CN115159853A - Nano microcrystalline transparent glass ceramic and raw material composition, method, application and system for preparing same - Google Patents
Nano microcrystalline transparent glass ceramic and raw material composition, method, application and system for preparing same Download PDFInfo
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- CN115159853A CN115159853A CN202210642053.8A CN202210642053A CN115159853A CN 115159853 A CN115159853 A CN 115159853A CN 202210642053 A CN202210642053 A CN 202210642053A CN 115159853 A CN115159853 A CN 115159853A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
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Abstract
The invention relates to the technical field of glass production, and discloses a composition and a system for preparing nano microcrystalline transparent glass ceramic, nano microcrystalline transparent glass ceramic and a preparation method and application thereof. Firstly, uniformly mixing alumina, quartz sand, potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium oxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium trioxide, antimony trioxide and cullet to obtain a batch. Then preparing the nano microcrystalline transparent glass ceramic by a continuous melting process of fractional melting. The process ensures the quality of the glass, has stable melting process, shortens the melting time of the glass and increases the melting rate of the glass. The nano microcrystalline transparent glass ceramic prepared by the invention has the advantages of obvious Faraday paramagnetic effect, high hardness, high strength, good toughness, excellent impact resistance, excellent chemical resistance stability, high light transmittance, uniform and fine crystals, simple preparation process and operation process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of glass production, in particular to a composition and a system for preparing nano microcrystalline transparent glass ceramic, nano microcrystalline transparent glass ceramic and a preparation method and application thereof.
Background
The nano microcrystal transparent glass is commonly called as glass crystal or ceramic glass, metal oxide crystal grains are added in the production process of the glass as crystal seeds, a new high-temperature crystallization step is added to enable the ceramic crystal in a glass matrix to grow and crystallize, the size of the crystal is small, the strength of the crystal is high, the glass has high strength and transparency, and simultaneously, a glass phase exists, so that the glass has the dual characteristics of glass and ceramic, and the nano microcrystal transparent glass has better firmness and surface hardness.
The nano microcrystalline glass has surface effect, volume effect, quantum size effect and macroscopic quantum tunneling effect, so that a series of physicochemical properties such as optical, mechanical, thermal, electromagnetic, chemical and catalytic properties can be generated.
The nano microcrystalline glass is an optical gain material consisting of a homogeneous glass phase and a well-dispersed nano crystalline phase, combines the advantages of a strong crystal field of nano crystals and good fiber forming capability of glass, and is considered as a potential gain medium of an optical fiber device. Compared with a glass crystal single-phase material, the material has the following advantages: on one hand, the crystal is dependent on a carrier with excellent processing performance and stable thermal/chemical performance; on the other hand, imparting special optical functionality to glass from crystals is an irreplaceable material in numerous optoelectronic devices.
The application development and industrialization of the nano-microcrystal are another important issue worthy of attention and enough attention should be paid. Although our country has achieved many research results of nano-microcrystalline and research on some systems approaches the level of developed countries, the gap between industrialization and application is still large compared with the advanced level in foreign countries.
CN113698095A discloses a glass composition, nano microcrystalline glass, a preparation method and an application thereof, wherein the glass composition contains 48-60wt% of SiO 2 25-35wt% of Al 2 O 3 5-10wt% of Na 2 O, 0-2wt% of K 2 O, 0-2wt% of B 2 O 3 2-6wt% of ZrO 2 1-3wt% of Li 2 O, 1.5-5wt% of TiO 2 And 1-4wt% of P 2 O 5 . The nano microcrystalline glass formed by the glass composition in the scheme has good light transmittance and good mechanical properties such as falling resistance, compression resistance and aging resistance.
CN111847886A discloses a tin dioxide-containing nano microcrystalline glass and a preparation method thereof, and the method comprises the steps of doping porous glass with a mixed solution containing tin ions and luminescent ions in sequence, carrying out primary heat treatment, and then carrying out acid treatment to effectively improve the transparency of the glass and improve the luminescent property of high silica glass.
CN104478219A discloses a nano-spinel microcrystalline glass, which comprises the following components: 56wt% -62wt% of SiO 2 (ii) a 19 to 23wt% of Al 2 O 3 (ii) a 6-15 wt% of ZnO; 2-6.5 wt% of MgO; 2-6wt% of TiO 2 (ii) a 2 to 7wt% of ZrO 2 . By adopting the scheme, the mechanical strength of the microcrystalline glass can be improved, and the microcrystalline microcrystal can be improvedMechanical properties of the glass.
CN112851122a discloses a high fracture toughness microcrystalline glass for a mobile phone backboard, comprising: 30-60% of a main crystalline phase which is composed of xonotlite and 5-10% of a secondary crystalline phase which is composed of one or two of xonotlite and calcium fluoride, and the balance of a glass phase; the composite material comprises the following components in percentage by mass: 50-63% of SiO 2 、1-5％Al 2 O 3 、15-20％CaO、6-12％Na 2 O、2-6％K 2 O、3-5％Li 2 O、3-6％CaF 2 、0-2％TiO 2 、1-3％ZrO 2 、0-3％Y 2 O 3 、3-7％B 2 O 3 、0-3％P 2 O 5 、0.1-0.5％Sb 2 O 3 . Through the technical scheme, the problem that the microcrystalline glass in the prior art cannot simultaneously have fracture toughness and chemical strengthening property is solved.
CN111003934a discloses a substrate glass for optical communication, which comprises in wt%: siO 2 2 ：30-50％；TiO 2 ：10-30％；R 2 O：15-30％；Al 2 O 3 ：0.5-10％；Y 2 O 3 ：0-10％；La 2 O 3 :0 to 10 percent; MO:0 to 20 percent; wherein R is 2 O is Li 2 O、Na 2 O、K 2 At least one of O; m is at least one of Mg, ca, sr, zn and Ba. The substrate glass for optical communication prepared by the scheme has higher transmittance in a 960-1600nm wave band, does not change color under the irradiation of space rays, has high elastic modulus and expansion coefficient matched with a plated film, has good heat resistance compared with a substrate for optical communication prepared by plastic, and has low cost compared with a substrate for optical communication prepared by microcrystalline glass.
However, the transparent glass ceramics prepared by the method still have the problems of long melting time, small glass melting rate, poor mechanical strength and the like.
Disclosure of Invention
The invention aims to solve the problems of long melting time, low glass melting rate and poor mechanical strength of the transparent glass ceramics in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a composition for producing a nanocrystalline transparent glass-ceramic, the composition comprising the following components stored independently of each other or in a mixture of two or more of them: quartz sand, aluminum oxide, potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium dioxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium oxide, antimony trioxide and cullet;
based on the total mass of the composition, the quartz sand content is 35-48wt%, the aluminum oxide content is 10-15wt%, the potassium nitrate content is 0.5-3wt%, the sodium carbonate content is 5-11wt%, the calcium carbonate content is 0.2-1.5wt%, the magnesium oxide content is 4.5-9wt%, the titanium dioxide content is 2.2-5wt%, the anhydrous boric anhydride content is 0.2-2.5wt%, the terbium heptaoxide content is 0.5-2.2wt%, the dysprosium oxide content is 0.1-0.6wt%, the antimony trioxide content is 0.1-0.3wt%, and the cullet content is 20-30wt%;
wherein the average grain diameter of the quartz sand is no more than 300 mu m, and the average grain diameter of the broken glass is no more than 5mm.
Preferably, based on the total mass of the composition, the content of the quartz sand is 40-45wt%, the content of the aluminum oxide is 10-12wt%, the content of the potassium nitrate is 1-3wt%, the content of the sodium carbonate is 5-9wt%, the content of the calcium carbonate is 1-1.5wt%, the content of the magnesium oxide is 4.5-6wt%, the content of the titanium dioxide is 2.5-3.5wt%, the content of the anhydrous boric anhydride is 0.5-2wt%, the content of the terbium heptaoxide is 1-2wt%, the content of the dysprosium oxide is 0.3-0.6wt%, the content of the antimony trioxide is 0.1-0.3wt%, and the content of the cullet is 20-27wt%.
Preferably, the composition further comprises Fe 2 O 3 And the Fe is based on the total mass of the composition 2 O 3 The content of (B) is 0.005-0.01wt%.
In a second aspect, the present invention provides a method for preparing a nanocrystalline transparent glass-ceramic, the method comprising:
(1) Mixing water and the components of the composition of the first aspect in contact to obtain a mixed material with a degree of homogeneity of not less than 98%;
(2) Sequentially carrying out first melting treatment on the mixed material in a first container, carrying out second melting treatment in a second container and carrying out homogenization treatment in a third container to obtain a molten material;
wherein the conditions of the first melting process at least include: the temperature is 1480-1580 ℃, and the time is 8-12h; the conditions of the second melting treatment at least include: stirring at 10-20rpm at 1400-1500 deg.C for 5-8 hr; the temperature of the first melting treatment is higher than that of the second melting treatment;
(3) And sequentially carrying out molding, crystallization and annealing on the molten material.
Preferably, in step (1), the water is used in an amount of 3 to 6wt% based on the total mass of the composition.
Preferably, in step (2), the temperature of the first melting process is 60 to 90 ℃ higher, more preferably 70 to 80 ℃ higher, than the temperature of the second melting process.
Preferably, in the step (3), the molding conditions include at least: the temperature is 550-1250 deg.C, and the time is 10-20min.
Preferably, in the step (3), the crystallization conditions at least include: the temperature is 700-950 ℃, and the time is 1-4h.
In a third aspect, the invention provides the nano microcrystalline transparent glass ceramic prepared by the method in the second aspect.
The fourth aspect of the invention provides an application of the nano microcrystalline transparent glass ceramic in the third aspect in mobile phone cover glass.
The invention provides a system for preparing nano microcrystalline transparent glass ceramic, which is applied to the method of the second aspect and comprises a melting area, a forming area and a heat treatment area which are sequentially connected, wherein the melting area comprises a first container, a second container and a third container which are sequentially communicated, the melting area is communicated with the forming area through a leakage injection pipe, the forming area comprises a pouring gate for glass forming and a mesh belt furnace for supporting forming materials, and the heat treatment area comprises a crystallization area and an annealing area.
The nano microcrystalline transparent glass ceramic formed by the composition provided by the invention has the characteristics of low melting temperature and high glass melting rate, and also has excellent mechanical properties such as four-point bending strength and the like.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the present invention;
FIG. 2 is a high-temperature differential scanning calorimetry curve of the nano-microcrystalline transparent glass-ceramic prepared in example 4 of the present invention;
FIG. 3 is a graph of a high temperature linear expansion test curve of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the present invention;
FIG. 4 is an X-ray diffraction energy spectrum of the nano-microcrystalline transparent glass-ceramic prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope photograph of a nanocrystalline transparent glass-ceramic prepared in example 4 of the present invention;
FIG. 6 is a graph showing the transmittance change of the nano-microcrystalline transparent glass-ceramic prepared in example 4 according to the present invention at different wavelengths in the visible light range;
FIG. 7 is a dielectric constant test curve diagram of the nano-microcrystalline transparent glass-ceramic prepared in example 4 of the present invention.
Description of the reference numerals
100. Melting zone 101, first container
102. Second container 103, third container
200. Molding zone 201, gate
202. Mesh belt furnace 300, heat treatment zone
301. Crystallization zone 302, annealing zone
400. A first platinum bushing 500 and a second platinum bushing
600. Third platinum bushing 700, cutting machine
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that, in various aspects of the present invention, the present invention is described only once in one aspect thereof without repeated description with respect to the same components in the aspects, and those skilled in the art should not be construed as limiting the present invention.
It should be noted that in the present invention, the raw materials that are not described can be obtained from general commercial sources, and those skilled in the art can purchase the raw materials according to needs, and in the present invention, detailed description is omitted.
In the present invention, unless otherwise specified, the room temperature or the room temperature both represent 25. + -. 2 ℃.
As described above, the first aspect of the present invention provides a composition for producing a nanocrystalline transparent glass-ceramic, the composition comprising the following components stored independently of each other or in a mixture of two or more of them: quartz sand, aluminum oxide, potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium dioxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium oxide, antimony trioxide and cullet;
based on the total mass of the composition, the content of the quartz sand is 35-48wt%, the content of the aluminum oxide is 10-15wt%, the content of the potassium nitrate is 0.5-3wt%, the content of the sodium carbonate is 5-11wt%, the content of the calcium carbonate is 0.2-1.5wt%, the content of the magnesium oxide is 4.5-9wt%, the content of the titanium dioxide is 2.2-5wt%, the content of the anhydrous boric anhydride is 0.2-2.5wt%, the content of the terbium heptaoxide is 0.5-2.2wt%, the content of the dysprosium oxide is 0.1-0.6wt%, the content of the antimony trioxide is 0.1-0.3wt%, and the content of the cullet is 20-30wt%;
wherein the average grain diameter of the quartz sand is not more than 300 mu m, and the average grain diameter of the broken glass is not more than 5mm.
The components of the cullet are not particularly required, and any glass known in the art can be used, and the cullet can be produced by any production line when the glass is cut, or produced by any production line when the glass quality inspection has defects which do not meet the production requirements, or obtained by melting quartz sand, aluminum oxide, potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium dioxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium trioxide, antimony trioxide and other raw materials in the composition.
Preferably, based on the total mass of the composition, the content of the quartz sand is 40-45wt%, the content of the aluminum oxide is 10-12wt%, the content of the potassium nitrate is 1-3wt%, the content of the sodium carbonate is 5-9wt%, the content of the calcium carbonate is 1-1.5wt%, the content of the magnesium oxide is 4.5-6wt%, the content of the titanium dioxide is 2.5-3.5wt%, the content of the anhydrous boric anhydride is 0.5-2wt%, the content of the terbium heptaoxide is 1-2wt%, the content of the dysprosium trioxide is 0.3-0.6wt%, the content of the antimony trioxide is 0.1-0.3wt%, and the content of the cullet is 20-27wt%. Under the optimal condition, the prepared nano microcrystalline transparent glass ceramic has more excellent mechanical properties.
Preferably, the composition further comprises Fe 2 O 3 And the Fe is based on the total mass of the composition 2 O 3 The content of (B) is 0.005-0.01wt%.
In the present invention, fe is described 2 O 3 Is introduced in the form of impurities.
As previously stated, a second aspect of the present invention provides a method of making a nanocrystalline transparent glass-ceramic, the method comprising:
(1) Mixing water and the components of the composition of the first aspect in contact to obtain a mixed material with a degree of homogeneity of not less than 98%;
(2) Sequentially carrying out first melting treatment on the mixed material in a first container, carrying out second melting treatment in a second container and carrying out homogenization treatment in a third container to obtain a molten material;
wherein the conditions of the first melting process at least include: the temperature is 1480-1580 ℃, and the time is 8-12h; the conditions of the second melting treatment at least include: stirring at 10-20rpm at 1400-1500 deg.C for 5-8 hr; the temperature of the first melting treatment is higher than that of the second melting treatment;
(3) And sequentially carrying out molding, crystallization and annealing on the molten material.
In the research process, the inventor finds that the composition provided by the invention is used for preparing the nano microcrystalline transparent glass ceramic by adopting a graded melting process, and the temperature of the first melting treatment is higher than that of the second melting treatment, so that the glass melting time can be obviously shortened and the glass melting rate can be improved on the premise of ensuring the glass quality.
The mixing sequence is not particularly required in the present invention, and the mixing can be performed by methods known in the art, and in order to obtain a mixed material with higher uniformity, preferably, in step (1), the contact mixing of water and each component of the composition comprises: mixing I potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium dioxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium trioxide and antimony trioxide under a first condition to obtain a mixture A, mixing II water, quartz sand, aluminum oxide and the mixture A under a second condition to obtain a mixture B, and mixing III the mixture B with cullet to obtain the mixed material.
The invention does not require particular equipment for carrying out the mixing I, the mixing II and the mixing III, which can be carried out using equipment known in the art, preferably the mixing I is carried out in a V-type rapid mixer, the mixing II is carried out in a QH-type mixer and the mixing III is carried out using a paddle stirrer.
In the present invention, in the step (1), the uniformity is measured by a conductance method.
Preferably, in step (1), the first condition includes: stirring speed is 5-10rpm, temperature is 20-40 deg.C, and time is 8-40min.
Preferably, in step (1), the second condition includes: stirring speed of 15-20rpm at 20-40 deg.C for 3-5min.
Preferably, in step (1), the third condition includes: stirring speed is 10-20rpm, temperature is 20-40 deg.C, and time is 3-5min.
Preferably, in step (1), the water is used in an amount of 3 to 6wt% based on the total mass of the composition.
Preferably, in step (2), the temperature of the first melting process is 60 to 90 ℃ higher, more preferably 70 to 80 ℃ higher, than the temperature of the second melting process. The inventors have found that, with the more preferred embodiment, it is possible to obtain a nanocrystalline transparent glass-ceramic having a higher melting rate while ensuring the quality of the glass.
Preferably, in step (2), the conditions of the homogenization treatment include at least: the target temperature is 1050-1150 ℃ and the time is 2-4h.
In the present invention, when not described to the contrary, the time of the homogenization treatment is measured from the instant when the temperature is decreased, and the time of the crystallization and the time of the annealing have the same definition, and are not described again here.
Preferably, in the step (3), the molding conditions include at least: the temperature is 550-1250 deg.C, and the time is 10-20min.
Preferably, in step (3), the crystallization conditions at least include: the temperature is 700-950 ℃, the cooling rate is 5-10 ℃/min, and the time is 1-4h.
The annealing operation is not particularly required by the invention, the annealing can be carried out by adopting a method known in the field, and illustratively, the crystallized material is cooled from 700 ℃ to below 50 ℃ at a cooling rate of 5-10 ℃/min in the invention.
In order to obtain the nano microcrystalline transparent glass ceramic with any length, the annealed material in the step (3) can be cut by frying.
As mentioned above, the third aspect of the present invention provides the nanocrystalline transparent glass-ceramic prepared by the method of the second aspect.
As mentioned above, the fourth aspect of the present invention provides the application of the nano-microcrystalline transparent glass-ceramic of the third aspect in cover glass of mobile phone.
As described above, the fifth aspect of the present invention provides a system for preparing a nanocrystalline transparent glass-ceramic, the system being applied to the method according to the second aspect, the system comprising a melting zone 100, a forming zone 200 and a heat treatment zone 300 which are connected in sequence, the melting zone 100 comprising a first container 101, a second container 102 and a third container 103 which are connected in sequence, the melting zone 100 being connected to the forming zone 200 through a leak pipe, the forming zone 200 comprising a gate 201 for glass forming and a mesh belt furnace 202 for holding forming material, and the heat treatment zone 300 comprising a crystallization zone 301 and an annealing zone 302.
Preferably, the first container 101 is communicated with the second container 102 through a first platinum leakage pipe 400, the second container 102 is communicated with the third container 103 through a second platinum leakage pipe 500, and the third container 103 is communicated with the molding zone 200 through a third platinum leakage pipe 600.
Preferably, the system further comprises a fryer 700 coupled to the heat treatment zone 300.
According to a particularly preferred embodiment of the present invention, the materials of the first platinum bushing 400, the second platinum bushing 500 and the third platinum bushing 600 each independently comprise 90-97wt% of metallic platinum and 3-10wt% of metallic palladium.
According to a particularly preferred embodiment of the invention, the material of the gate 201 is 304 stainless steel.
The following provides a preferred embodiment of the present invention for preparing a nanocrystalline transparent glass-ceramic with reference to fig. 1:
(1) Mixing water and the components of the composition of the first aspect in contact to obtain a mixed material with a degree of homogeneity of not less than 98%;
(2) Performing first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid I, allowing the glass liquid I to enter a stirring tank furnace through a first platinum leakage pipe for second melting treatment to obtain glass liquid II, and allowing the glass liquid III to enter a cooling homogenizing furnace through a second platinum leakage pipe for homogenizing treatment to obtain a molten material;
wherein the conditions of the first melting process at least include: the temperature is 1480-1580 ℃, and the time is 8-12h; the conditions of the second melting treatment at least include: stirring at 10-20rpm at 1400-1500 deg.C for 5-8 hr; the temperature of the first melting treatment is higher than that of the second melting treatment;
(3) And the molten material is leaked and injected on the pouring gate through the third platinum leakage pipe, and the molten material falling into the pouring gate is brought into the annealing furnace by the mesh belt furnace to be crystallized and annealed in sequence.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials and instruments used are commercially available unless otherwise specified.
Glass cullet: 30g of potassium nitrate, 90g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 35g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide, 2g of antimony trioxide, 410g of quartz sand and 120g of aluminum oxide are melted at 1500 ℃ for 5 hours and crushed to have an average particle size of 4mm;
quartz sand: average particle size 210 μm, available from Pacific quartz, inc., jiangsu;
in the following examples, the uniformity test method is: taking 100g of mixed materials, putting the mixed materials into a 105 ℃ oven, drying to constant weight, cooling, taking 50g of cooled mixed materials, dividing the cooled mixed materials into 10 groups, each group is 5g, putting each group of cooled mixed materials into a beaker, adding 200mL of pure water, standing for 5min, stirring in a 40rpm magnetic stirrer for 5min, taking out, standing for 5min, detecting by using a conductivity tester respectively, recording the conductivity of each group of mixed materials, solving a standard deviation of the detected conductivity, and calculating the uniformity;
wherein, the calculation formula of the uniformity is as follows: uniformity = (1-standard deviation) × 100%.
Example 1
The embodiment provides a method for preparing nano microcrystalline transparent glass ceramic, which comprises the following steps:
(1) Mixing I30 g of potassium nitrate, 90g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 35g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide under a first condition to obtain a mixture A, mixing II 50g of water, 410g of quartz sand, 120g of aluminum oxide and the mixture A under a second condition to obtain a mixture B, and mixing III the mixture B and 210g of cullet to obtain a mixed material; the uniformity of the mixed material is 98.6%;
wherein the first condition is: stirring speed is 8rpm, temperature is room temperature, and time is 25min;
the second condition is: the stirring speed was 18rpm, the temperature was room temperature and the time was 3min.
The third condition is: stirring at 15rpm at room temperature for 3min;
(2) Carrying out first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid I, enabling the glass liquid I to enter a stirring tank furnace through a first platinum leakage pipe to carry out second melting treatment to obtain glass liquid II, enabling the glass liquid II to enter a cooling homogenizing furnace through a second platinum leakage pipe, and cooling to 1115 ℃ through 4 hours to obtain a molten material;
wherein the conditions of the first melting treatment are as follows: the temperature is 1525 ℃, and the time is 11h;
the conditions of the second melting treatment are as follows: stirring at 1445 ℃ for 7h at 18 rpm;
(3) The molten material is leaked and injected on the pouring gate through the third platinum leakage pipe for molding, the molten material falling into the pouring gate is brought into an annealing furnace at 750 ℃ by a mesh belt furnace, and after crystallization is carried out for 2 hours, the temperature is reduced from 700 ℃ to room temperature at the cooling rate of 8 ℃/min, so that the nano microcrystalline transparent glass ceramic is obtained;
wherein the molding conditions are as follows: the temperature was 1150 ℃ and the time was 15min.
Example 2
The embodiment provides a method for preparing nano microcrystalline transparent glass ceramic, which comprises the following steps:
(1) Mixing I30 g of potassium nitrate, 50g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 35g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide under a first condition to obtain a mixture A, mixing II 40g of water, 400g of quartz sand, 110g of aluminum oxide and the mixture A under a second condition to obtain a mixture B, and mixing III the mixture B and 270g of cullet to obtain a mixed material; the uniformity of the mixed material is 98.9%;
wherein the first condition is: stirring speed is 8rpm, temperature is room temperature, and time is 30min;
the second condition is: the stirring speed was 18rpm, the temperature was room temperature and the time was 3min.
The third condition is: stirring at 15rpm at room temperature for 3min;
(2) Carrying out first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid I, enabling the glass liquid I to enter a stirring tank furnace through a first platinum leakage pipe to carry out second melting treatment to obtain glass liquid II, enabling the glass liquid II to enter a cooling homogenizing furnace through a second platinum leakage pipe, and cooling to 1120 ℃ for 4 hours to obtain a molten material;
wherein the conditions of the first melting treatment are as follows: the temperature is 1540 ℃, and the time is 12h;
the conditions of the second melting treatment are as follows: the stirring speed is 20rpm, the temperature is 1465 ℃, and the time is 8 hours;
(3) The molten material is leaked and injected on the pouring gate through the third platinum leakage pipe for molding, the molten material falling into the pouring gate is brought into an annealing furnace at 850 ℃ by a mesh belt furnace, and after crystallization is carried out for 4 hours, the temperature is reduced from 700 ℃ to room temperature at the cooling rate of 10 ℃/min to obtain nano microcrystalline transparent glass ceramic;
wherein the molding conditions are as follows: the temperature is 1235 deg.C and the time is 9min.
Example 3
The embodiment provides a method for preparing nano microcrystalline transparent glass ceramic, which comprises the following steps:
(1) Mixing I30 g of potassium nitrate, 70g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 25g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide under a first condition to obtain a mixture A, mixing II 60g of water, 450g of quartz sand, 120g of aluminum oxide and the mixture A under a second condition to obtain a mixture B, and mixing III the mixture B and 200g of cullet to obtain a mixed material; the uniformity of the mixed material is 98.7%;
wherein the first condition is: stirring speed is 8rpm, temperature is room temperature, and time is 35min;
the second condition is: the stirring speed was 18rpm, the temperature was room temperature and the time was 3min.
The third condition is: stirring at 15rpm at room temperature for 3min;
(2) Carrying out first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid I, enabling the glass liquid I to enter a stirring tank furnace through a first platinum leakage pipe to carry out second melting treatment to obtain glass liquid II, enabling the glass liquid II to enter a cooling homogenizing furnace through a second platinum leakage pipe, and cooling to 1130 ℃ for 4 hours to obtain a molten material;
wherein the conditions of the first melting treatment are as follows: the temperature is 1550 ℃ and the time is 10h;
the conditions of the second melting treatment are as follows: the stirring speed is 15rpm, the temperature is 1475 ℃, and the time is 8 hours;
(3) The molten material is leaked and injected on the pouring gate through the third platinum leakage pipe for molding, the molten material falling into the pouring gate is brought into an annealing furnace with the temperature of 890 ℃ by a mesh belt furnace, and after crystallization is carried out for 4 hours, the temperature is reduced from 700 ℃ to room temperature at the cooling rate of 8 ℃/min, so that the nano microcrystalline transparent glass ceramic is obtained;
wherein the molding conditions are as follows: the temperature is 1250 ℃ and the time is 9min.
Example 4
The embodiment provides a method for preparing nano microcrystalline transparent glass ceramic, which comprises the following steps:
(1) Mixing I with 20g of potassium nitrate, 110g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 25g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide under a first condition to obtain a mixture A, mixing II with 30g of water, 350g of quartz sand, 140g of aluminum oxide and the mixture A under a second condition to obtain a mixture B, and mixing III with 250g of cullet to obtain a mixed material; the uniformity of the mixed material is 98.5%;
wherein the first condition is: stirring speed is 8rpm, temperature is room temperature, and time is 20min;
the second condition is: the stirring speed was 18rpm, the temperature was room temperature and the time was 3min.
The third condition is: stirring at 15rpm at room temperature for 3min;
(2) Carrying out first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid I, enabling the glass liquid I to enter a stirring tank furnace through a first platinum leakage pipe to carry out second melting treatment to obtain glass liquid II, enabling the glass liquid II to enter a cooling homogenizing furnace through a second platinum leakage pipe, and cooling to 1060 ℃ for 4 hours to obtain a molten material;
wherein the conditions of the first melting treatment are as follows: the temperature is 1485 ℃ and the time is 8h;
the conditions of the second melting treatment are as follows: the stirring speed is 10rpm, the temperature is 1415 ℃, and the time is 5h;
(3) The molten material is leaked and injected on the pouring gate through the third platinum leakage pipe for molding, the molten material falling into the pouring gate is brought into an annealing furnace at 750 ℃ by a mesh belt furnace, and after 2h of crystallization, the temperature is reduced from 700 ℃ to room temperature at the cooling rate of 5 ℃/min, so that the nano microcrystalline transparent glass ceramic is obtained;
wherein the molding conditions are as follows: the temperature is 1130 deg.C and the time is 9min.
Example 5
A nanocrystalline transparent glass-ceramic was prepared by the method of example 1 except that in step (1), 30g of potassium nitrate, 100g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 25g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of tetrapyrodybium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide were mixed I under the first condition to obtain a mixture A, and 50g of water, 370g of quartz sand, 130g of aluminum oxide and the mixture A were mixed II under the second condition to obtain a mixture B, and the mixture B was mixed III with 240g of cullet to obtain the mixed material.
The rest of the procedure was the same as in example 1.
Example 6
A nanocrystalline transparent glass ceramic was prepared by the method of example 1, except that, in step (2), the temperature of the first melting treatment was 1535 ℃.
The rest of the procedure was the same as in example 1.
Example 7
A nanocrystalline transparent glass ceramic was prepared by the method of example 1, except that, in step (2), the temperature of the second melting process was 1465 ℃.
The rest of the procedure was the same as in example 1.
Example 8
A nanocrystalline transparent glass-ceramic was prepared according to the method of example 1, except that, in the step (2), the melting treatment was performed only once;
the specific operation method comprises the following steps:
(1) Same as in step (1) of example 1;
(2) Carrying out first melting treatment on the mixed material in a glass tank furnace to obtain glass liquid, entering a cooling homogenizing furnace through a second platinum leakage pipe, and cooling to 1115 ℃ after 4 hours to obtain a molten material;
wherein the conditions of the first melting treatment are as follows: the temperature is 1525 ℃ and the time is 18h;
(3) Same as in step (3) of example 1.
Comparative example 1
A nanocrystalline transparent glass-ceramic was prepared according to the method of example 1, except that in step (1), 30g of potassium nitrate, 40g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 35g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide were mixed I under the first condition to obtain a mixture A, 50g of water, 500g of quartz sand, 95g of aluminum oxide and the mixture A were mixed II under the second condition to obtain a mixture B, and the mixture B was mixed III with 195g of cullet to obtain the mixed material.
The rest of the procedure was the same as in example 1.
Comparative example 2
A nanocrystalline transparent glass-ceramic was prepared according to the method of example 1, except that in step (1), 30g of potassium nitrate, 120g of sodium carbonate, 10g of calcium carbonate, 50g of magnesium oxide, 35g of titanium dioxide, 20g of anhydrous boric anhydride, 20g of terbium heptaoxide, 3g of dysprosium trioxide and 2g of antimony trioxide were mixed I under the first condition to obtain a mixture A, 50g of water, 300g of quartz sand, 160g of aluminum oxide and the mixture A were mixed II under the second condition to obtain a mixture B, and the mixture B was mixed III with 250g of cullet to obtain the mixed material.
The remaining procedure was the same as in example 1.
Test example
The nano microcrystalline transparent glass ceramics prepared in the examples and the comparative examples are subjected to performance tests, wherein the performance tests comprise density, four-point bending strength, crystallization temperature, linear expansion coefficient, expansion transition temperature, expansion softening temperature, light transmittance and melting rate, and specific test results are shown in table 1.
Wherein, the density of the glass is measured by adopting an Archimedes method;
four-point bending strength was measured using a universal testing machine with reference to ASTM E-1820;
the crystallization temperature was measured using an STA-409 differential scanning calorimeter (from Chinesco, germany);
the linear expansion coefficient, the expansion transition temperature and the expansion softening temperature were measured by a DIL402PC thermal expansion instrument (available from Nachi Germany);
measuring the light transmittance of glass with the thickness of 0.68mm at the wavelength of 550nm by using a GD 751-type spectrophotometer (purchased from Tianjin Telius technologies, inc.);
the melting rate is calculated as: 0.024Q/Q, formula (1);
in the formula (1), Q represents the amount of heat transferred to a unit melting area by the combustion flame, and has a unit of kj/m 2 ·h；
q represents the heat required to melt 1kg of molten glass in kj/kg.
TABLE 1
| Example numbering | Density, g/cm 3 | Four point bending strength, MPa | Crystallization temperature,. Degree.C | Light transmittance% |
| Example 1 | 2.61 | 470 | 891.5 | 92.8 |
| Example 2 | 2.59 | 440 | 870.1 | 91.2 |
| Example 3 | 2.64 | 460 | 890.6 | 91.1 |
| Example 4 | 2.58 | 430 | 890.9 | 91.6 |
| Example 5 | 2.61 | 410 | 870.4 | 90.2 |
| Example 6 | 2.58 | 463 | 879.5 | 90.5 |
| Example 7 | 2.54 | 468 | 880.6 | 90.5 |
| Example 8 | 2.61 | 452 | 869 | 90.7 |
| Comparative example 1 | 2.56 | 389 | 715 | 89.5 |
| Comparative example 2 | 5.54 | 359 | 682 | 88.7 |
Table 1 (continuation watch)
| Example numbering | Coefficient of linear expansion,. Degree.C | Expansion transition temperature,. Degree.C | Expansion softening temperature,. Degree.C | Melting Rate, t/m 2 .d |
| Example 1 | 93.3×10 -7 | 712.9 | 846.2 | 4.1 |
| Example 2 | 92.4×10 -7 | 710.4 | 860.7 | 3.8 |
| Example 3 | 92.8×10 -7 | 700.5 | 870.4 | 3.8 |
| Example 4 | 95.3×10 -7 | 670.1 | 753.0 | 3.8 |
| Example 5 | 96.5×10 -7 | 690.8 | 831.2 | 3.9 |
| Example 6 | 95.8×10 -7 | 710.5 | 865.2 | 4.0 |
| Example 7 | 96.8×10 -7 | 695.9 | 875.1 | 3.9 |
| Example 8 | 95.7×10 -7 | 705.8 | 876.2 | 3.5 |
| Comparative example 1 | 100.2×10 -7 | 728.9 | 894.8 | 3.6 |
| Comparative example 2 | 99.8×10 -7 | 732.1 | 895.7 | 3.7 |
The results in table 1 show that the composition provided by the invention is used for preparing the nano microcrystalline transparent glass ceramic by adopting a graded melting process, and the temperature of the first melting treatment is higher than that of the second melting treatment, so that the glass melting time can be obviously shortened and the glass melting rate can be improved on the premise of ensuring the glass quality.
The invention exemplarily provides a high-temperature differential scanning calorimetry analysis curve, a high-temperature linear expansion test curve map, an X-ray diffraction energy spectrum, a scanning electron microscope picture, a light transmittance picture in a visible light range and a dielectric constant test curve of the nano microcrystalline transparent glass ceramic prepared in the embodiment 4 of the invention, which are respectively shown in fig. 2 to fig. 7.
The STA-409 differential scanning calorimeter (from Asahi-Schlegel, germany) of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the invention is used for measuring the crystallization temperature, and the specific test result is shown in figure 2.
As can be seen from FIG. 2, the devitrification temperature of the nano-crystalline transparent glass ceramic prepared in example 4 of the present invention is 890.9 ℃.
The linear expansion coefficient, expansion transition temperature and expansion softening temperature of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the present invention were measured by a DIL402PC thermal expansion instrument (available from sans, germany) and the results are shown in fig. 3.
As can be seen from FIG. 3, the linear expansion coefficient of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the present invention is 95.3 × 10 within the range of α 50-450 deg.C -7 The expansion transition temperature is 670.1 ℃ per DEG C, and the expansion softening temperature is 753.0 ℃.
The crystallinity and the crystal grain size of the nano-crystallite transparent glass ceramic prepared in example 4 of the present invention were measured by an X-ray diffractometer (model ARL EQUINOX 3000, available from shanghaidi instruments science and technology ltd), and the measurement results are shown in fig. 4.
As can be seen from FIG. 4, the nanocrystalline transparent glass-ceramic prepared in example 4 of the present invention has a crystallinity of 97.88% and a grain size of 1.5nm.
The microstructure of the nano-crystalline transparent glass ceramic prepared in example 4 of the present invention was observed by a JMS-5610LV type scanning electron microscope (available from Japan Electron Co., ltd.), and the specific results are shown in FIG. 5.
As can be seen from FIG. 5, the crystals in the nano-microcrystalline transparent glass-ceramic prepared in example 4 of the present invention are 1-10nm spherical or spheroidal and are uniformly distributed.
The transmittance of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the present invention in the visible light range was measured by using a GD751 type spectrophotometer (available from tianjin delusters technologies ltd.) when the thickness was 0.68mm, and the specific test result is shown in fig. 6.
As can be seen from FIG. 6, the transmittance of the nano-microcrystalline transparent glass ceramic prepared in example 4 of the present invention at a wavelength of 550nm is 91.6% at a thickness of 0.68 mm.
The dielectric properties of the nano-microcrystalline transparent glass ceramic prepared in example 4 and prepared by the method of the present invention were measured at a frequency of 20Hz to 1MHz using an impedance analyzer (model No. E4991A, available from Blueautomated science and technology Co., ltd., dongguan), and the results are shown in FIG. 7.
As can be seen from FIG. 7, the dielectric constant of the nano microcrystalline transparent glass ceramic prepared by the invention is 10 after 200KHz, and is relatively stable.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for preparing a nanocrystalline transparent glass-ceramic, the composition comprising the following components stored independently of each other or in a mixture of two or more of them: quartz sand, aluminum oxide, potassium nitrate, sodium carbonate, calcium carbonate, magnesium oxide, titanium dioxide, anhydrous boric anhydride, terbium heptaoxide, dysprosium oxide, antimony trioxide and cullet;
based on the total mass of the composition, the content of the quartz sand is 35-48wt%, the content of the aluminum oxide is 10-15wt%, the content of the potassium nitrate is 0.5-3wt%, the content of the sodium carbonate is 5-11wt%, the content of the calcium carbonate is 0.2-1.5wt%, the content of the magnesium oxide is 4.5-9wt%, the content of the titanium dioxide is 2.2-5wt%, the content of the anhydrous boric anhydride is 0.2-2.5wt%, the content of the terbium heptaoxide is 0.5-2.2wt%, the content of the dysprosium oxide is 0.1-0.6wt%, the content of the antimony trioxide is 0.1-0.3wt%, and the content of the cullet is 20-30wt%;
wherein the average grain diameter of the quartz sand is not more than 300 mu m, and the average grain diameter of the broken glass is not more than 5mm.
2. The composition according to claim 1, wherein the quartz sand is present in an amount of 40 to 45wt%, the aluminum oxide is present in an amount of 10 to 12wt%, the potassium nitrate is present in an amount of 1 to 3wt%, the sodium carbonate is present in an amount of 5 to 9wt%, the calcium carbonate is present in an amount of 1 to 1.5wt%, the magnesium oxide is present in an amount of 4.5 to 6wt%, the titanium dioxide is present in an amount of 2.5 to 3.5wt%, the anhydrous boric anhydride is present in an amount of 0.5 to 2wt%, the terbium heptaoxide is present in an amount of 1 to 2wt%, the dysprosium oxide is present in an amount of 0.3 to 0.6wt%, the antimony trioxide is present in an amount of 0.1 to 0.3wt%, and the cullet is present in an amount of 20 to 27wt%, based on the total mass of the composition.
3. The composition of claim 1 or 2, further comprising Fe 2 O 3 And the Fe is based on the total mass of the composition 2 O 3 The content of (B) is 0.005-0.01wt%.
4. A method of making a nanocrystalline transparent glass-ceramic, the method comprising:
(1) Mixing water and the components of the composition of any one of claims 1 to 3 in contact with each other to obtain a mixed material with an evenness degree of not less than 98%;
(2) Sequentially carrying out first melting treatment on the mixed material in a first container, carrying out second melting treatment in a second container and carrying out homogenization treatment in a third container to obtain a molten material;
wherein the conditions of the first melting process at least include: the temperature is 1480-1580 ℃, and the time is 8-12h; the conditions of the second melting treatment at least include: stirring at 10-20rpm at 1400-1500 deg.C for 5-8 hr; the temperature of the first melting treatment is higher than that of the second melting treatment;
(3) And sequentially carrying out molding, crystallization and annealing on the molten material.
5. The method according to claim 4, wherein in step (1), the water is used in an amount of 3 to 6wt% based on the total mass of the composition.
6. The method according to claim 4 or 5, wherein in step (2) the temperature of the first melting process is 60-90 ℃, preferably 70-80 ℃ higher than the temperature of the second melting process.
7. The method according to any one of claims 4 to 6, wherein in step (3), the molding conditions include at least: the temperature is 550-1250 ℃, and the time is 10-20min; and/or
In the step (3), the crystallization conditions at least include: the temperature is 700-950 ℃, and the time is 1-4h.
8. Nanocrystalline transparent glass-ceramics obtainable by the process according to any one of claims 4 to 7.
9. The application of the nano microcrystalline transparent glass ceramic in cover glass of a mobile phone.
10. A system for preparing nanocrystalline transparent glass-ceramics, which is applied to the method according to claims 4-7, characterized by comprising a melting zone (100), a forming zone (200) and a heat treatment zone (300) connected in sequence, wherein the melting zone (100) comprises a first container (101), a second container (102) and a third container (103) which are connected in sequence, the melting zone (100) is communicated with the forming zone (200) through a drain pipe, the forming zone (200) comprises a sprue (201) for glass forming and a mesh belt furnace (202) for supporting forming materials, and the heat treatment zone (300) comprises a crystallization zone (301) and an annealing zone (302).
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100126225A1 (en) * | 2008-11-25 | 2010-05-27 | Josh Ding | Method for homogenizing a glass melt |
| CN104496186A (en) * | 2014-12-31 | 2015-04-08 | 海南大学 | Cordierite-based nanometer glass-ceramic and preparation method thereof |
| CN105236733A (en) * | 2015-09-09 | 2016-01-13 | 湖北戈碧迦光电科技股份有限公司 | Titanium-containing high-lanthanum and low-niobium optical glass preparation method |
| CN105621869A (en) * | 2014-10-31 | 2016-06-01 | 陕西盛迈石油有限公司 | Large-size mesh-belt type annealing furnace for touch screen glass |
| CN206556416U (en) * | 2017-03-06 | 2017-10-13 | 东莞市鑫迪机械设备有限公司 | A kind of modified meshbeltfurnace heating system insulation construction |
| CN211226887U (en) * | 2019-09-27 | 2020-08-11 | 成都光明光电股份有限公司 | Forming device for optical glass strip material with extremely thick specification |
| CN111592224A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Magnesium aluminum silicate nanocrystalline transparent ceramic, preparation method and product thereof |
| CN216273748U (en) * | 2021-09-29 | 2022-04-12 | 宜兴市艳阳天炉业有限公司 | Continuous uniform annealing mesh belt furnace for optical glass strip |
-
2022
- 2022-06-07 CN CN202210642053.8A patent/CN115159853A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100126225A1 (en) * | 2008-11-25 | 2010-05-27 | Josh Ding | Method for homogenizing a glass melt |
| CN105621869A (en) * | 2014-10-31 | 2016-06-01 | 陕西盛迈石油有限公司 | Large-size mesh-belt type annealing furnace for touch screen glass |
| CN104496186A (en) * | 2014-12-31 | 2015-04-08 | 海南大学 | Cordierite-based nanometer glass-ceramic and preparation method thereof |
| CN105236733A (en) * | 2015-09-09 | 2016-01-13 | 湖北戈碧迦光电科技股份有限公司 | Titanium-containing high-lanthanum and low-niobium optical glass preparation method |
| CN206556416U (en) * | 2017-03-06 | 2017-10-13 | 东莞市鑫迪机械设备有限公司 | A kind of modified meshbeltfurnace heating system insulation construction |
| CN211226887U (en) * | 2019-09-27 | 2020-08-11 | 成都光明光电股份有限公司 | Forming device for optical glass strip material with extremely thick specification |
| CN111592224A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Magnesium aluminum silicate nanocrystalline transparent ceramic, preparation method and product thereof |
| CN216273748U (en) * | 2021-09-29 | 2022-04-12 | 宜兴市艳阳天炉业有限公司 | Continuous uniform annealing mesh belt furnace for optical glass strip |
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