CN116573860B - Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof - Google Patents
Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof Download PDFInfo
- Publication number
- CN116573860B CN116573860B CN202310529922.0A CN202310529922A CN116573860B CN 116573860 B CN116573860 B CN 116573860B CN 202310529922 A CN202310529922 A CN 202310529922A CN 116573860 B CN116573860 B CN 116573860B
- Authority
- CN
- China
- Prior art keywords
- glass
- cata
- transparent
- transparent glass
- nanocrystalline
- 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.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 110
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 11
- 239000011575 calcium Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 62
- 239000002159 nanocrystal Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 18
- 241000286904 Leptothecata Species 0.000 claims description 13
- 238000002834 transmittance Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000005357 flat glass Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002419 bulk glass Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 16
- 238000005424 photoluminescence Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000013081 microcrystal Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- 238000005464 sample preparation method Methods 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001831 conversion spectrum Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/671—Chalcogenides
- C09K11/673—Chalcogenides with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
- C09K11/7703—Chalogenides with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
- G02B7/007—Pressure-resistant sight glasses
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to transparent microcrystalline glass containing calcium tantalate nanocrystals, and a preparation method and application thereof. The transparent glass ceramics comprises the following components: caO:26-34mol%, ta 2O5: 27-33mol% and Al 2O3: 34-44mol%. According to the invention, the transparent microcrystalline glass containing CaTa 2O6 nano-crystals is prepared for the first time by optimizing a composition formula in a CaO-Ta 2O5-Al2O3 glass system. In addition, 0.05-4mol% of rare earth or transition metal ions can be doped in the transparent glass ceramics, and the obtained transparent glass ceramics doped with the rare earth or transition metal ions and containing CaTa 2O6 nano crystals has excellent photoluminescence performance.
Description
Technical Field
The invention relates to the technical field of inorganic material science, in particular to transparent microcrystalline glass containing CaTa 2O6 nano crystals and a preparation method and application thereof.
Background
Glass ceramics are composite materials in which crystals are dispersed in a glass matrix, and are generally obtained by controlled crystallization of a matrix glass. Microcrystalline glass has the dual advantages of crystals and glass. Since the invention of glass ceramics by Stookey doctor in the 50 th century, glass ceramics have been widely used in the fields of aerospace, electronics, machinery, construction, biology, laser, etc. However, due to the heterogeneous nature of the glass-ceramics, light scattering generated at the interface between the crystalline phase and the amorphous phase makes the glass-ceramics easily opaque. According to Reyleigh-Gans theory, the following two conditions are required to be satisfied in order to obtain transparent glass ceramics: 1) The size of the crystalline phase is as small as possible, should be smaller than the wavelength of visible light; 2) The refractive index difference between the crystalline phase and the residual glass phase is as small as possible. The dispersed nanocrystalline endows the transparent microcrystalline glass with special functions in the fields of optics and the like, and the transparent microcrystalline glass has good mechanical property and thermal stability, so that the transparent microcrystalline glass has wide application prospect in the fields of optics and photons. Therefore, the development of the novel transparent glass ceramics has important significance for the exploration of the optical functions of the glass ceramics.
Disclosure of Invention
The invention aims to solve the technical problem of providing the transparent microcrystalline glass containing CaTa 2O6 nano crystals and the preparation method thereof, aiming at the defects in the prior art, and the novel transparent microcrystalline glass with the characteristics of high thermal stability, high crystallinity, high light transmittance, wide optical window, high refractive index, high hardness, rare earth or transition metal ion doped fluorescence performance and the like is obtained.
The object of the invention is achieved by at least one of the following technical solutions.
Transparent glass ceramics containing CaTa 2O6 nano-crystals, wherein the transparent glass ceramics consists of a calcium source, a tantalum source and an aluminum source, wherein the calcium source is calculated by CaO, the tantalum source is calculated by Ta 2O5, the aluminum source is calculated by Al 2O3, and the mole percentages of the components are as follows:
26-34mol% CaO,27-33mol% Ta 2O5 and 34-44mol% Al 2O3, wherein the sum of the CaO, ta 2O5 and Al 2O3 molar amounts satisfies 100%.
Further, the CaTa 2O6 nanocrystalline has a cubic phase.
