Black high-hardness heat-resistant microcrystalline glassware and preparation method thereof

Abstract

The application belongs to the technical field of glass materials, and particularly relates to a black high-hardness heat-resistant microcrystalline glassware and a preparation method thereof. The black high-hardness heat-resistant microcrystalline glassware is prepared by taking silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, metal manganese coated with silica, and black tourmaline as raw materials, and through the processes of high-temperature melting mixing, compression molding, annealing and tempering. The black high-hardness heat-resistant microcrystalline glassware has excellent performance, high hardness and good heat resistance, and has potential market value.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of glass materials, and particularly relates to a black high-hardness heat-resistant microcrystalline glassware and a preparation method thereof. BACKGROUND

[0002] With the increasing demand of modern industry and life for high-temperature application scenarios, glassware is increasingly widely used in various high-temperature equipment. Traditional glass materials are difficult to meet the long-term stable use under extreme temperature conditions due to poor heat shock resistance and insufficient hardness. And the current glassware strengthening methods are mostly through formula optimization, physical mixing of other materials and other ways, and rarely directly produce microcrystalline strengthening structure in glassware.

[0003] For example, the Chinese patent application with the publication number CN114195390A provides a black microcrystalline glass and a preparation method thereof, the chemical composition of which is SiO2: 55-65%, Al2O3: 2-5%, CaO: 10-15%, MgO: 0.2-2%, Na2O: 6-10%, K2O: 5-10%, Ce2O3: 0.1-1%, F: 3-8%, MnO2: 1-4%, Cr2O3: 1-3%, NiO: 1-3%, CuO: 0.5-2%, Co2O3: 0.1-2% in terms of mass percentage. The black microcrystalline glass only optimizes the formula, so its hardness still has room for optimization, and the black microcrystalline glass does not have heat shock resistance.

[0004] In summary, it is necessary to develop a high-hardness heat-resistant microcrystalline glassware directly producing microcrystalline strengthening structure in situ to meet the current technical requirements. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a black high-hardness heat-resistant microcrystalline glassware and a preparation method thereof. The present application uses silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silicon dioxide coated metal manganese and black tourmaline as raw materials, and a black high-hardness heat-resistant microcrystalline glassware is prepared through the processes of high-temperature melting mixing, pressing forming, annealing and tempering by producing microcrystalline strengthening structure in situ. The black high-hardness heat-resistant microcrystalline glassware has excellent performance, high hardness and good heat resistance, and has potential market value.

[0006] To achieve this purpose, the technical solution described below is adopted in the present application:

[0007] In a first aspect, this application provides a black, high-hardness, heat-resistant microcrystalline glass vessel, the raw materials of which include silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silicon dioxide-coated metallic manganese, and black tourmaline; wherein the silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and silicon dioxide-coated... The mass ratio of coated metallic manganese and black tourmaline is: (55.0~72.0): (8.0~18.0): (6.0~15.0): (2.0~4.0): (3.0~10.0): (0~2.0): (0~1.5): (0~1.2): (4.0~12.0): (0.3~1.2): (0.1~0.4): (0~3.0): (0~3.0): (3.0~10.0): (1.0~8.0)

[0008] Secondly, this application provides a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel, comprising the following steps:

[0009] The mixture is prepared by uniformly mixing silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline, and then heating and melting it at 1400-1600℃ to obtain a mixture.

[0010] The mixture is pressed into shape to obtain the molded material;

[0011] The molding material is placed in a holding furnace at 550-650℃ for annealing to obtain annealed material;

[0012] Tempering and annealing material: First, heat the annealing material to 600-650℃, hold it at that temperature, and then cool it rapidly to obtain black, high-hardness, heat-resistant microcrystalline glassware.

[0013] Compared with the prior art, the beneficial effects of this application are as follows:

[0014] When preparing black, high-hardness, heat-resistant microcrystalline glassware under high-temperature conditions, the manganese metal coated with silica remains stable even when directly subjected to high-temperature treatment in oxygen or air without the use of inert gas protection, due to the protection of silica. However, when all components are melted and mixed together, the manganese metal is released along with the melting of its silica coating. Under the combined action of high temperature and oxygen, it rapidly oxidizes, ultimately forming manganese tetroxide in situ within the molten glass. This in-situ formed manganese tetroxide can act as a network intermediate or modifier at high temperatures, participating in the formation of the silica-oxygen network in the glass, filling the gaps in the network, and generating a microcrystalline reinforced structure, making the glass structure denser and significantly improving the hardness and heat resistance of the resulting microcrystalline glassware. Furthermore, it can act as a colorant to further enhance the black appearance of the microcrystalline glassware. In addition, the chemical composition of black tourmaline, one of the components, is mainly composed of boron-containing aluminum and iron silicates. Its silicon-oxygen tetrahedra and ring structures can further combine with the silicon-oxygen network of glass at high temperatures, optimizing the microstructure of glass and thus further improving the hardness and heat resistance of the resulting microcrystalline glassware. Attached Figure Description

[0015] Figure 1 This is a picture of a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0016] Figure 2 This is a schematic diagram of the preparation process of silica-coated metallic manganese.

[0017] Figure 3 This is a schematic diagram of the preparation process of black, high-hardness, heat-resistant microcrystalline glassware. Detailed Implementation

[0018] The technical solutions of this application will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of this application, used to illustrate the concept of this application; these descriptions are illustrative and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of this application. In addition to the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the content disclosed in the claims and description of this application, including technical solutions that make any obvious substitutions and modifications to the embodiments described herein.

[0019] The terminology used in this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0020] The singular forms “for,” “a,” “any,” “any,” and “the” used in this application are intended to include the plural forms unless the context clearly indicates otherwise.

[0021] Furthermore, the terms "first" and "second" appearing in this application are for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0022] Firstly, such as Figure 1 As shown, this application provides a black, high-hardness, heat-resistant microcrystalline glass vessel; the raw materials used include silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silicon dioxide-coated metallic manganese, and black tourmaline; wherein the silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and silicon dioxide coating... The mass ratio of metallic manganese to black tourmaline is: (55.0~72.0): (8.0~18.0): (6.0~15.0): (2.0~4.0): (3.0~10.0): (0~2.0): (0~1.5): (0~1.2): (4.0~12.0): (0.3~1.2): (0.1~0.4): (0~3.0): (0~3.0): (3.0~10.0): (1.0~8.0)

[0023] In one possible implementation, the method for preparing the silica-coated metallic manganese is as follows: Figure 2 As shown, it includes the following steps:

[0024] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0025] Add a silane coupling agent to a manganese metal suspension, stir and react for 1-2 hours, then add ammonia water and adjust the pH to 9-11 to obtain an activated manganese metal suspension.

[0026] Tetraethyl orthosilicate was added dropwise to the activated manganese metal suspension under stirring conditions;

[0027] The reaction system was heated to 50-80°C and stirred continuously for 2-6 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0028] The solid product was placed in a vacuum oven and dried at 100–120°C for 8–10 hours to obtain silica-coated metallic manganese.

[0029] In one possible implementation, the silane coupling agent comprises any one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, propyltriethoxyisocyanate, and tetramethylguanidinopropyltrimethoxysilane.

[0030] In one possible implementation, the mass ratio of the silane coupling agent to metallic manganese is (1-5):(95-99).

[0031] In one possible implementation, the mass ratio of tetraethyl orthosilicate to metallic manganese is (1-5):1.

[0032] Secondly, this application provides a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel, such as... Figure 3 As shown, it includes the following steps:

[0033] The mixture is prepared by uniformly mixing silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline, and then heating and melting it at 1400-1600℃ to obtain a mixture.

[0034] The mixture is pressed into shape to obtain the molded material;

[0035] The molding material is placed in a holding furnace at 550-650℃ for annealing to obtain annealed material;

[0036] Tempering and annealing material: First, heat the annealing material to 600-650℃, hold it at that temperature, and then cool it rapidly to obtain black, high-hardness, heat-resistant microcrystalline glassware.

[0037] In one possible implementation, the mixture compression molding process includes the following steps:

[0038] Preheat the pressing mold to 1150-1250℃;

[0039] The molten mixture is cooled to 1150–1250°C and then added to the mold;

[0040] Set the pressure of the pressing equipment to 100-150 MPa and the temperature to 1250℃ for pressing;

[0041] After pressing, the temperature is reduced to 600-650℃ at a cooling rate of 20℃ / h; then reduced to 500-550℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0042] In one possible implementation, the annealing process of the molding material includes the following specific steps:

[0043] The temperature of the holding furnace is reduced to 400-450℃ at a rate of 5℃ / min and held for 15 minutes; then the temperature of the holding furnace is reduced to room temperature at a rate of 25℃ / min.

[0044] In one possible implementation, during the heating and holding process of the annealed material tempering treatment: the heating rate is 10℃ / min, and the holding time is 45min.

[0045] In one possible implementation, during the rapid cooling process after the annealed material has undergone heat treatment and is held at a temperature of 5°C / min, the temperature is first reduced to 250°C; then, it is reduced to room temperature at a rate of 25°C / min.

[0046] In one possible implementation, the surface of the black, high-hardness, heat-resistant microcrystalline glassware has a Mohs hardness of 6.5 to 7 and a thermal shock resistance of ≥150℃.

[0047] The following will describe in detail, with reference to different embodiments, a black high-hardness heat-resistant microcrystalline glass vessel and its preparation method provided in this application.

[0048] Example 1

[0049] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0050] 1. Preparation of silica-coated metallic manganese:

[0051] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0052] γ-aminopropyltriethoxysilane was added to a manganese metal suspension, and the mixture was stirred for 1 hour. Then, ammonia was added to adjust the pH to 9, thereby obtaining an activated manganese metal suspension. The mass ratio of γ-aminopropyltriethoxysilane to manganese metal was 2:98.

[0053] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 3:1.

[0054] The reaction system was heated to 50°C and stirred continuously for 6 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0055] The solid product was placed in a vacuum oven and dried at 100°C for 10 hours to obtain silica-coated metallic manganese.

[0056] 2. Preparation of the mixture:

[0057] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1450°C to obtain a mixture.

[0058] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 58.0:9.0:7.0:3.0:5.0:1.0:0.5:0.5:5.5:0.7:0.2:1.0:1.0:5.0:2.6.

[0059] 3. Mixed material compression molding:

[0060] Prepare the pressing equipment and molds, and preheat the molds to 1200℃;

[0061] The molten mixture is cooled to 1200℃ and then added to the mold;

[0062] The pressing equipment is set to a pressure of 100 MPa and a temperature of 1250℃ for pressing.

[0063] After pressing, the temperature is reduced to 650℃ at a cooling rate of 20℃ / h; then reduced to 500℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0064] 4. Annealing:

[0065] The molding material was placed in a holding furnace at 550°C, and the furnace temperature was reduced to 400°C at a rate of 5°C / min. The material was then held at 400°C for 15 minutes. The furnace temperature was then reduced to room temperature at a rate of 25°C / min to obtain the annealed material.

[0066] 5. Tempering treatment:

[0067] First, heat the annealing material to 600℃ at a rate of 10℃ / min and hold for 45min.

[0068] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0069] Example 2

[0070] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0071] 1. Preparation of silica-coated metallic manganese:

[0072] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0073] γ-glycidoxypropyltrimethoxysilane was added to a suspension of metallic manganese, and the mixture was stirred for 1.5 h. Then, ammonia was added to adjust the pH to 10 to obtain an activated suspension of metallic manganese. The mass ratio of γ-glycidoxypropyltrimethoxysilane to metallic manganese was 1:99.

[0074] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 1:1.

[0075] The reaction system was heated to 60°C and stirred continuously for 4 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0076] The solid product was placed in a vacuum oven and dried at 110°C for 9 hours to obtain silica-coated metallic manganese.

[0077] 2. Preparation of the mixture:

[0078] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1500℃ to obtain a mixture.

[0079] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 60.0:10.0:7.0:2.0:4.0:1.0:0.5:0.5:4.0:0.8:0.2:1.0:1.0:5.0:3.0.

[0080] 3. Mixed material compression molding:

[0081] Prepare the pressing equipment and molds, and preheat the molds to 1150℃;

[0082] The molten mixture is cooled to 1150℃ and then added to the mold;

[0083] The pressing equipment is set to a pressure of 120 MPa and a temperature of 1250 °C for pressing.

[0084] After pressing, the temperature is reduced to 630℃ at a cooling rate of 20℃ / h; then reduced to 520℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0085] 4. Annealing:

[0086] The molding material was placed in a holding furnace at 580°C, and the furnace temperature was reduced to 430°C at a rate of 5°C / min. The material was held at 430°C for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25°C / min to obtain the annealed material.

[0087] 5. Tempering treatment:

[0088] First, heat the annealing material to 620℃ at a rate of 10℃ / min and hold for 45min.

[0089] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0090] Example 3

[0091] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0092] 1. Preparation of silica-coated metallic manganese:

[0093] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0094] Propyltriethoxysilane isocyanate was added to a suspension of metallic manganese, and the mixture was stirred for 2 hours. Then, ammonia was added to adjust the pH to 11, thereby obtaining an activated suspension of metallic manganese. The mass ratio of propyltriethoxysilane to metallic manganese was 3:97.

[0095] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 2:1.

[0096] The reaction system was heated to 80°C and stirred continuously for 2 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0097] The solid product was placed in a vacuum oven and dried at 120°C for 8 hours to obtain silica-coated metallic manganese.

[0098] 2. Preparation of the mixture:

[0099] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1550℃ to obtain a mixture.

[0100] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 63.0:9.0:7.0:2.5:3.0:1.5:0.7:0.6:4.5:0.9:0.3:1.0:1.0:3.0:2.0.

[0101] 3. Mixed material compression molding:

[0102] Prepare the pressing equipment and molds, and preheat the molds to 1250℃;

[0103] The molten mixture is cooled to 1250℃ and then added to the mold;

[0104] The pressing equipment is set to a pressure of 150 MPa and a temperature of 1250 °C for pressing.

[0105] After pressing, the temperature is reduced to 650℃ at a cooling rate of 20℃ / h; then reduced to 550℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0106] 4. Annealing:

[0107] The molding material was placed in a holding furnace at 600℃, and the furnace temperature was reduced to 425℃ at a rate of 5℃ / min. The material was held at 425℃ for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25℃ / min to obtain the annealed material.

[0108] 5. Tempering treatment:

[0109] First, heat the annealing material to 650℃ at a rate of 10℃ / min and hold it for 45min.

[0110] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0111] Example 4

[0112] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0113] 1. Preparation of silica-coated metallic manganese:

[0114] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0115] Tetramethylguanidinopropyltrimethoxysilane was added to a suspension of metallic manganese, and the mixture was stirred for 1.2 h. Then, ammonia was added to adjust the pH to 9.5 to obtain an activated suspension of metallic manganese. The mass ratio of tetramethylguanidinopropyltrimethoxysilane to metallic manganese was 4:96.

[0116] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 5:1.

[0117] The reaction system was heated to 55°C and stirred continuously for 5 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0118] The solid product was placed in a vacuum oven and dried at 105°C for 9.5 hours to obtain silica-coated metallic manganese.

[0119] 2. Preparation of the mixture:

[0120] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1480℃ to obtain a mixture.

[0121] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 55.0:12.0:9.0:2.0:3.5:1.2:0.6:0.4:5.0:0.6:0.2:1.5:1.5:4.0:3.5.

[0122] 3. Mixed material compression molding:

[0123] Prepare the pressing equipment and molds, and preheat the molds to 1220℃;

[0124] The molten mixture is cooled to 1220℃ and then added to the mold;

[0125] The pressing equipment is set to a pressure of 140 MPa and a temperature of 1250 °C for pressing.

[0126] After pressing, the temperature is reduced to 640℃ at a cooling rate of 20℃ / h; then reduced to 510℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0127] 4. Annealing:

[0128] The molding material was placed in a holding furnace at 620°C, and the furnace temperature was reduced to 440°C at a rate of 5°C / min. The material was held at 440°C for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25°C / min to obtain the annealed material.

[0129] 5. Tempering treatment:

[0130] First, heat the annealing material to 640℃ at a rate of 10℃ / min and hold for 45min.

[0131] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0132] Example 5

[0133] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0134] 1. Preparation of silica-coated metallic manganese:

[0135] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0136] Tetramethylguanidinopropyltrimethoxysilane was added to a suspension of metallic manganese, and the mixture was stirred for 1.8 h. Then, ammonia was added to adjust the pH to 10.5 to obtain an activated suspension of metallic manganese. The mass ratio of tetramethylguanidinopropyltrimethoxysilane to metallic manganese was 5:95.

[0137] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 4:1.

[0138] The reaction system was heated to 70°C and stirred continuously for 3 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0139] The solid product was placed in a vacuum oven and dried at 115°C for 8.5 hours to obtain silica-coated metallic manganese.

[0140] 2. Preparation of the mixture:

[0141] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1520℃ to obtain a mixture.

[0142] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 70.0:8.0:6.0:2.0:3.0:0.3:0.3:0.2:4.0:0.5:0.2:0.5:0.5:3.0:1.5.

[0143] 3. Mixed material compression molding:

[0144] Prepare the pressing equipment and molds, and preheat the molds to 1180℃;

[0145] The molten mixture is cooled to 1180℃ and then added to the mold;

[0146] The pressing equipment is set to a pressure of 130 MPa and a temperature of 1250 °C for pressing.

[0147] After pressing, the temperature is reduced to 615℃ at a cooling rate of 20℃ / h; then reduced to 525℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0148] 4. Annealing:

[0149] The molding material was placed in a holding furnace at 625°C, and the furnace temperature was reduced to 430°C at a rate of 5°C / min. The material was held at 430°C for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25°C / min to obtain the annealed material.

[0150] 5. Tempering treatment:

[0151] First, heat the annealing material to 635℃ at a rate of 10℃ / min and hold for 45min.

[0152] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0153] Example 6

[0154] like Figure 3 As shown, a method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0155] 1. Preparation of silica-coated metallic manganese:

[0156] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0157] γ-glycidoxypropyltrimethoxysilane was added to a suspension of metallic manganese, and the mixture was stirred for 1.6 h. Then, ammonia was added to adjust the pH to 10.8 to obtain an activated suspension of metallic manganese. The mass ratio of γ-glycidoxypropyltrimethoxysilane to metallic manganese was 2.5:97.5.

[0158] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 5:1.

[0159] The reaction system was heated to 75°C and stirred continuously for 5 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0160] The solid product was placed in a vacuum oven and dried at 118°C for 8.2 hours to obtain silica-coated metallic manganese.

[0161] 2. Preparation of the mixture:

[0162] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is put into a melting furnace and heated to 1540℃ to obtain a mixture.

[0163] The mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is 56.0:11.0:9.0:3.0:4.0:0.7:0.7:0.6:4.0:0.7:0.3:1.5:1.5:4.0:3.0.

[0164] 3. Mixed material compression molding:

[0165] Prepare the pressing equipment and molds, and preheat the molds to 1220℃;

[0166] The molten mixture is cooled to 1220℃ and then added to the mold;

[0167] The pressing equipment is set to a pressure of 115 MPa and a temperature of 1250℃ for pressing.

[0168] After pressing, the temperature is reduced to 620℃ at a cooling rate of 20℃ / h; then reduced to 540℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0169] 4. Annealing:

[0170] The molding material was placed in a holding furnace at 640℃, and the furnace temperature was reduced to 420℃ at a rate of 5℃ / min. The material was held at 420℃ for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25℃ / min to obtain the annealed material.

[0171] 5. Tempering treatment:

[0172] First, heat the annealing material to 630℃ at a rate of 10℃ / min and hold it for 45min.

[0173] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0174] Comparative Example 1

[0175] A method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0176] 1. Preparation of the mixture:

[0177] The mixture of silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and black tourmaline is put into a melting furnace and heated to 1450℃ to obtain a mixture.

[0178] The mass ratio of silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and black tourmaline is 63.0:9.0:7.0:3.0:5.0:1.0:0.5:0.5:5.5:0.7:0.2:1.0:1.0:2.6.

[0179] 2. Mixed material compression molding:

[0180] Prepare the pressing equipment and molds, and preheat the molds to 1200℃;

[0181] The molten mixture is cooled to 1200℃ and then added to the mold;

[0182] The pressing equipment is set to a pressure of 100 MPa and a temperature of 1250℃ for pressing.

[0183] After pressing, the temperature is reduced to 650℃ at a cooling rate of 20℃ / h; then reduced to 500℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0184] 3. Annealing:

[0185] The molding material was placed in a holding furnace at 550°C, and the furnace temperature was reduced to 400°C at a rate of 5°C / min. The material was then held at 400°C for 15 minutes. The furnace temperature was then reduced to room temperature at a rate of 25°C / min to obtain the annealed material.

[0186] 4. Tempering treatment:

[0187] First, heat the annealing material to 600℃ at a rate of 10℃ / min and hold for 45min.

[0188] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0189] Comparative Example 2

[0190] A method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0191] 1. Preparation of silica-coated metallic manganese:

[0192] Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension.

[0193] Propyltriethoxysilane isocyanate was added to a suspension of metallic manganese, and the mixture was stirred for 2 hours. Then, ammonia was added to adjust the pH to 11, thereby obtaining an activated suspension of metallic manganese. The mass ratio of propyltriethoxysilane to metallic manganese was 3:97.

[0194] Tetraethyl orthosilicate was added dropwise to an activated manganese metal suspension under stirring conditions; the mass ratio of tetraethyl orthosilicate to manganese metal was 2:1.

[0195] The reaction system was heated to 80°C and stirred continuously for 2 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol.

[0196] The solid product was placed in a vacuum oven and dried at 120°C for 8 hours to obtain silica-coated metallic manganese.

[0197] 2. Preparation of the mixture:

[0198] The mixture of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and silica-coated metallic manganese is uniformly mixed and then added to a melting furnace and heated to 1550°C to obtain a mixture.

[0199] The mass ratio of silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, and silicon dioxide-coated metallic manganese is 65.0:9.0:7.0:2.5:3.0:1.5:0.7:0.6:4.5:0.9:0.3:1.0:1.0:3.0.

[0200] 3. Mixed material compression molding:

[0201] Prepare the pressing equipment and molds, and preheat the molds to 1250℃;

[0202] The molten mixture is cooled to 1250℃ and then added to the mold;

[0203] The pressing equipment is set to a pressure of 150 MPa and a temperature of 1250 °C for pressing.

[0204] After pressing, the temperature is reduced to 650℃ at a cooling rate of 20℃ / h; then reduced to 550℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0205] 4. Annealing:

[0206] The molding material was placed in a holding furnace at 600℃, and the furnace temperature was reduced to 425℃ at a rate of 5℃ / min. The material was held at 425℃ for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25℃ / min to obtain the annealed material.

[0207] 5. Tempering treatment:

[0208] First, heat the annealing material to 650℃ at a rate of 10℃ / min and hold it for 45min.

[0209] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0210] Comparative Example 3

[0211] A method for preparing a black, high-hardness, heat-resistant microcrystalline glass vessel includes the following steps:

[0212] 1. Preparation of the mixture:

[0213] The mixture of silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite and lithium oxide is put into a melting furnace and heated to melt at 1540℃ to obtain a mixture.

[0214] The mass ratio of silicon dioxide, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, and lithium oxide is 63.0:11.0:9.0:3.0:4.0:0.7:0.7:0.6:4.0:0.7:0.3:1.5:1.5.

[0215] 2. Mixed material compression molding:

[0216] Prepare the pressing equipment and molds, and preheat the molds to 1220℃;

[0217] The molten mixture is cooled to 1220℃ and then added to the mold;

[0218] The pressing equipment is set to a pressure of 115 MPa and a temperature of 1250℃ for pressing.

[0219] After pressing, the temperature is reduced to 620℃ at a cooling rate of 20℃ / h; then reduced to 540℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

[0220] 3. Annealing:

[0221] The molding material was placed in a holding furnace at 640℃, and the furnace temperature was reduced to 420℃ at a rate of 5℃ / min. The material was held at 420℃ for 15 minutes. Then the furnace temperature was reduced to room temperature at a rate of 25℃ / min to obtain the annealed material.

[0222] 4. Tempering treatment:

[0223] First, heat the annealing material to 630℃ at a rate of 10℃ / min and hold it for 45min.

[0224] Then, the temperature is first lowered to 250℃ at a rate of 5℃ / min; then, it is lowered to room temperature at a rate of 25℃ / min to obtain a black, high-hardness, heat-resistant microcrystalline glass vessel.

[0225] The high-hardness heat-resistant microcrystalline glassware prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to performance tests. The specific test results are as follows:

[0226] Referring to GB / T 4547-2007, the maximum temperature difference Δt of the high-hardness heat-resistant microcrystalline glassware prepared in Examples 1-6 and Comparative Examples 1-3 without breakage was tested to demonstrate the heat resistance performance of the high-hardness heat-resistant microcrystalline glassware prepared in Examples 1-6 and Comparative Examples 1-3.

[0227] Referring to GB / T 9966.5-2020, the Mohs hardness of the high-hardness heat-resistant microcrystalline glassware prepared in Examples 1-6 and Comparative Examples 1-3 was tested.

[0228] The test results are shown in Table 1 below:

[0229] Table 1. Performance test results of the high-hardness heat-resistant microcrystalline glassware prepared in Examples 1-6 and Comparative Examples 1-3.

[0230]

[0231]

[0232] As can be seen from the test results provided in Table 1, the data of the black high-hardness heat-resistant microcrystalline glassware materials prepared by each group of embodiments in this application are all better than those of the comparative examples.

[0233] This is because, in Examples 1-6, the silica-coated manganese metal, protected by silica, avoids rapid oxidation even when directly treated at high temperatures in oxygen or air without the use of inert gas protection. Therefore, the manganese metal remains stable before all components are melted and mixed together. When all components are melted and mixed together, the manganese metal is released as the silica coating melts, and rapidly oxidizes under the combined action of high temperature and oxygen, ultimately generating manganese tetroxide in situ within the molten glass. The in-situ generated manganese tetroxide can, on the one hand, act as a network intermediate or modifier at high temperatures, participating in the formation of the silica-oxygen network in the glass, filling the gaps in the silica-oxygen network, and generating a microcrystalline reinforced structure in situ, making the glass structure denser and significantly improving the hardness and heat resistance of the resulting microcrystalline glassware; on the other hand, it can act as a colorant to further enhance the black appearance of the resulting microcrystalline glassware. In addition, the chemical composition of black tourmaline, one of the components, is mainly composed of boron-containing aluminum and iron silicates. Its silicon-oxygen tetrahedra and ring structures can further combine with the silicon-oxygen network of glass at high temperatures, optimizing the microstructure of glass and thus further improving the hardness and heat resistance of the resulting microcrystalline glassware.

[0234] In Comparative Example 1, no silicon dioxide-coated manganese was used when preparing the microcrystalline glassware, so manganese tetroxide could not be formed in situ. Consequently, manganese tetroxide would not be able to generate a microcrystalline reinforcing structure in situ at high temperatures, making the glass structure more compact. As a result, the hardness and heat resistance of the microcrystalline glassware were significantly reduced.

[0235] In Comparative Example 2, black tourmaline was not used when preparing the microcrystalline glassware, so the microstructure of the glass could not be further optimized at high temperatures, and the hardness and heat resistance of the final microcrystalline glassware were reduced to a certain extent.

[0236] In Comparative Example 3, neither the silica-coated manganese nor the black tourmaline was used in the preparation of the microcrystalline glassware, so none of the above effects were achieved, and the final microcrystalline glassware had the worst hardness and heat resistance.

[0237] The applicant declares that the above description is only a specific implementation of this application, but the protection scope of this application is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application fall within the protection and disclosure scope of this application.

Claims

1. A black, high-hardness, heat-resistant microcrystalline glass vessel, characterized in that, The raw materials used include silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline; the mass ratio of silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline is as follows: The values ​​are: (55.0~72.0): (8.0~18.0): (6.0~15.0): (2.0~4.0): (3.0~10.0): (0~2.0): (0~1.5): (0~1.2): (4.0~12.0): (0.3~1.2): (0.1~0.4): (0~3.0): (0~3.0): (3.0~10.0): (1.0~8.0).

2. The black, high-hardness, heat-resistant microcrystalline glassware as described in claim 1, characterized in that, The method for preparing the silica-coated metallic manganese includes the following steps: Manganese metal powder was ultrasonically dispersed in anhydrous ethanol to form a manganese metal suspension. Add a silane coupling agent to a manganese metal suspension, stir and react for 1-2 hours, then add ammonia water and adjust the pH to 9-11 to obtain an activated manganese metal suspension. Tetraethyl orthosilicate was added dropwise to the activated manganese metal suspension under stirring conditions; The reaction system was heated to 50-80°C and stirred continuously for 2-6 hours. The solid product was then collected by centrifugation and washed three times with anhydrous ethanol. The solid product was placed in a vacuum oven and dried at 100–120°C for 8–10 hours to obtain silica-coated metallic manganese.

3. The black, high-hardness, heat-resistant microcrystalline glassware as described in claim 2, characterized in that, The silane coupling agent includes any one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, propyltriethoxyisocyanate, and tetramethylguanidinopropyltrimethoxysilane.

4. The black, high-hardness, heat-resistant microcrystalline glassware as described in claim 2, characterized in that, The mass ratio of the silane coupling agent to metallic manganese is (1-5):(95-99).

5. The black, high-hardness, heat-resistant microcrystalline glassware as described in claim 2, characterized in that, The mass ratio of tetraethyl orthosilicate to metallic manganese is (1-5):

1.

6. The method for preparing the black, high-hardness, heat-resistant microcrystalline glassware according to any one of claims 1 to 5, characterized in that, Includes the following steps: The mixture is prepared by uniformly mixing silica, sodium oxide, aluminum oxide, potassium oxide, boron oxide, magnesium oxide, calcium oxide, zinc oxide, sodium fluorosilicate, iron oxide, manganese oxide, fluorite, lithium oxide, silica-coated metallic manganese, and black tourmaline, and then heating and melting it at 1400-1600℃ to obtain a mixture. The mixture is pressed into shape to obtain the molded material; The molding material is placed in a holding furnace at 550-650℃ for annealing to obtain annealed material; Tempering and annealing material: First, heat the annealing material to 600-650℃, hold it at that temperature, and then cool it rapidly to obtain black, high-hardness, heat-resistant microcrystalline glassware.

7. The method for preparing the black, high-hardness, heat-resistant microcrystalline glassware as described in claim 6, characterized in that, The mixture compression molding process includes the following steps: Preheat the pressing mold to 1150-1250℃; The molten mixture is cooled to 1150–1250°C and then added to the mold; Set the pressure of the pressing equipment to 100-150 MPa and the temperature to 1250℃ for pressing; After pressing, the temperature is reduced to 600-650℃ at a cooling rate of 20℃ / h; then reduced to 500-550℃ at a cooling rate of 10℃ / h, and the mold is removed to obtain the molded material.

8. The method for preparing the black, high-hardness, heat-resistant microcrystalline glassware as described in claim 6, characterized in that, The specific steps in the annealing process of the molding material are as follows: The temperature of the holding furnace is reduced to 400-450℃ at a rate of 5℃ / min and held for 15 minutes; then the temperature of the holding furnace is reduced to room temperature at a rate of 25℃ / min.

9. The method for preparing the black, high-hardness, heat-resistant microcrystalline glassware as described in claim 6, characterized in that, During the heating and holding process of the annealed material tempering treatment: the heating rate is 10℃ / min, and the holding time is 45min; During the rapid cooling process after the annealed material has undergone heat preservation during tempering treatment: the temperature is first reduced to 250°C at a rate of 5°C / min; then it is reduced to room temperature at a rate of 25°C / min.

10. The method for preparing the black, high-hardness, heat-resistant microcrystalline glassware as described in claim 6, characterized in that, The surface of the black, high-hardness, heat-resistant microcrystalline glassware has a Mohs hardness of 6.5 to 7 and a thermal shock resistance of ≥150℃.

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