CN116477930A - Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent - Google Patents
Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent Download PDFInfo
- Publication number
- CN116477930A CN116477930A CN202310264663.3A CN202310264663A CN116477930A CN 116477930 A CN116477930 A CN 116477930A CN 202310264663 A CN202310264663 A CN 202310264663A CN 116477930 A CN116477930 A CN 116477930A
- Authority
- CN
- China
- Prior art keywords
- nucleating agent
- transparent ceramic
- nanocrystalline
- metal nucleating
- size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000137 annealing Methods 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000005674 electromagnetic induction Effects 0.000 claims abstract description 28
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010955 niobium Substances 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 31
- 238000000498 ball milling Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 239000011812 mixed powder Substances 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 15
- 239000002419 bulk glass Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005347 annealed glass Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000005036 potential barrier Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000008235 industrial water Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000004476 mid-IR spectroscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/404—Refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention discloses a method for preparing large-size nanocrystalline transparent ceramic by a nano metal nucleating agent, which comprises the following steps: a is that 1.1 Al 2.2 Si 1.8 O 8 Wherein A is one of Sr, ca and Ba, and is prepared by adopting a glass full crystallization method, a nano metal nucleating agent is added in the preparation, the nano metal nucleating agent is one of tungsten, molybdenum, tantalum and niobium, the adding amount of the nano metal nucleating agent is 0.005-0.01 according to the mole percentage, and the size of the nano metal nucleating agent is 40-80 nm. According to the invention, the nano metal nucleating agent is added into the aluminosilicate component, and then the improved electromagnetic induction annealing platform is combined, so that on one hand, the in-situ uniform heating of the large-size glass precursor is realized, and the controlled crystallization is realized; on the other hand, the nucleating agent can change the crystallization mode from surface crystallization to bulk crystallization mode, reduce crystallization temperature and crystallization potential barrier, thereby obtaining large-size nano-crystalline silicate ceramic with simple process,the method is environment-friendly and can be industrialized.
Description
Technical Field
The invention belongs to the technical field of transparent ceramic material preparation, and particularly relates to a method for preparing large-size nanocrystalline transparent ceramic by using a nano metal nucleating agent.
Background
Transparent ceramics are polycrystalline materials that allow the passage of incident photons without significant absorption and internal scattering. Compared with other optical materials such as glass, single crystal and the like, the transparent ceramic not only has good transparency, but also has the advantages of high strength, high hardness, high heat conductivity, corrosion resistance and the like, and has important application in the fields of illumination, laser, transparent armor and the like. At present, the preparation of transparent ceramics mainly adopts the classical ceramic preparation process, and the basic steps of the preparation of the transparent ceramics comprise powder preparation, dry pressing or cold isostatic pressing and sintering. However, the transparent ceramic is prepared by using a classical preparation process, which has extremely severe requirements on raw materials, equipment, molding and sintering processes, and high-purity, high-dispersivity and high-sintering-activity nano powder and high-temperature and high-pressure equipment are often required, so that high cost is caused, and further commercialization of the nano powder is limited.
The glass full crystallization method is a new method for obtaining ceramic materials by carrying out heating treatment on bulk glass and fully controlling crystallization. The method uses the glass method, and is very expected to realize the preparation of transparent ceramics with large size. Meanwhile, the glass is obtained by cooling and solidifying a melt, so that common raw material powder is used, the dependence of the traditional ceramic technology on nanoscale raw materials is avoided, and high density is realized without expensive high-temperature and high-pressure sintering equipment because the glass is natural and has no pores. Thus, this method is expected to significantly reduce the cost of transparent ceramics. However, since most transparent ceramic components do not contain glass network formers, the size of such ceramics prepared by the glass total crystallization method is only 1 to 5mm, and it is obviously difficult to meet the practical application requirements. In addition, due to the poor thermal conductivity of glass, for large-sized glass precursors, it is difficult to achieve uniform heating and controlled crystallization to obtain a specific microstructure, and thus it is difficult to prepare large-sized transparent full-crystallization ceramic materials.