Further, the calcium source is one of an oxide, a carbonate or a hydroxide of calcium; the tantalum source is an oxide of tantalum; the aluminum source is one of an oxide or hydroxide of aluminum.
Further, the density of the transparent glass ceramics is 5.857-5.979g/cm 3, the crystallinity is 55-62vol%, the Vickers microhardness is 11.58-12.10GPa, the visible light transmittance is 74-81%, and the infrared cut-off wavelength is 7 μm.
Further, the transparent glass ceramic containing CaTa 2O6 nano-crystals also comprises rare earth or transition metal ions with the doping amount of 0.05-4 mol%.
Further, the source of the rare earth or transition metal ions is one of oxides, fluorides or nitrates of Er 3+、Eu3+ or Ni 2+.
The invention provides a method for preparing the transparent glass ceramics containing CaTa 2O6 nano-crystals, which comprises the following steps:
1) And (3) mixing glass materials: weighing raw materials according to a proportion, and then placing the raw materials into a mortar for mixing to obtain a uniformly mixed glass mixture;
2) Tabletting and forming: placing the glass mixture obtained in the step 1) into a mold, performing compression molding, and demolding to obtain a sheet-shaped glass mixture;
3) Presintering: placing the sheet glass mixture obtained in the step 2) in a muffle furnace for presintering to obtain a block glass mixture;
4) Pneumatic suspension laser melting to prepare glass: preparing glass from the bulk glass mixture obtained in the step 3) by a pneumatic suspension laser melting method;
5) And (3) microcrystallizing treatment: and (3) placing the glass obtained in the step (4) into a muffle furnace for heat treatment to obtain the transparent microcrystalline glass containing CaTa 2O6 nano-crystals.
Further, the heat treatment temperature in the step 5) is 880-930 ℃, the heat preservation time is 1-20 hours, and then the furnace cooling is carried out to the room temperature.
Further, the transparent glass ceramics containing CaTa 2O6 nano crystals are applied to optical window materials and fluorescent conversion matrix materials.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) The transparent microcrystalline glass containing CaTa 2O6 nano-crystals is prepared into matrix glass by a pneumatic suspension laser melting method, and the transparent microcrystalline glass containing CaTa 2O6 nano-crystals with high thermal stability, high crystallinity, high light transmittance, wide optical window, high refractive index and high hardness can be obtained by a one-step microcrystallization treatment method, the density is 5.857-5.979g/cm 3, the crystallinity is 55-62vol%, the Vickers microhardness is 11.58-12.10GPa, the visible light transmittance is 74-81%, and the infrared cut-off wavelength is 7 mu m.
2) The transparent glass ceramic containing CaTa 2O6 nano-crystals provided by the invention can be doped with 0.05-4mol% of one of rare earth or transition metal ions containing Er 3 +、Eu3+ or Ni 2+. The up-conversion luminous intensity of the Er 3+ doped CaTa 2O6 transparent glass ceramics is enhanced by 14 times compared with that of the matrix glass, and the half width of near infrared luminescence is increased from 64nm of the glass to 86nm of the transparent glass ceramics; near infrared luminous half width of the CaTa 2O6 transparent glass ceramics doped with Ni 2+ can reach 277nm; the Eu 3+ doped CaTa 2O6 transparent glass ceramics has stronger red light emission. Therefore, the transparent glass ceramics containing CaTa 2O6 nano crystals can be used as a high-strength optical window material and a novel fluorescent conversion matrix material, and has potential application in the aspects of laser illumination, laser display and the like.
Drawings
FIGS. 1-13 show XRD patterns and transmittance spectra of examples 1-13, respectively.
FIGS. 14-25 are graphs showing XRD patterns and transmittance spectra of comparative examples 1-12.
FIG. 26 is a DSC of the matrix glass prepared in example 14.
FIG. 27 is a temperature-time curve of the microcrystal treatment of CaTa 2O6 nm-crystal-containing transparent glass-ceramic prepared in example 14.
FIG. 28 is an XRD pattern of CaTa 2O6 nanocrystalline-containing transparent glass-ceramic and matrix glass prepared in example 14.
FIG. 29 is a TEM image of CaTa 2O6 nanocrystalline-containing transparent glass-ceramic prepared in example 9.
FIG. 30 is a HRTEM chart of CaTa 2O6 nanocrystalline-containing transparent glass ceramic prepared in example 9.
FIG. 31 is a photograph of CaTa 2O6 nanocrystalline-containing transparent glass ceramic prepared in example 9.
FIG. 32 is a transmission spectrum of CaTa 2O6 nanocrystalline-containing transparent glass-ceramic prepared in example 9. FIG. 33 is a graph showing refractive indices of CaTa 2O6 -nanocrystalline-containing transparent glass-ceramic and matrix glass prepared in example 9.
FIG. 34 is a near infrared emission spectrum of Er 3+ doped transparent glass ceramics containing CaTa 2O6 nanocrystals and a substrate glass obtained in example 15.
FIG. 35 is an upconversion emission spectrum of Er 3+ doped transparent glass ceramics containing CaTa 2O6 nanocrystals and matrix glass obtained in example 15.
FIG. 36 shows excitation spectra and emission spectra of Eu 3+ doped CaTa 2O6 nanocrystalline-containing transparent glass ceramics and matrix glass obtained in example 16.
FIG. 37 is a near infrared emission spectrum of the Ni 2+ doped CaTa 2O6 nanocrystalline-containing transparent glass ceramics and matrix glass obtained in example 17.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Examples 1 to 13
The preparation method of the transparent microcrystalline glass containing CaTa 2O6 nanocrystalline comprises the following specific steps:
1) And (3) mixing glass materials: the raw materials are respectively weighed according to the mole percentage shown in the table 1, and then the raw materials are placed in a mortar for mixing, so as to obtain a uniformly mixed glass mixture;
2) Tabletting and forming: placing the glass mixture obtained in the step 1) into a stainless steel die, adopting a table tablet press to press and mold, and demolding to obtain a sheet glass mixture;
3) Presintering: placing the sheet glass mixture obtained in the step 2) into a corundum crucible, placing the crucible into a muffle furnace for presintering, setting the temperature to be 1000 ℃, and preserving the heat for 6 hours to obtain a block glass mixture;
4) Pneumatic suspension laser melting to prepare glass: placing the block-shaped glass mixture obtained in the step 3) on a pneumatic suspension nozzle, suspending the block-shaped glass mixture by adjusting the size of air flow, adjusting the power of a laser to enable the block-shaped glass mixture to be completely melted, keeping the melt stably suspended for about ten seconds under the action of the air flow to enable the glass mixture to be completely and uniformly mixed, then turning off the laser, and rapidly cooling the melt to room temperature under the action of the air flow to obtain glass;
5) And (3) microcrystallizing treatment: and (3) placing the glass obtained in the step (4) into a muffle furnace for heat treatment, setting the temperature to 890 ℃, and preserving the heat for 1 hour.
As shown in figures 1-13, XRD tests prove that the obtained samples are transparent microcrystalline glass only separating out the CaTa 2O6 nano-crystals of the cubic phase, and the maximum transmittance can reach 74-81%.
TABLE 1 raw material ratios (mole percent) of examples 1-13
| CaO(mol％) | Ta2O5(mol％) | Al2O3(mol％) | |
| Example 1 | 26 | 30 | 44 |
| Example 2 | 27 | 31 | 42 |
| Example 3 | 29 | 29 | 42 |
| Example 4 | 31 | 27 | 42 |
| Example 5 | 28 | 32 | 40 |
| Example 6 | 30 | 30 | 40 |
| Example 7 | 32 | 28 | 40 |
| Example 8 | 29 | 33 | 38 |
| Example 9 | 31 | 31 | 38 |
| Example 10 | 33 | 29 | 38 |
| Example 11 | 32 | 32 | 36 |
| Example 12 | 34 | 30 | 36 |
| Example 13 | 33 | 33 | 34 |
Comparative example 1
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 15:45:40, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less, and the Ta 2O5 content is more. Colorless transparent glass was obtained by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1 to 13, the obtained sample was white opaque ceramic, and as shown in fig. 14, XRD test revealed that, in addition to CaTa 2O6 of precipitated cubic phase, caAl 2O4 phase was precipitated in the sample, and the proportion of crystalline phase was small, the residual glass phase was large, and precipitation of second phase and change of composition of residual glass phase led to failure in obtaining transparent glass ceramics containing only cubic phase CaTa 2O6 nanocrystals in the comparative example.
Comparative example 2
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 20:40:40, sample preparation methods and conditions were the same as in examples 1-13. Ta 2O5 is more abundant and CaO is less abundant. Colorless transparent glass was obtained by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1 to 13, the obtained sample was white opaque ceramic, and as shown in fig. 15, XRD test revealed that, in addition to CaTa 2O6 of precipitated cubic phase, caAl 2O4 phase was precipitated in the sample, and the proportion of crystalline phase was small, the residual glass phase was large, and precipitation of second phase and change of composition of residual glass phase led to failure in obtaining transparent glass ceramics containing only cubic phase CaTa 2O6 nanocrystals in the comparative example.
Comparative example 3
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 10:41.4:48.6, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less, and the Ta 2O5 and Al 2O3 contents are more. Colorless transparent glass can be prepared by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1-13, the obtained sample is white opaque ceramic, and XRD test shows that besides CaTa 2O6 of precipitated cubic phase, ta 2O5 phase is precipitated in the sample, the proportion of crystal phase is small, the residual glass phase is more, and the precipitation of second phase and the change of the composition of the residual glass phase lead to the fact that the comparative example cannot obtain transparent microcrystalline glass only containing cubic phase CaTa 2O6 nanocrystalline.
Comparative example 4
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 20:36.8:43.2 sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less than the Ta 2O5 content. Colorless transparent glass can be prepared by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1-13, the obtained sample is white opaque ceramic, and XRD test shows that besides the CaTa 2O6 of cubic phase precipitation, caAl 2O4 impurity phase is also precipitated in the sample, and the precipitation of second phase leads the comparative example to fail to obtain transparent microcrystalline glass containing only cubic phase CaTa 2O6 nano crystals.
Comparative example 5
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 16:30:54, sample preparation methods and conditions were the same as in examples 1-13. The higher Al 2O3 content results in higher melting point of the component, higher crystallization tendency and poorer glass forming capability. The samples prepared by pneumatic suspension laser melting are semitransparent glass, and after the same microcrystalline treatment as in examples 1-13, the samples are white opaque ceramics, and XRD tests show that besides the CaTa 2O6 of cubic phase, al 2O3 impurity phase is precipitated, and the precipitation of second phase leads to the fact that the comparative example cannot obtain transparent microcrystalline glass only containing cubic phase CaTa 2O6 nanocrystals.
Comparative example 6
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 10:45:45, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less, and the Ta 2O5 and Al 2O3 contents are more. Colorless transparent glass can be prepared by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1-13, the obtained sample is white opaque ceramic, and XRD test shows that besides CaTa 2O6 of precipitated cubic phase, caAl 2O4 phase is precipitated in the sample, the crystal phase proportion is small, the residual glass phase is more, and the precipitation of the second phase and the change of the composition of the residual glass phase lead the comparative example not to obtain transparent microcrystalline glass only containing cubic phase CaTa 2O6 nanocrystalline.
Comparative example 7
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 10:36:54, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less, and the Ta 2O5 and Al 2O3 contents are more. Colorless transparent glass was obtained by pneumatic suspension laser melting, and after the same microcrystal treatment as in examples 1 to 13, the obtained sample was white opaque ceramic, and XRD test revealed that, in addition to the cubic phase CaTa 2O6, a hetero phase such as Al 2O3 was precipitated, and the precipitation of the hetero phase led to the failure of the comparative example to obtain transparent glass ceramics containing only cubic phase CaTa 2O6 nanocrystals.
Comparative example 8
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 35:32.5:32.5, sample preparation method and conditions were the same as in examples 1-13. The CaO content is slightly greater than the Ta 2O5 content, while the Al 2O3 content is less. The sample obtained by pneumatic suspension laser melting was colorless and transparent glass, and after the same microcrystal treatment as in examples 1 to 13, the sample was semitransparent glass ceramics, and XRD test revealed that a small amount of Ta 2O2.2 phase was precipitated in addition to the CaTa 2O6 of cubic phase, the maximum transmittance in the visible light region was only 3%, and the precipitation of the second phase resulted in that the comparative example could not obtain transparent glass ceramics containing only CaTa 2O6 nanocrystals of cubic phase.
Comparative example 9 raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 25:29:46, sample preparation method and conditions were the same as in examples 1-13. The higher melting point of the component, the higher crystallization tendency and the poorer glass forming capability are caused by the higher content of Al 2O3. The samples obtained by pneumatic suspension laser melting were glass, and after the same microcrystallization treatment as in examples 1 to 13, the samples were opaque ceramics, and XRD test revealed that, in addition to the CaTa 2O6 of the cubic phase, a hetero phase such as Al 2O3 was precipitated, and the precipitation of the hetero phase led to failure in obtaining transparent glass ceramics containing only the cubic phase CaTa 2O6 nanocrystals in this comparative example.
Comparative example 10
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 25:33:42, sample preparation methods and conditions were the same as in examples 1-13. The sample prepared by pneumatic suspension laser melting is semitransparent phase-separated glass with small CaO content, and after the same microcrystal treatment as in examples 1-13, the sample is semitransparent microcrystalline glass, and XRD test shows that Ta 2O2.2 phase is precipitated in addition to the CaTa 2O6 of cubic phase, the proportion of crystal phase is small, the residual glass phase is more, the maximum transmittance in the visible light area is 28%, and the precipitation of second phase and the change of the composition of the residual glass phase lead the comparative example not to obtain transparent microcrystalline glass only containing cubic phase CaTa 2O6 nano crystals.
Comparative example 11
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 27:35:38, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is less than the Ta 2O5 content. The sample obtained by pneumatic suspension laser melting is colorless and transparent glass, and after the same microcrystal treatment as in examples 1-13, the sample is semitransparent glass ceramics, and XRD test shows that Ta 2O2.2 phase is precipitated in addition to the CaTa 2O6 of cubic phase, the proportion of crystal phase is small, the residual glass phase is more, the maximum transmittance of visible light area is only 12%, and the precipitation of second phase and the change of the composition of residual glass phase lead the comparative example not to obtain transparent glass ceramics containing cubic phase CaTa 2O6 nanocrystalline only.
Comparative example 12
Raw materials, caO, were weighed according to the mole percentages shown in table 2: ta 2O5：Al2O3 = 35:31:34, sample preparation methods and conditions were the same as in examples 1-13. The CaO content is slightly larger than the Ta 2O5 content, and the Al 2O3 content is less. The sample obtained by pneumatic suspension laser melting was colorless and transparent glass, and after the same microcrystal treatment as in examples 1 to 13, the sample was semitransparent glass ceramics, and XRD test revealed that a small amount of Ta 2O2.2 phase was precipitated in addition to the CaTa 2O6 of cubic phase, the maximum transmittance in the visible light region was only 3%, and the precipitation of the second phase resulted in that the comparative example could not obtain transparent glass ceramics containing only CaTa 2O6 nanocrystals of cubic phase.
Table 2 the raw material ratios (mole percent content) of comparative examples 1 to 12
Example 14
This example is substantially the same as example 9, except that the heat treatment time is set to 2, 4, 6, 8, 10 hours.
As obtained by DSC (as shown in fig. 26), the glass transition temperature is high by T g =823 ℃, the crystallization peak-to-peak temperature is 898 ℃, and the thermal stability is better. The glass was subjected to the microcrystallization treatment shown in FIG. 27 based on the glass characteristic temperature obtained by DSC. According to XRD (shown in figure 28), the matrix glass is in an amorphous form, crystal phase precipitation is carried out after microcrystallization treatment, and comparison shows that the precipitated crystal phase is CaTa 2O6 of a cubic phase only and the crystallinity is 55-62vol%, so that transparent microcrystalline glass containing CaTa 2O6 nanocrystals is obtained after microcrystallization treatment. According to TEM (as shown in fig. 29), it was observed that the nano-crystallites were uniformly dispersed in the glass matrix. According to HRTEM (as shown in fig. 30), it was observed that the precipitated nanocrystals agglomerated together to form one large grain. The transparent glass ceramic has high transparency in a visible light region (shown in figure 31), the density is 5.857-5.979g/cm 3, the Vickers microhardness is 11.58-12.10GPa (shown in table 3), the visible light transmittance can reach 81%, and the infrared cut-off wavelength is 7 mu m (shown in figure 32). As shown in fig. 33, the refractive index of the transparent glass ceramic sample is improved compared with the substrate glass sample, and the refractive index n d (wavelength 587.6 nm) =1.973 has a higher refractive index.
TABLE 3 Density and Vickers microhardness of transparent glass ceramics obtained in example 9 and example 14
Example 15
Preparing Er 3+ doped transparent microcrystalline glass containing CaTa 2O6 nanocrystals, wherein the glass frit comprises the following components in percentage by weight: 31:31:38 mole percent of the raw materials. In the sample preparation process, except that the microcrystal condition is 900 ℃, the temperature is kept for 20 hours, other preparation methods and conditions are the same as those of examples 1-13, and the Er 3+ doped transparent microcrystalline glass containing CaTa 2O6 nano-crystals is obtained.
Under the excitation of 980nm laser, the fluorescence spectrum of the near infrared band is measured by a fluorescence spectrometer (as shown in fig. 34), broadband near infrared luminescence with a luminescence peak at 1.550 μm is monitored, and the half-height width of the fluorescence peak of the transparent microcrystalline glass is increased from 64nm to 86nm compared with that of the matrix glass corresponding to Er 3+：4I13/2→4I15/2 transition. The up-conversion luminescence spectrum in the visible light band was measured by a fluorescence spectrometer under excitation with 980nm laser (as shown in fig. 35). The up-conversion spectrum has a green light peak with a peak position of 550nm and a red light peak with a peak position of 670nm, which correspond to transitions of Er 3+：2H11/2,4S3/2→4I15/2 and 4F9/2→4I15/2 respectively, and the transparent glass ceramics mainly emits green light. Compared with the matrix glass, the up-conversion luminescence peak of the transparent microcrystalline glass is split, and the fluorescence intensity is enhanced by 14 times.
Example 16
Preparing Eu 3+ doped transparent microcrystalline glass containing CaTa 2O6 nanocrystalline, wherein the glass frit comprises the following components in terms of Eu 2O3：CaO：Ta2O5：Al2O3 =0.5: 30:30:40 mole percent of raw materials are weighed. In the sample preparation process, except that the microcrystal condition is 900 ℃, the temperature is kept for 1h, and other preparation methods and conditions are the same as those of examples 1-13, so that the Eu 3+ doped transparent microcrystalline glass containing CaTa 2O6 nano-crystals is obtained.
Excitation and emission spectra were measured using a fluorescence spectrometer (as shown in fig. 36), the excitation spectrum consisting of a broad band in the ultraviolet region, which is the charge transport band of O-Eu, and a narrow band in the visible region, which is the 4f-4f transition band of Eu 3+. After the transparent glass ceramics is excited by a xenon lamp 398nm, a red luminescence peak at about 600nm appears, which corresponds to Eu 3+：5D0→7F2 transition.
Example 17
Preparing transparent microcrystalline glass doped with Ni 2+ and containing CaTa 2O6 nanocrystalline, wherein the glass frit comprises the following components: caO: ta 2O5：Al2O3 = 0.3:33:29:38 mole percent of the raw materials. In the sample preparation process, except that the microcrystal condition is 880 ℃, the temperature is kept for 5 hours, and other preparation methods and conditions are the same as those of examples 1-13, so that the transparent microcrystalline glass doped with Ni 2+ and containing CaTa 2O6 nano crystals is obtained.
The emission spectrum in the near infrared band was measured with a fluorescence spectrometer under excitation with 980nm laser (as shown in fig. 37), no luminescence was observed in the matrix glass, whereas broadband near infrared luminescence with a center wavelength at 1230nm and a shoulder at 1420nm was monitored in the transparent glass ceramic, corresponding to an octahedral coordinated Ni 2+：3T2(F)→3A2 (F) transition, the half width of the fluorescence peak being 277nm.
Claims (8)
1. The transparent glass ceramic containing CaTa 2O6 nano crystals is characterized by comprising a calcium source, a tantalum source and an aluminum source, wherein the calcium source is calculated by CaO, the tantalum source is calculated by Ta 2O5, the aluminum source is calculated by Al 2O3, and the mole percentages of the components are as follows:
26-34mol% of CaO,27-33mol% of Ta 2O5 and 34-44mol% of Al 2O3, wherein the sum of the mol% of CaO, ta 2O5 and Al 2O3 meets 100%, the crystal form of CaTa 2O6 nanocrystalline is cubic phase, the transparent glass ceramics is prepared by pneumatic suspension laser melting, and then the glass is subjected to heat treatment to obtain the transparent glass ceramics, the heat treatment temperature is 880-930 ℃, the heat preservation time is 1-20 hours, and then the glass ceramics are cooled to room temperature along with a furnace.
2. The CaTa 2O6 nanocrystalline containing transparent glass ceramic according to claim 1, wherein the calcium source is one of an oxide, carbonate or hydroxide of calcium; the tantalum source is an oxide of tantalum; the aluminum source is one of an oxide or hydroxide of aluminum.
3. The transparent glass-ceramic containing CaTa 2O6 nanocrystals according to claim 1, wherein the density of the transparent glass-ceramic is 5.857-5.979g/cm 3, the crystallinity is 55-62vol%, the vickers microhardness is 11.58-12.10GPa, the visible light transmittance is 74-81%, and the infrared cut-off wavelength is 7 μm.
4. The transparent glass-ceramic containing CaTa 2O6 nanocrystals according to claim 1, further comprising rare earth or transition metal ions in an amount of 0.05 to 4 mol%.
5. The CaTa 2O6 nanocrystalline containing transparent glass-ceramic according to claim 4, wherein the source of rare earth or transition metal ions is one of oxides, fluorides or nitrates of Er 3+、Eu3+ or Ni 2+.
6. A method for preparing the CaTa 2O6 nanocrystalline-containing transparent glass ceramics according to any one of claims 1 to 5, which is characterized by comprising the following steps:
1) And (3) mixing glass materials: weighing raw materials according to a proportion, and then placing the raw materials into a mortar for mixing to obtain a uniformly mixed glass mixture;
2) Tabletting and forming: placing the glass mixture obtained in the step 1) into a mold, performing compression molding, and demolding to obtain a sheet-shaped glass mixture;
3) Presintering: placing the sheet glass mixture obtained in the step 2) in a muffle furnace for presintering to obtain a block glass mixture;
4) Pneumatic suspension laser melting to prepare glass: preparing glass from the bulk glass mixture obtained in the step 3) by a pneumatic suspension laser melting method;
5) And (3) microcrystallizing treatment: and (3) placing the glass obtained in the step (4) into a muffle furnace for heat treatment to obtain the transparent microcrystalline glass containing CaTa 2O6 nano-crystals.
7. The method for producing a transparent glass ceramic containing CaTa 2O6 nanocrystals according to claim 6, wherein the heat treatment temperature in step 5) is 880-930 ℃, the holding time is 1-20 hours, and then cooling to room temperature with a furnace.
8. Use of a CaTa 2O6 nanocrystalline-containing transparent glass-ceramic according to any one of claims 1 to 5 in optical window materials and fluorescent conversion matrix materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310529922.0A CN116573860B (en) | 2023-05-11 | 2023-05-11 | Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310529922.0A CN116573860B (en) | 2023-05-11 | 2023-05-11 | Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116573860A CN116573860A (en) | 2023-08-11 |
| CN116573860B true CN116573860B (en) | 2024-05-17 |
Family
ID=87544758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310529922.0A Active CN116573860B (en) | 2023-05-11 | 2023-05-11 | Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116573860B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265026A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof |
| JP2011093764A (en) * | 2009-10-30 | 2011-05-12 | Ohara Inc | Glass ceramic and method for producing the same |
| JP2011098869A (en) * | 2009-11-07 | 2011-05-19 | Ohara Inc | Glass ceramic, method for manufacturing the same, photocatalytically functional compact and hydrophilic compact |
| CN107082561A (en) * | 2017-04-01 | 2017-08-22 | 武汉理工大学 | A kind of calcium tantalum aluminate glass and its production and use |
-
2023
- 2023-05-11 CN CN202310529922.0A patent/CN116573860B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265026A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof |
| JP2011093764A (en) * | 2009-10-30 | 2011-05-12 | Ohara Inc | Glass ceramic and method for producing the same |
| JP2011098869A (en) * | 2009-11-07 | 2011-05-19 | Ohara Inc | Glass ceramic, method for manufacturing the same, photocatalytically functional compact and hydrophilic compact |
| CN107082561A (en) * | 2017-04-01 | 2017-08-22 | 武汉理工大学 | A kind of calcium tantalum aluminate glass and its production and use |
Non-Patent Citations (3)
| Title |
|---|
| High Elastic Moduli of a 54Al2O3-46Ta2O5 Glass Fabricated via Containerless Processing;Rosales-Sosa, GA 等;《scientificreports》(第第5期期);15233 * |
| M. Sales等.The Phase Diagram CaO-Al2O3-Ta2O5 and the Crystal Structures of Ca2AlTaO6 and CaAlTaO5.《Journal of Solid State Chemistry》.1999,第第143卷卷第62-68页. * |
| The Phase Diagram CaO-Al2O3-Ta2O5 and the Crystal Structures of Ca2AlTaO6 and CaAlTaO5;M. Sales等;《Journal of Solid State Chemistry》;第第143卷卷;第62-68页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116573860A (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ming et al. | An ultra-high yield of spherical K 2 NaScF 6: Mn 4+ red phosphor and its application in ultra-wide color gamut liquid crystal displays | |
| JP6341618B2 (en) | Nanostructured glasses and glass-ceramics that are transparent in the visible and infrared ranges | |
| Zaid et al. | Synthesis and characterization of low cost willemite based glass–ceramic for opto-electronic applications | |
| Gao et al. | Effect of crystalline fraction on upconversion luminescence in Er3+/Yb3+ Co-doped NaYF4 oxyfluoride glass-ceramics | |
| Effendy et al. | Structural and optical properties of Er3+-doped willemite glass-ceramics from waste materials | |
| US11312655B2 (en) | Divalent manganese-doped all-inorganic perovskite quantum dot glass and preparation method thereof | |
| Yuan et al. | Effect of glass network modifier R2O (R= Li, Na and K) on upconversion luminescence in Er3+/Yb3+ co-doped NaYF4 oxyfluoride glass-ceramics | |
| CN110002762A (en) | A kind of Yb3+And CsPbBr3Borogermanates glass, preparation method and the application of nanocrystalline doping | |
| CN107540227B (en) | Europium-doped feldspar phase-containing microcrystalline glass and preparation method thereof | |
| Yan et al. | Luminescence and energy transfer of Dy3+-Eu3+ co-doped glass-ceramics containing ZnMoO4 | |
| Lei et al. | ZrO2-doped transparent glass-ceramics embedding ZnO nano-crystalline with enhanced defect emission for potential yellow-light emitter applications | |
| CN109928640B (en) | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof | |
| Gao et al. | Dual-mode photoluminescence from nanocrystalline Mn2+-doped Li, Zn-aluminosilicate glass ceramics | |
| Dymshits et al. | Transparent materials based on semiconducting ZnO: glass-ceramics and optical ceramics doped with rare-earth and transition-metal ions | |
| Gao et al. | Effect of glass-ceramics network intermediate Al2O3 content on up-conversion luminescence in Er3+/Yb3+ co-doped NaYF4 oxy-fluoride glass-ceramics | |
| Cruz et al. | Rare-earth doped transparent oxyfluoride glass-ceramics: processing is the key | |
| CN116573860B (en) | Transparent microcrystalline glass containing calcium tantalate nanocrystalline and preparation method and application thereof | |
| Xiao et al. | Efficient and broadband near-infrared emission of Cr3+-doped glass-ceramics for near-infrared light sources applications | |
| CN108314325B (en) | Self-crystallization microcrystalline glass with ultra-wideband near-infrared luminescence and preparation method and application thereof | |
| CN108409148B (en) | Infrared incoherent LED excited upconversion NaLuF4Glass-ceramic and method for producing the same | |
| CN107162427B (en) | A kind of high power semiconductor light source activation glass ceramics and its preparation method and application | |
| CN113912291B (en) | All-inorganic perovskite quantum dot fluorescent glass and preparation method and application thereof | |
| CN108558204B (en) | Spectrum-adjustable Eu and Dy-doped luminescent glass and preparation method thereof | |
| Maia et al. | Amorphous and crystalline borate nanocompounds doped with europium ions | |
| CN109437572B (en) | Precipitated BaTbF5Nanocrystalline germanosilicate microcrystalline glass and preparation 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |