare earth elements comprise erbium, samarium, dysprosium and europium, each element accounts for 0.5% of the total mass, and the total mass is 2%; the fluxing agent is formed by mixing lithium tetraborate and lithium metaborate according to the mass ratio of 1: 1, and the total adding amount is 7% of the total mass. The addition of rare earth elements and the uniform distribution of the rare earth elements in a glass matrix are accurately controlled, and the hierarchical addition of the rare earth elements such as erbium, samarium, dysprosium and europium not only optimizes the chemical activity of the rare earth elements, but also enhances the absorption and shielding effects on different types of radiation.

Description

Technical Field

[0001] The invention relates to the technical field of special glass manufacturing, in particular to a preparation method and a melting method of radiation-resistant neutral borosilicate medical special glass container material. Background Art

[0002] In the medical industry, especially in the fields of radioactive material handling, storage and radiotherapy, there are extremely high requirements for the materials used, including their radiation resistance, mechanical strength, chemical stability and optical properties. As an indispensable component in these fields, medical glass containers need to have excellent performance to ensure patient safety and treatment effects. These containers not only need to block or reduce the potential harm of radiation to the human body and the environment, but also maintain sufficient transparency to facilitate medical staff to observe the internal conditions.

[0003] In the prior art, standard borosilicate glass or glass materials that are enhanced with lead to enhance radiation resistance are usually used. These materials can meet medical purposes to a certain extent, for example, by adding lead or other heavy metals to increase the density of glass, thereby improving its ability to block gamma rays and X-rays. However, the increased heavy metal content often leads to more complicated material handling and melting processes and higher energy consumption.

[0004] Although existing technologies provide basic solutions, they still have significant shortcomings. For example, the addition of heavy metals can enhance radiation resistance, but it will also affect the optical transparency and chemical stability of the material and increase the environmental burden. In addition, the traditional high-temperature melting process is not only energy-intensive, but also prone to internal stress and microscopic defects in the glass. These problems limit the application potential of the material in high-standard medical environments. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a method for preparing and melting radiation-resistant neutral borosilicate medical special glass container materials, which solves the problem that the traditional high-temperature melting process not only has high energy consumption but also easily generates internal stress and microscopic defects in the glass.

[0006] To achieve the above objectives, the present invention is implemented by the following technical scheme: A method for preparing a radiation-resistant neutral borosilicate medical special glass container material comprises the following steps and components: Components and their proportions: Boron source: boron carbonate and boric acid, mixed in a mass ratio of 1:1, with a total proportion of 50% of the total mass of boron element; Silicon source: silica sand, the added amount accounts for 25% of the total mass; Nano zinc oxide nanoparticles: Nano zinc oxide nanoparticles surface-modified with silane coupling agent, added in an amount of 1.5% of the total mass; Rare earth elements: erbium, samarium, dysprosium, europium, each element accounts for 0.5% of the total mass, a total of 2%; Flux: lithium tetraborate and lithium metaborate, mixed in a mass ratio of 1:1, with a total addition amount of 7% of the total mass; step: Step 1: mixing boron carbonate, boric acid, silica sand and surface-modified nano zinc oxide nanoparticles in the above proportions to form a preliminary material; Step 2: in the process of mixing the initial materials, boron carbonate, boric acid, nano zinc oxide nanoparticles modified by silica sand are gradually added with erbium, samarium, dysprosium and europium in the proportions described in step 1; Step 3: The initial mixture containing rare earth elements is further mixed with a flux to lower the melting point and increase the fluidity of the melt to complete the preparation.

[0007] Preferably, the silane coupling agent is tetraethoxysilane, which is used to improve the dispersibility of zinc oxide nanoparticles. The reaction amount of the tetraethoxysilane used for surface modification is 5 grams of tetraethoxysilane per 100 grams of zinc oxide nanoparticles.

[0008] Preferably, the added amount of silica sand accounts for 20% to 30% of the total mass.

[0009] Preferably, the average particle size of the nano zinc oxide nanoparticles is 30 nanometers.

[0010] Preferably, the rare earth elements are added in the following order: erbium is added first, followed by samarium, then dysprosium, and finally europium, and the amount of each rare earth element added is controlled to be 1% of the total mass.

[0011] Preferably, the invention further comprises a flux, wherein the flux comprises lithium tetraborate and lithium metaborate, which are mixed in a mass ratio of 1:1.

[0012] Preferably, the total amount of the flux added is 8% of the total mass.

[0013] The method for melting radiation-resistant neutral borosilicate medical special glass container material comprises the following steps: Step 1: Place the prepared glass raw material into a high-temperature furnace and heat it in an environment filled with helium; Step 2: Control the temperature in the furnace to gradually rise to 1680°C, and maintain a constant temperature to ensure that the glass material is completely melted and mixed evenly; Step 3: During the melting process, flux is added continuously at optimized time intervals through an electronically controlled dosing system to maintain the chemical homogeneity of the melt.

[0014] In the step 1, the pressure of the helium environment is maintained at 1.5 to 2.0 atmospheres. This pressure range helps to minimize bubble generation in the glass melt and improve the optical quality and structural uniformity of the glass.

[0015] Preferably, in step three, the melting step continues to maintain the temperature for at least 2 hours after reaching 1680° C. to ensure that all components are fully fused and the chemical reaction is completely carried out, thereby improving the radiation resistance of the final product.

[0016] The present invention provides a formula, preparation and melting method of a radiation-resistant neutral borosilicate medical special glass container material. It has the following beneficial effects: 1. The present invention significantly enhances the radiation resistance of the material by precisely controlling the addition of rare earth elements and their uniform distribution in the glass matrix. The layered addition of rare earth elements such as erbium, samarium, dysprosium, europium, etc. not only optimizes their chemical activity, but also enhances the absorption and shielding effects of different types of radiation; 2. The present invention uses temperature gradient control technology at a lower melting temperature to effectively reduce the internal stress and microscopic defects in the glass products, thereby improving the mechanical strength of the finished product. In addition, the carefully selected balance of the ratio of the boron source and the silicon source, as well as the special surface treatment of the nano zinc oxide nanoparticles during the preparation process, further increase the chemical stability of the glass, so that it can maintain its performance even in extreme environments; 3. The present invention performs surface modification on nanoparticles during the preparation process, so that they are more evenly distributed in the glass matrix, which not only enhances the UV shielding ability of the material, but also improves the transparency and optical properties of the glass. The optimized flux ratio and melting technology ensure the uniformity of the glass melt during the melting and cooling process, thereby reducing optical defects and improving the optical quality of the finished product, making it more suitable for medical containers and equipment that require high transparency; 4. The present invention reduces energy consumption and waste of raw materials in the manufacturing process through improved melting technology and material processing methods. In particular, the temperature gradient control technology and low-temperature melting strategy adopted reduce the high-energy high-temperature operation time and reduce the emission of volatile substances caused by high temperature. These improvements not only reduce production costs, but also reduce the impact of the production process on the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a flow chart of the preparation method of the present invention; Figure 2 The figure is a flow chart of the melting method of the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1, please refer to the attached Figure 1 The embodiment of the present invention provides a method for preparing a radiation-resistant neutral borosilicate medical special glass container material, comprising the following steps and components: Components and their proportions: Boron source: boron carbonate and boric acid, mixed in a mass ratio of 1:1, with a total proportion of 50% of the total mass of boron element; Silicon source: silica sand, the added amount accounts for 25% of the total mass; Nano zinc oxide nanoparticles: Nano zinc oxide nanoparticles surface-modified with silane coupling agent, added in an amount of 1.5% of the total mass; Rare earth elements: erbium, samarium, dysprosium, europium, each element accounts for 0.5% of the total mass, a total of 2%; Flux: lithium tetraborate and lithium metaborate, mixed in a mass ratio of 1:1, with a total addition amount of 7% of the total mass; step: Step 1: mixing boron carbonate, boric acid, silica sand and surface-modified nano zinc oxide nanoparticles in the above proportions to form a preliminary material; Step 2: in the process of mixing the initial materials, boron carbonate, boric acid, nano zinc oxide nanoparticles modified by silica sand are gradually added with erbium, samarium, dysprosium and europium in the proportions described in step 1; Step 3: The initial mixture containing rare earth elements is further mixed with a flux to lower the melting point and increase the fluidity of the melt to complete the preparation.

[0020] Among them, the preparation formula of nano zinc oxide nanoparticles surface modified by silane coupling agent is: .

[0021] Through this surface modification reaction, the surface of the nano zinc oxide nanoparticles obtains a layer of organic siliconization, which not only improves its dispersibility in composite materials, but also may enhance its performance in specific applications, such as enhancing UV blocking ability in radiation-resistant neutral borosilicate medical specialty glass. In addition, the modified nanoparticles are easier to combine with other organic or inorganic materials, providing more possibilities for the manufacture of high-performance composite materials.

[0022] The silane coupling agent is tetraethoxysilane, which is used to improve the dispersibility of zinc oxide nanoparticles. The reaction amount of tetraethoxysilane used for surface modification is 5 grams of tetraethoxysilane per 100 grams of zinc oxide nanoparticles to ensure that a uniform silanization layer is formed on the surface of the zinc oxide nanoparticles.

[0023] The amount of silica sand added accounts for 20% of the total mass.

[0024] The average particle size of nano zinc oxide nanoparticles is 30 nanometers. By controlling the size of the nanoparticles, the material's UV absorption capacity and radiation resistance are enhanced.

[0025] The addition of rare earth elements follows a specific order: erbium is added first, followed by samarium, then dysprosium, and finally europium. The amount of each rare earth element added is controlled to 1% of the total mass. This order and proportion optimizes the spectral absorption range and radiation resistance of the glass.

[0026] The invention comprises a flux, wherein the flux comprises lithium tetraborate and lithium metaborate, which are mixed in a mass ratio of 1:1. The mixing ratio is helpful to reduce the overall melting point and improve the fluidity during melting.

[0027] The total amount of flux added is 8% of the total mass.

[0028] Example 2, please refer to the attached Figure 2 This embodiment provides a method for melting radiation-resistant neutral borosilicate medical special glass container material based on the above embodiment, comprising the following steps: Step 1: Place the prepared glass raw material into a high-temperature furnace and heat it in an environment filled with helium; Step 2: Control the temperature in the furnace to gradually rise to 1680°C, and maintain a constant temperature to ensure that the glass material is completely melted and mixed evenly; Step 3: During the melting process, flux is added continuously at optimized time intervals through an electronically controlled dosing system to maintain the chemical homogeneity of the melt.

[0029] In step 1, the pressure of the helium environment is maintained at 1.5 to 2.0 atmospheres, which helps to minimize bubble generation in the glass melt and improve the optical quality and structural uniformity of the glass.

[0030] In step three, the melting step continues to maintain the temperature of 1680° C. for at least 2 hours after reaching the temperature, so as to ensure that all components are fully fused and the chemical reaction is completely carried out, thereby improving the radiation resistance of the final product.

[0031] Step 1: Preparation of initial material In this embodiment, the preparation of the initial material involves the following detailed steps: Raw material preparation: First, boron carbonate and boric acid are selected as boron sources. These two compounds not only provide the boron element required for the glass matrix, but are also used to improve radiation resistance due to their high neutron absorption cross-section. Silica sand, as a silicon source, provides the necessary silicon-oxygen skeleton for the glass and enhances the structural strength of the glass. When selecting boron carbonate and boric acid as boron sources, the differences in chemical properties and reactivity between the two are taken into account. Boron carbonate provides a higher melting point depression effect, while boric acid provides good chemical stability. This 1:1 ratio is designed to balance the two properties and optimize the thermal stability and chemical corrosion resistance of the glass.

[0032] Nanoparticle treatment: Surface-modified zinc oxide nanoparticles are used. These nanoparticles are treated with silane coupling agents to improve their dispersibility and stability in the glass matrix, while enhancing their ability to block UV radiation. This is achieved by controlling the chemical functional groups on the surface of the nanoparticles. The surface modification of the zinc oxide nanoparticles not only improves their dispersibility in the glass matrix, but also increases their ability to absorb ultraviolet rays. This treatment process involves reacting the zinc oxide nanoparticles with silane coupling agents under specific conditions to form a stable chemical bonding layer, thereby improving their stability and radiation resistance at high temperatures.

[0033] Mixing: Mix the above raw materials in a specific ratio. The mixing process is carried out at room temperature using high-efficiency stirring equipment to ensure that all ingredients are evenly dispersed to form a uniform initial material. This step is critical because the uniformity of the initial material directly affects the quality and performance of the final product.

[0034] Step 2: Rare Earth Elements Addition In this embodiment, the rare earth elements are added as follows: Selection of rare earth elements: Erbium, samarium, dysprosium, and europium are selected as key components of radiation-resistant materials. These elements are selected because they can effectively absorb radiation of different wavelengths, thereby improving the overall radiation resistance of the material; These rare earth elements are added layer by layer using precise metering equipment and control systems to ensure the amount and uniformity of addition at each step. This is accomplished through a program-controlled automated dosing system that ensures the complete incorporation and chemical uniformity of each element.

[0035] Addition order and proportion: Rare earth elements are added to the mixed initial material in the order of erbium, samarium, dysprosium, and europium. The addition of each element is controlled to ensure that each element is evenly distributed and the total addition amount is controlled to 1% of the total mass. This precisely controlled addition order and proportion is key to optimizing the spectral absorption and radiation resistance of the glass.

[0036] Step 3: Use of flux In this embodiment, the addition of flux specifically includes: Flux type: lithium tetraborate and lithium metaborate are selected as fluxes, which are used to lower the melting point of the melt and increase fluidity; The choice and ratio of flux directly affects the melting temperature and fluidity of the glass. The combination of lithium tetraborate and lithium metaborate is specially selected to optimize the melting point and reduce evaporation losses at high temperatures.

[0037] Mixing ratio: The flux is mixed in a 1:1 mass ratio, and the total amount is 8% of the total mass. This precise control of the ratio and total amount is based on the need to improve melting efficiency and molding quality.

[0038] Melting method In this embodiment, the melting method includes: High temperature melting: Put the prepared glass raw material into a high temperature furnace, heat it to 1680℃ in an environment filled with helium, and keep this temperature for at least 2 hours. Helium, as an inert gas, can prevent the melt from oxidation and help eliminate bubbles in the melt, thereby improving the optical quality and structural uniformity of the glass.

[0039] Precise control of temperature and time: This step is critical to ensure that all chemical reactions are thorough and that material properties are uniform, thereby ensuring radiation resistance and mechanical stability of the final product.

[0040] In a preferred embodiment, a multi-stage rare earth element addition strategy In order to further improve the performance of radiation-resistant neutral borosilicate medical special glass container materials, this preferred embodiment proposes a multi-stage rare earth element addition strategy. This strategy aims to optimize the distribution and functional efficiency of rare earth elements in the glass matrix, and achieve more efficient chemical integration and better material performance by controlling the addition timing and environment.

[0041] Step 1: Initial addition of erbium and samarium Operation: Erbium and samarium are first added at the initial stage of the melting process, when the melt temperature reaches about 1400°C. At this stage, the melt is relatively stable, and the lower temperature is conducive to the uniform distribution of erbium and samarium, avoiding aggregation caused by rapid reaction at high temperature.

[0042] Technical advantages: Adding erbium and samarium at a lower temperature helps them blend more evenly into the melt. These elements can gradually react with the glass matrix during the subsequent heating process to improve its stability and radiation resistance.

[0043] Step 2: Adding Dysprosium and Europium in the Medium Term Operation: When the melt temperature rises to about 1550°C, dysprosium and europium are added. This temperature point is before the material is nearly completely melted and the chemical activity increases, ensuring that the two rare earth elements can be quickly integrated in a more active chemical environment.

[0044] Technical Advantages: The addition of dysprosium and europium is placed in the medium term, taking advantage of their strong spectral absorption properties at higher temperatures, which helps them to disperse rapidly throughout the melt and provide immediate chemical and structural modifications.

[0045] Improved radiation resistance: Through a multi-stage addition strategy, each rare earth element is added at the most suitable temperature and chemical environment, which not only optimizes their distribution in the glass matrix, but also enhances the overall radiation resistance of the material.

[0046] Enhanced material uniformity: This strategy avoids the uneven distribution and aggregation that may be caused by adding all rare earth elements at once, ensuring that each element can be effectively integrated into the glass matrix, thereby improving product consistency and reliability.

[0047] In a preferred embodiment, 1. Principle and implementation of temperature gradient control; Technical principle: Temperature gradient control technology is based on the sensitivity of melt fluidity, chemical reaction rate and physical properties of materials to temperature. By setting different zones in the furnace to different temperatures, a temperature gradient from low temperature to high temperature can be created. This gradient helps control the reaction kinetics of complex chemical components, especially when multiple chemical components are involved in reaction and dissolution.

[0048] Steps: A lower temperature (e.g. 1400°C) is set at the loading end of the furnace, and the temperature is gradually increased toward the center and outlet of the furnace until it reaches 1680°C. This setting allows the initial material to start preheating and pre-reacting at a lower temperature, avoiding uneven chemical reactions and material defects caused by rapid heating.

[0049] 2. Combined with the specific implementation of the above technical solutions Combine steps 1 and 2: Before adding rare earth elements and flux, the glass raw material is pretreated using temperature gradient control technology. At this time, the raw material is preheated in a lower temperature zone, so that the boron, silicon source and nano zinc oxide nanoparticles gradually adapt to the high temperature environment and optimize their chemical reaction state.

[0050] As the raw material gradually moves to the high temperature area, rare earth elements such as erbium, samarium, dysprosium, and europium are gradually added. As the temperature gradually rises, these elements are more easily evenly distributed and react more completely, thereby improving the radiation resistance of the material.

[0051] Combined with step three: The addition of flux is carried out when the temperature is close to the highest point. The high temperature at this time helps the flux to dissolve quickly and promotes the homogenization of the entire glass melt. Due to the existence of the temperature gradient, the flux melts and also promotes the fluidity of the entire melt in the furnace, avoiding local overheating or material accumulation that may occur at a single high temperature.

[0052] Comparative Example 1: Main ingredients: silica 72%, boric acid 15%, sodium oxide 10%, aluminum oxide 3%; Preparation and melting method: After mixing the above raw materials, melt them at a high temperature of about 1500℃, stir continuously to ensure uniform composition, and then slowly cool them to form glass.

[0053] Comparative Example 2: Main ingredients: silica 70%, boric acid 15%, sodium oxide 8%, lead oxide 5%, aluminum oxide 2%; Preparation and melting method: Lead oxide is added to standard borosilicate glass to enhance radiation resistance. The raw materials are mixed and melted at 1600℃ to ensure that the lead oxide is fully integrated into the glass structure.

[0054] Comparative Example 3: Main ingredients: silica 73%, boric acid 15%, sodium oxide 8%, potassium oxide 4%; Preparation and melting method: Potassium oxide is added to improve the transparency and optical properties of the glass. The raw materials are mixed and melted in a kiln at a temperature of about 1500°C to ensure full mixing and uniform melting.

[0055] Experimental design: Experimental setup: Sample preparation: According to the formulations of the above embodiments and comparative examples, corresponding glass samples were prepared.

[0056] Test conditions: All samples were prepared and tested under the same environmental conditions to ensure comparability of the results.

[0057] Performance Test: Radiation resistance: Use a standard radiation source to irradiate the sample and measure its radiation blocking rate.

[0058] Mechanical Strength: The compressive strength of the samples was evaluated by a standard compression test.

[0059] Optical properties: measure the light transmittance and refractive index of samples.

[0060] .

[0061] Through the above test comparison and data analysis, it can be seen that Example 1 has obvious advantages in radiation resistance and mechanical strength, which proves the effectiveness of the multi-stage rare earth element addition strategy and temperature gradient controlled melting technology. The application of these technologies not only improves the functionality of glass materials, but also enhances its application potential in the medical field.

[0062] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing radiation-resistant neutral borosilicate medical special glass container material, characterized in that: The method comprises the following steps and components: Components and their proportions: Boron source: boron carbonate and boric acid, mixed in a mass ratio of 1:1, and the added amount is 50% of the total mass; Silicon source: silica sand, the added amount accounts for 25% of the total mass; Nano zinc oxide nanoparticles: Nano zinc oxide nanoparticles surface-modified with silane coupling agent, added in an amount of 1.5% of the total mass; Rare earth elements: erbium, samarium, dysprosium, europium, each element accounts for 0.5% of the total mass, a total of 2%; Flux: lithium tetraborate and lithium metaborate, mixed in a mass ratio of 1:1, with a total addition amount of 7% of the total mass; step: Step 1: mixing boron carbonate, boric acid, silica sand and surface-modified nano zinc oxide nanoparticles in the above proportions to form a preliminary material; Step 2: in the process of mixing the initial materials, boron carbonate, boric acid, nano zinc oxide nanoparticles modified by silica sand are gradually added with erbium, samarium, dysprosium and europium in the proportions described in step 1; Step 3: The initial mixture containing rare earth elements is further mixed with a flux to lower the melting point and increase the fluidity of the melt to complete the preparation.

2. The method for preparing the radiation-resistant neutral borosilicate medical special glass container material according to claim 1, characterized in that: The silane coupling agent is tetraethoxysilane, and the reaction amount of the tetraethoxysilane used for surface modification is 5 grams of tetraethoxysilane per 100 grams of zinc oxide nanoparticles.

3. The method for preparing the radiation-resistant neutral borosilicate medical special glass container material according to claim 1, characterized in that: The added amount of the silica sand accounts for 20% to 30% of the total mass.

4. The method for preparing the radiation-resistant neutral borosilicate medical special glass container material according to claim 1, characterized in that: The average particle size of the nano zinc oxide nanoparticles is 30 nanometers.

5. The method for preparing the radiation-resistant neutral borosilicate medical special glass container material according to claim 1, characterized in that: The order of adding the rare earth elements is: first add erbium, then samarium, then dysprosium, and finally europium, and the amount of each rare earth element added is controlled to be 1% of the total mass.

6. The method for preparing the radiation-resistant neutral borosilicate medical special glass container material according to claim 1, characterized in that: The total amount of the flux added is 8% of the total mass.

7. A method for melting the radiation-resistant neutral borosilicate medical special glass container material prepared according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1: Place the prepared glass raw material into a combustion furnace and heat it in an environment filled with helium; Step 2: Control the temperature in the furnace to gradually rise to 1680°C, and maintain a constant temperature to ensure that the glass material is completely melted and mixed evenly; Step 3: During the melting process, flux is added continuously at optimized time intervals through an electronically controlled dosing system to maintain the chemical homogeneity of the melt.

8. The method for melting the radiation-resistant neutral borosilicate medical special glass container material according to claim 7, characterized in that: In the step 1, the pressure of the helium environment is maintained at 1.5 to 2.0 atmospheres.

9. The method for melting the radiation-resistant neutral borosilicate medical special glass container material according to claim 7, characterized in that: In the step 3, the melting step continues to maintain the temperature of 1680° C. for at least 2 hours after reaching the temperature.

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