Allix.M et al report a large Sr size 1.1 Al 2.2 Si 1.8 O 8 Hexagonal phase silicate transparent ceramics (diameter-30 mm, thickness-1.5 mm) and exhibit very high optical transmittance T 800nm 90% (DOI: 10.1021/cm 5037106). The precipitated grains of the ceramic show high orientation, so that the non-cubic silicate ceramic with micron-sized grains shows very high transmittance. However, the transmission mechanism based on highly oriented grains severely limits its thickness, making the transparent material very thin, and highly oriented micron-sized grains make the mechanical properties of the material undesirable, which all limit its application in transparent armor. Therefore, the development of a method for preparing large-size nanocrystalline aluminosilicate transparent ceramics is of great importance.
Disclosure of Invention
One of the purposes of the invention is to provide a method for preparing large-size nanocrystalline transparent ceramics by using a nano metal nucleating agent.
The second object of the present invention is to provide a large-sized, nanocrystalline transparent ceramic produced by the above method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides a method for preparing large-size nanocrystalline transparent ceramic by using a nano metal nucleating agent, which adopts a glass total crystallization method and comprises the following specific operation steps:
(a) Pressing the buttonAccording to chemical formula A 1.1 Al 2.2 Si 1.8 O 8 The stoichiometric ratio of each element respectively weighs A with the purity of more than 99.99 percent 2 CO 3 、Al 2 O 3 、SiO 2 As a raw material, adding a nano metal nucleating agent, performing wet ball milling on the powder mixture, and drying to obtain mixed powder; wherein A is one of Ca, sr and Ba, the nano metal nucleating agent is one of tungsten W, molybdenum Mo, tantalum Ta and niobium Nb, the adding amount of the nano metal nucleating agent is 0.005-0.01 according to mole percent, and the size is 40-80 nm;
(b) Placing the mixed powder into a crucible of an electromagnetic induction smelting furnace, introducing inert gas into the furnace, then raising the temperature, performing a powder calcining procedure, and then continuously raising the temperature of the mixed powder until the mixed powder is completely melted;
(c) Operating an electromagnetic induction smelting furnace, casting the mixed powder melt onto a water-cooling copper mold for cooling and solidifying to obtain a bulk glass precursor;
(d) Operating an electromagnetic induction melting furnace, placing a glass precursor in an annealing platform wound by an electromagnetic induction coil, and annealing the bulk glass; and then continuously heating the annealed glass precursor in an annealing platform for crystallization treatment, and finally obtaining the aluminosilicate transparent ceramic.
Preferably, in the step (a), the ball milling medium of the wet ball milling is ethanol, the ball milling time is 10-20 h, the ball milling rotating speed is 200r/min, and the ball-to-material ratio is 1.2:1.
Preferably, in step (b), the crucible is one of a graphite, platinum rhodium or tungsten crucible.
Preferably, in the step (b), the inert gas is one of argon, nitrogen or a mixed gas of the argon and the nitrogen, and the flow rate is 4-8L/min.
Preferably, in the step (b), the temperature rising rate is 80-120 ℃/min, the powder calcining process is 800-1000 ℃, the temperature is kept for 7-13 h, the melting process is 1500-1800 ℃, and the temperature is kept for 0.2-3 h.
Preferably, in the step (c), the temperature of the water-cooled copper mold is controlled by an industrial water chiller, the temperature of the copper plate is always less than or equal to 35 ℃, and the cooling rate during cooling is 200-300 ℃/min.
Preferably, in the step (d), the annealing temperature is 700-950 ℃ and the annealing time is 3-18 h.
Preferably, in the step (d), the crystallization treatment mode is 950-1100 ℃, and the heat treatment is carried out for 0.2-10 hours.
On the other hand, the invention also provides the large-size nano-crystalline aluminosilicate transparent ceramic prepared by the preparation method.
The aluminosilicate transparent ceramic is a completely devitrified ceramic material, and the size of ceramic grains is 50-100 nm.
In the aluminosilicate transparent ceramic, the nano metal nucleating agent is a necessary condition, and the glass crystallization can be changed into a bulk crystallization mode from surface crystallization only when the condition is met, so that the large-size glass can be uniformly heated, the microstructure of special nano grains is obtained, and the nano-size nucleating agent does not influence the optical transmittance of the material.
The aluminosilicate transparent ceramic of the present invention has a large size (100X 100-500X 500 mm) 2 ) Nano-grain (GS 50-100 nm) and high optical transmittance (T) 800nm --70～85％)。
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is implemented by the method shown in the A 1.1 Al 2.2 Si 1.8 O 8 The nano metal nucleating agent is added into the aluminosilicate component, and then the electromagnetic induction annealing platform is combined and improved, so that on one hand, the in-situ uniform heating of the large-size glass precursor can be realized, the controlled crystallization can be well realized, and the microstructure can be controlled; on the other hand, the nucleating agent can change the crystallization mode from surface crystallization to bulk crystallization mode, and reduce crystallization temperature and crystallization potential barrier, thereby obtaining large-size nano-crystalline silicate ceramic, wherein the grain size is 50-100 nm; in addition, the nano-metal nucleating agent does not affect the optical transmittance of the material itself due to nano-scale.
2. The transparent ceramic of the present invention has a large size (100X 100 to 500X 500 mm) 2 ) Nano-grain (GS 50-100 nm) and high optical transmissionRate (T) 800nm 70-85 percent), wherein the special nano grain structure not only can obtain high optical transmittance, but also can obviously improve the mechanical property of the nano grain structure, so that the aluminosilicate transparent ceramic prepared by the invention can be used in the national defense fields such as transparent armor and the like.
3. The invention adopts the glass full crystallization method to prepare the large-size nanocrystalline transparent ceramic, has simple process, does not need high-cost nano spherical powder, high-pressure forming and sintering equipment, has high price advantage, is green and environment-friendly, and can be applied to engineering preparation.
Drawings
FIG. 1 is a schematic diagram of an electromagnetic induction melting furnace constructed in accordance with the present invention; in the figure, a 1-electromagnetic induction coil, a 2-crucible, a 3-water-cooled copper mold, a 4-furnace tilting handle, a 5-cylinder, a 6-annealing platform and a 7-industrial water chiller are shown;
FIG. 2 is a diagram of a transparent ceramic material according to example 1 of the present invention;
FIG. 3 is an XRD pattern of a sample prepared in example 1 of the present invention;
FIG. 4 is a cross-sectional SEM image of a sample prepared according to example 1 of the present invention;
FIG. 5 is a graph showing transmittance of a sample prepared in example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The implementation of the invention requires setting up a set of electromagnetic induction smelting furnace device, as shown in figure 1, the electromagnetic induction smelting furnace device comprises a smelting furnace, a water-cooling copper mold 3, an annealing platform 6 and an industrial water chiller 7, wherein the smelting furnace comprises a furnace body, a crucible 2 and an electromagnetic induction coil 1, the electromagnetic induction coil 1 is wound on the peripheral wall of the crucible 2, the crucible 2 is arranged in the furnace body, an electromagnetic field is generated through the electromagnetic induction coil 1, the crucible 2 heats, and a furnace tilting handle 4 for manually tilting the furnace body is further arranged on one side of the furnace body.
The water-cooling copper mold 3 is arranged right below the furnace body, the temperature of the water-cooling copper mold 3 is controlled by the industrial water chiller 7, and the opening and closing of the water-cooling copper mold is controlled by the air cylinder 5.
The annealing platform 6 is arranged under the water-cooled copper mold 3, the electromagnetic induction coil 1 is wound on the peripheral wall of the annealing platform 6, and an electromagnetic field is generated through the electromagnetic induction coil 1, so that the annealing platform 6 heats. The annealing platform 6 is integrated in the smelting furnace, so that a rapid annealing function can be realized, and the annealing treatment and the crystallization treatment can be performed through the annealing platform 6.
Example 1: preparation of 0.992Sr 1.1 Al 2.2 Si 1.8 O 8 -0.008W transparent ceramic
The Sr with the purity more than 99.99 percent is weighed according to the mole ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 15 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon into the furnace, heating at a speed of 6L/min and a heating rate of 100 ℃/min, preserving the temperature at 900 ℃ for 10 hours for calcining the powder, and then raising the temperature to 1750 ℃ for 1 hour for completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; and operating the air cylinder 5 to open the mould, placing the glass in the annealing platform 6, preserving the temperature at 850 ℃ for 8 hours, performing annealing heat treatment to remove internal stress, performing heat treatment on the glass doped with the metal nucleating agent through an electromagnetic induction coil on the annealing platform, and preserving the temperature at 1030 ℃ for 5 hours to finally obtain the silicate transparent ceramic.
Fig. 2 is an optical photograph of the silicate transparent piezoelectric ceramic of the present example 1.
FIG. 3 is an XRD pattern of a sample prepared in accordance with example 1, showing that the ceramic is fully crystallized Sr 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics.
FIG. 4 is a SEM image of a cross-section of a sample prepared in this example 1, which shows that the average size of the crystal grains is 55nm. Therefore, the nano metal nucleating agent and the designed annealing platform consisting of the electromagnetic induction coil can obtain transparent ceramics with nano grains.
FIG. 5 is a graph showing the transmittance of the sample prepared in example 1 of the present invention, which shows that the transmittance is very high in a very wide range of the mid-IR spectrum, and the transmittance at 800nm is 85%.
Example 2: preparation of 0.995Sr 1.1 Al 2.2 Si 1.8 O 8 -0.005W transparent ceramic
The Sr with the purity more than 99.99 percent is weighed according to the mole ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 10 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 4L/min and a heating rate of 80 ℃/min, preserving heat at 800 ℃ for 13h for calcining, and then raising the temperature to 1800 ℃ for 0.2h for completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 900 ℃ for 3 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 1100 ℃ for 0.5 hour, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 2 is similar to that of FIG. 3, and is fully crystallized Sr 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in table 1, the average grain size of the sample prepared in example 2 was 85nm. The optical transmittance at 800nm was 81%.
Example 3: preparation of 0.99Sr 1.1 Al 2.2 Si 1.8 O 8 -0.01W transparent ceramic
The Sr with the purity more than 99.99 percent is weighed according to the mole ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 20 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 8L/min and a heating rate of 120 ℃/min, preserving heat at 1000 ℃ for 7h for calcining, and then raising the temperature to 1720 ℃ for 3 daysh, completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto a 3-water-cooling copper mold for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 820 ℃ for 13h, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 1000 ℃ for 10h, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 3 is similar to that of FIG. 3, and is fully crystallized Sr 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 3 was 70nm. Its optical transmission at 800nm was 83%.
Example 4 preparation of 0.995Ca 1.1 Al 2.2 Si 1.8 O 8 -0.005W transparent ceramic
Weighing Ca with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 10 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 4L/min and a heating rate of 80 ℃/min, preserving heat at 800 ℃ for 13h for calcining powder, and then raising the temperature to 1590 ℃ for preserving heat for 0.2h to enable the mixed powder to be completely melted; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 800 ℃ for 5 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 1000 ℃ for 0.5 hour, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 4 is similar to that of FIG. 3, and is fully crystallized Ca 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, example 4 prepared samplesThe average grain size of the product was 98nm. Its optical transmission at 800nm was 74%.
Example 5 preparation of 0.992Ca 1.1 Al 2.2 Si 1.8 O 8 -0.008W transparent ceramic
Weighing Ca with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 15 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 6L/min and a heating rate of 100 ℃/min, preserving heat at 800 ℃ for 13h for calcining, and then raising the temperature to 1550 ℃ for 1.5h for completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 750 ℃ for 12 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 970 ℃ for 5 hours, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 5 is similar to that of FIG. 3, and is fully crystallized Ca 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 4 was 74nm. The optical transmittance at 800nm was 79%.
Example 6 preparation of 0.99Ca 1.1 Al 2.2 Si 1.8 O 8 -0.001W transparent ceramic
Weighing Ca with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 20 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon gas, and maintaining the temperature at 800 ℃ at a flow rate of 8L/min and a heating rate of 120 ℃/minCalcining the powder at the temperature of 13h, and then heating to 1500 ℃ and preserving heat for 3h to enable the mixed powder to be completely melted; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 700 ℃ for 18 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 950 ℃ for 10 hours, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 6 is similar to that of FIG. 3, and is fully crystallized Ca 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 4 was 88nm. Its optical transmission at 800nm was 76%.
Example 7, preparation of 0.995Ba 1.1 Al 2.2 Si 1.8 O 8 -0.005W transparent ceramic
Weighing Ba with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 10 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 4L/min and a heating rate of 80 ℃/min, preserving heat at 1000 ℃ for 7 hours for calcining, and then raising the temperature to 1800 ℃ for 0.2 hours for completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mold, the glass is placed in an annealing platform 6, the temperature is kept at 950 ℃ for 3 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 1100 ℃ for 0.2 hour, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 7 is similar to that of FIG. 3, and is fully crystallized Ba 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 7 was 92nm. Its optical transmission at 800nm was 70%.
Example 8 preparation of 0.992Ba 1.1 Al 2.2 Si 1.8 O 8 -0.008W transparent ceramic
Weighing Ba with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 20 hours, and drying to obtain mixed raw materials; placing the mixed raw materials into a crucible 2 (tungsten crucible is adopted in the embodiment), introducing argon, heating at a speed of 6L/min and a heating rate of 100 ℃/min, preserving heat at 950 ℃ for 10 hours for calcining, and then raising the temperature to 1760 ℃ for 1.5 hours for completely melting the mixed powder; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 900 ℃ for 12 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 970 ℃ for 5 hours, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 8 is similar to that of FIG. 3, and is fully crystallized Ca 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 8 was 82nm. The optical transmittance at 800nm was 79%.
Example 9 preparation of 0.99Ba 1.1 Al 2.2 Si 1.8 O 8 -0.001W transparent ceramic
Weighing Ba with purity higher than 99.99% according to the molar ratio of the components 2 CO 3 、Al 2 O 3 、SiO 2 Placing the powder raw materials into an alumina ball milling tank, adding high-purity alumina balls and ethanol, ball milling for 20 hours, and drying to obtain mixed raw materials; the mixed raw material was placed in a crucible 2 (tungsten crucible is used in this example), argon gas was introduced, andthe flow rate is 8L/min, the heating rate is 120 ℃/min, the powder calcining is carried out at 900 ℃ for 13h, then the temperature is increased to 1720 ℃ for 3h, and the mixed powder is completely melted; operating the furnace handle 4, casting the powder melt onto the water-cooling copper mold 3 for cooling and solidifying to obtain a bulk glass precursor; the cylinder 5 is operated to open the mould, the glass is placed in an annealing platform 6, the temperature is kept at 700 ℃ for 18 hours, annealing heat treatment is carried out to remove internal stress, the electromagnetic induction coil on the designed annealing platform is used for carrying out heat treatment on the glass doped with the metal nucleating agent, and the temperature is kept at 950 ℃ for 10 hours, so that the silicate transparent ceramic is finally obtained.
The XRD test pattern of the sample prepared in this example 9 is similar to that of FIG. 3, and is fully crystallized Ca 1.1 Al 2.2 Si 1.8 O 8 And (3) ceramics. As shown in Table 1, the average grain size of the sample prepared in example 9 was 88nm. Its optical transmission at 800nm was 76%.
Table 1 shows the average grain sizes and optical transmittance of the sample materials of examples 1 to 9
In the description of the present invention, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (10)
1. A method for preparing large-size nanocrystalline transparent ceramic by using nano metal nucleating agent is characterized by adopting a glass total crystallization method, and comprises the following specific operation steps:
(a) According to formula A 1.1 Al 2.2 Si 1.8 O 8 The stoichiometric ratio of each element respectively weighs A with the purity of more than 99.99 percent 2 CO 3 、Al 2 O 3 、SiO 2 As a raw material, adding a nano metal nucleating agent, performing wet ball milling on the powder mixture, and drying to obtain mixed powder; wherein A is one of Ca, sr and Ba, the nano metal nucleating agent is one of tungsten W, molybdenum Mo, tantalum Ta and niobium Nb, the adding amount of the nano metal nucleating agent is 0.005-0.01 according to mole percent, and the size is 40-80 nm;
(b) Placing the mixed powder into a crucible of an electromagnetic induction smelting furnace, introducing inert gas into the furnace, then raising the temperature, performing a powder calcining procedure, and then continuously raising the temperature of the mixed powder until the mixed powder is completely melted;
(c) Operating an electromagnetic induction smelting furnace, casting the mixed powder melt onto a water-cooling copper mold for cooling and solidifying to obtain a bulk glass precursor;
(d) Operating an electromagnetic induction melting furnace, placing a glass precursor in an annealing platform wound by an electromagnetic induction coil, and annealing the bulk glass; and then continuously heating the annealed glass precursor in an annealing platform for crystallization treatment, and finally obtaining the aluminosilicate transparent ceramic.
2. The method for preparing large-size nanocrystalline transparent ceramic by using a nanocrystalline metal nucleating agent according to claim 1, wherein in the step (a), the ball milling medium of the wet ball milling is ethanol, the ball milling time is 10-20 h, the ball milling rotating speed is 200r/min, and the ball-to-material ratio is 1.2:1.
3. The method for preparing large-sized, nanocrystalline transparent ceramic using nanocrystalline metal nucleating agent according to claim 1, wherein in step (b), the crucible is one of graphite, platinum rhodium, or tungsten crucible.
4. The method for preparing large-sized nanocrystalline transparent ceramic by means of a nanocrystalline metal nucleating agent according to claim 1, wherein in the step (b), the inert gas is one of argon, nitrogen or a mixed gas of the argon and the nitrogen, and the flow rate is 4-8L/min.
5. The method for preparing large-size nanocrystalline transparent ceramic by using a nanocrystalline metal nucleating agent according to claim 1, wherein in the step (b), the heating rate is 80-120 ℃/min, the powder calcining procedure is 800-1000 ℃, the temperature is kept for 7-13 h, the melting procedure is 1500-1800 ℃, and the temperature is kept for 0.2-3 h.
6. The method for preparing large-size nanocrystalline transparent ceramic by using a nanocrystalline metal nucleating agent according to claim 1, wherein in the step (c), the temperature of a water-cooled copper mold is controlled by an industrial-grade cold water machine, the temperature of the copper plate is always less than or equal to 35 ℃, and the cooling rate is 200-300 ℃/min during cooling.
7. The method for preparing large-sized nanocrystalline transparent ceramic by means of nanocrystalline metal nucleating agents according to claim 1, wherein the annealing temperature is 700-950 ℃ and the annealing time is 3-18 h.
8. The method for preparing large-sized nanocrystalline transparent ceramic by means of nanocrystalline metal nucleating agents according to claim 1, wherein in the step (d), the crystallization treatment mode is 950-1100 ℃, and the heat treatment is performed for 0.2-10 hours.
9. A large-sized, nanocrystalline aluminosilicate transparent ceramic produced by the production method according to any one of claims 1 to 8.
10. The large-size, nanocrystalline aluminosilicate transparent ceramic according to claim 9, wherein the ceramic grain size of the transparent ceramic is 50-100 nm, and the optical transmittance at a wavelength of 800nm is 70-85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310264663.3A CN116477930A (en) | 2023-03-17 | 2023-03-17 | Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310264663.3A CN116477930A (en) | 2023-03-17 | 2023-03-17 | Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116477930A true CN116477930A (en) | 2023-07-25 |
Family
ID=87225815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310264663.3A Pending CN116477930A (en) | 2023-03-17 | 2023-03-17 | Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116477930A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070042889A1 (en) * | 2005-02-08 | 2007-02-22 | Ivoclar Vivadent Ag | Lithium silicate glass ceramic |
| CN101746954A (en) * | 2009-12-18 | 2010-06-23 | 中国科学院上海光学精密机械研究所 | Preparing method for saturable absorber of cobalt-doped magnesia-alumina-silica based glass ceramics |
| CN104355545A (en) * | 2014-09-24 | 2015-02-18 | 南京邮电大学 | Transparent glass ceramic having double-frequency light absorption and conversion capability and preparation method for transparent glass ceramic |
| WO2017120990A1 (en) * | 2016-01-13 | 2017-07-20 | 广东工业大学 | Process for preparing net-size, complex-shape transparent ceramic piece |
| DE102018221827A1 (en) * | 2018-12-14 | 2020-06-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of a glass ceramic and glass ceramic |
| CN111511696A (en) * | 2017-10-23 | 2020-08-07 | 康宁股份有限公司 | Glass-ceramic and glass |
| CN111592225A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Lithium-aluminum silicate nanocrystalline transparent ceramic, preparation method thereof and product |
| CN112028492A (en) * | 2020-09-04 | 2020-12-04 | 江苏师范大学 | YAG-Al2O3Nano laminated composite transparent ceramic and preparation method thereof |
-
2023
- 2023-03-17 CN CN202310264663.3A patent/CN116477930A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070042889A1 (en) * | 2005-02-08 | 2007-02-22 | Ivoclar Vivadent Ag | Lithium silicate glass ceramic |
| CN101746954A (en) * | 2009-12-18 | 2010-06-23 | 中国科学院上海光学精密机械研究所 | Preparing method for saturable absorber of cobalt-doped magnesia-alumina-silica based glass ceramics |
| CN104355545A (en) * | 2014-09-24 | 2015-02-18 | 南京邮电大学 | Transparent glass ceramic having double-frequency light absorption and conversion capability and preparation method for transparent glass ceramic |
| WO2017120990A1 (en) * | 2016-01-13 | 2017-07-20 | 广东工业大学 | Process for preparing net-size, complex-shape transparent ceramic piece |
| CN111511696A (en) * | 2017-10-23 | 2020-08-07 | 康宁股份有限公司 | Glass-ceramic and glass |
| DE102018221827A1 (en) * | 2018-12-14 | 2020-06-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of a glass ceramic and glass ceramic |
| CN111592225A (en) * | 2020-04-29 | 2020-08-28 | 深圳精匠云创科技有限公司 | Lithium-aluminum silicate nanocrystalline transparent ceramic, preparation method thereof and product |
| CN112028492A (en) * | 2020-09-04 | 2020-12-04 | 江苏师范大学 | YAG-Al2O3Nano laminated composite transparent ceramic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110407213B (en) | (Ta, nb, ti, V) C high-entropy carbide nano powder and preparation method thereof | |
| CN103011827A (en) | Preparation method of zirconium diboride ceramic with in-situ-introduced boron as additive | |
| Gao et al. | Influence of Y2O3 on microstructure, crystallization, and properties of MgO-Al2O3-SiO2 glass-ceramics | |
| US20180105470A1 (en) | Bonded zirconia refractories and methods for making the same | |
| CN108546109B (en) | Preparation method of large-size AZO magnetron sputtering target with controllable oxygen vacancy | |
| CN114031297B (en) | Cordierite-based porous glass ceramic and preparation method thereof | |
| JP2013209245A (en) | Production method for ceramic composite | |
| NL2030121B1 (en) | Method for preparing large-size high-quality potassium tantalum niobate ceramic target material | |
| CN114293159B (en) | Preparation method of nickel-based alloy target | |
| CN100366581C (en) | Making process of C/C heater for monocrystal silicon drawing furnace and polycrystal silicon smelting furnace | |
| CN106064936B (en) | Preparation method of high-purity mullite ceramic material | |
| Liu et al. | Inhibiting crystallization of fused silica ceramic at high temperature with addition of α-Si3N4 | |
| Li et al. | Improved microstructure and optical properties of Nd: YAG ceramics by hot isostatic pressing | |
| CN102864343A (en) | Preparation method for in-situ aluminium base composite material inoculant | |
| CN116477930A (en) | Method for preparing large-size nanocrystalline transparent ceramic through nano metal nucleating agent | |
| CN113754284B (en) | Preparation method of glass ceramic and industrial microwave oven | |
| CN110697725B (en) | Preparation method of lithium disilicate whisker | |
| CN103922814A (en) | Zirconium oxide refractory product with composite structure | |
| CN109180209B (en) | Method for preparing silicon carbide nanowire reinforced graphite-silicon carbide composite material by adopting in-situ self-generation method | |
| CN112159230A (en) | Preparation method of large-size aluminum carbo-silicate and method for improving high-temperature performance of magnesia carbon brick based on addition of large-size aluminum carbo-silicate | |
| CN108002389B (en) | The method and silicon powder of zinc bismuth alloy coated Si magnesium granules preparation foam-like silicon powder | |
| CN110845229A (en) | LaBiO3Film, LaBiO3Ceramic target material and preparation method thereof | |
| CN116178009B (en) | High-orientation potassium-sodium niobate-based transparent piezoelectric ceramic and preparation method thereof | |
| Mann et al. | Novel amorphous precursor densification to transparent Nd: Y2O3 ceramics | |
| TW201348459A (en) | Molybdenum (Mo) sputtering target and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |