CN115504672A - Infrared glass ceramic with chromium ions doped in various similar ways and preparation method thereof - Google Patents
Infrared glass ceramic with chromium ions doped in various similar ways and preparation method thereof Download PDFInfo
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 78
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 230000005684 electric field Effects 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 229910016569 AlF 3 Inorganic materials 0.000 claims abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims abstract description 3
- 239000008395 clarifying agent Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000011651 chromium Substances 0.000 claims description 29
- 238000000137 annealing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 17
- 239000006060 molten glass Substances 0.000 claims description 15
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006121 base glass Substances 0.000 claims description 13
- 238000010899 nucleation Methods 0.000 claims description 13
- 230000006911 nucleation Effects 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910020068 MgAl Inorganic materials 0.000 claims description 4
- 229910017857 MgGa Inorganic materials 0.000 claims description 4
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 229910017625 MgSiO Inorganic materials 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910019018 Mg 2 Si Inorganic materials 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 4
- 229910052804 chromium Inorganic materials 0.000 claims 4
- 230000005012 migration Effects 0.000 claims 1
- 238000013508 migration Methods 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000003384 imaging method Methods 0.000 abstract description 2
- 230000004297 night vision Effects 0.000 abstract description 2
- -1 rare earth ions Chemical class 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 238000010309 melting process Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- 230000005284 excitation Effects 0.000 description 7
- 239000012458 free base Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004186 food analysis Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- 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
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
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Abstract
The invention discloses a preparation method of chromium ion doped multiphase near infrared glass ceramic, which comprises MgO and SiO 2 、Al 2 O 3 、ZnO、Ga 2 O 3 、AlF 3 、K 2 CO 3 And the sintering aid, the clarifying agent, the nucleating agent, the rare earth ions (RE) and the chromium ions are prepared by a multi-melting process and an alternating electric field induced nucleation-crystallization process. The raw materials of the invention are easy to obtain, and the prepared glass ceramic with various crystal phases which coexist can be effectively excited by blue light and ultraviolet light, and has the advantages ofLong wavelength, wide half-peak width, high thermal stability, high quantum efficiency and the like; specifically, the crystal phases precipitated in the glass ceramic are more than or equal to 2, the emission peak is between 600 and 1700nm, and the peak value>800nm, half-peak width of 150-350nm, luminous intensity at 150 deg.C higher than 80% of that at room temperature, and internal quantum efficiency>50 percent, is particularly suitable for near infrared light sources in the detection fields of biomedical imaging, night vision, food detection and the like.
Description
Technical Field
The invention belongs to the technical field of glass ceramic materials, and particularly relates to an infrared glass ceramic with multiple similar chromium ion doping and a preparation method thereof, which can be applied to the fields of food analysis, health monitoring, iris recognition, infrared shooting and the like.
Background
Near Infrared (NIR) light in the wavelength range of 650-1700nm, which is in the region between the visible and infrared regions of the electromagnetic spectrum, can penetrate into biological tissue without damage, has highly attenuating properties. Therefore, the NIR spectrum technology taking NIR light as a light source has the characteristics of no damage and quick detection, and is suitable for the real-time nondestructive detection fields of food analysis, health monitoring, iris recognition, infrared shooting and the like. However, the lack of efficient, miniaturized broadband NIR light sources is one of the bottlenecks in implementing this technology.
At present, commercial NIR light sources comprise halogen tungsten lamps, organic light emitting diodes, super-continuous lasers and the like, but have the defects of unstable spectrum, narrow emission spectrum, high energy consumption, short service life, more generated heat and the like, and the application of the NIR light sources in the NIR spectrum technology is limited. In contrast, the NIR-LED light source converted by the fluorescent powder shows better application prospect, but the NIR light source packaged by the blue light LED combined with the NIR fluorescent powder still has the inherent powder defects of difficult control of fluorescent powder coating uniformity and thickness, low heat conductivity coefficient of an organic packaging material, recession of high-temperature efficiency, serious light scattering and the like. Compared with an NIR light source packaged by fluorescent powder, the NIR light source packaged by the blue light LED and the NIR glass ceramic avoids using organic packaging glue, overcomes the inherent defects of powder materials, and has the advantages of high chemical stability, high temperature stability and heat conductivity, wide raw material composition range, simple preparation process, easiness in manufacturing various complex shapes and the like. Therefore, the NIR light source formed by combining the blue LED with the NIR glass ceramic packaging shows great advantages.
The chromium ion doped glass ceramic is widely researched by numerous scholars due to excellent physicochemical and optical properties. Patent with application number CN201410031022.4 discloses transition metal ion Cr 4+ Doped single-phase glass ceramic and preparation method thereof, wherein crystal phase precipitated in the glass ceramic is Li 1.14 Zn 1.43-x Mg x SiO 4 (0.01<x<0.1 Emission peak range of 1000-1600nm can be seen from the emission spectrum of the glass ceramic; although the emission peak range of the glass ceramic is wider, the glass ceramic lacks of luminescent components of 600-1000nm, and the crystallinity of the glass ceramic is lower from the XRD pattern of the glass ceramic, which influences the luminescent intensity of the glass ceramic, thereby limiting the application of the glass ceramic in real life. Anastasia Babkina et al reported a transparent LiAl 7 B 4 O 17 :Cr 3+ A preparation method of the glass ceramic and an application thereof (Journal of Non-Crystalline Solids 534 (2020) 119947), under the excitation of 532nm light, the glass ceramic shows more than 50% of quantum efficiency. However, the emission spectrum coverage range of the glass ceramic is short and only located in the range of 650-800nm, the emission peak is about 700nm, and the half-peak width is narrow, so that the multi-scene application of the glass ceramic in the actual life is influenced. Weirong Lan et al disclose a Cr 3+ Doped SiO 2 -ZnGa 2 O 4 :Cr 3+ Under the excitation of 414nm light, the glass ceramic shows NIR luminescence in a range of 620-850, but the glass ceramic has narrower half-peak width and lower luminescence efficiency, thereby influencing the practical use. Compared with single-phase glass ceramic, the multiphase glass ceramic can selectively enrich and isolate luminescent ions in different crystal phases while crystallizingIn the method, not only can the fluorescence quenching between the luminescent ions be effectively inhibited, and the high-efficiency luminescence of the glass ceramic be realized, but also the broadband and long-wavelength luminescence superior to that of single-phase glass ceramic can be realized. Through effective regulation and control of the chromium ion doped glass ceramic, various microcrystals containing octahedral lattice sites or tetrahedral lattice sites can be separated out, and Cr is induced 3+ Or Cr 4+ Ions are selectively doped in octahedral lattices or tetrahedral lattices of different crystal phases, so that efficient and broadband NIR luminescence is realized. Therefore, the chromium ion doped multiphase glass ceramic is a promising NIR luminescent material.
Disclosure of Invention
The invention aims to provide infrared glass ceramic doped with chromium ions and a preparation method thereof, wherein the preparation raw materials are easy to obtain, the price is low, the process is simple, and the industrial production is easy to realize; the obtained chromium ion doped glass ceramic can be effectively excited by blue light and ultraviolet light, and has the characteristics of long wavelength, wide half-peak width, high thermal stability, high quantum efficiency and the like.
The chromium ion doped multiphase near-infrared glass ceramic is characterized in that the base glass comprises the following components in percentage by mol: mgO:5 to 20 percent; siO 2 2 ：20～60％；Al 2 O 3 ：5～25％；Ga 2 O 3 ：0～15％；ZnO：0～15％；AlF 3 ：5～25％；K 2 CO 3 ：0～10％；RE 2 O 3 ：0～5％；Cr 2 O 3 ：0.05～5％；CrO 2 ：0～5％；B 2 O 3 、Na 2 O and Li 2 Total content of O: 1 to 20 percent; clarifying agent Sb 2 O 3 Is 0.5-2 wt.% of the total mass of other raw materials.
The chromium ion doped multiphase near infrared glass ceramic is characterized in that the chromium ion source in the raw material components is Cr 2 O 3 Or Cr 2 O 3 And CrO 2 A combination of (1); RE 2 O 3 Is Yb 2 O 3 、Nd 2 O 3 、Ce 2 O 3 One or more of the above.
The chromium ion is doped with multiple phasesThe near infrared glass ceramic is characterized in that the sintering aid is B 2 O 3 、Na 2 O or Li 2 One or more combinations of O.
The chromium ion doped multiphase near infrared glass ceramic is characterized in that sintering aid is introduced by corresponding borate or carbonate or fluoride.
The chromium ion doped multiphase near infrared glass ceramic is characterized in that the nucleating agent is ZrO 2 、TiO 2 One or a plurality of combinations of nano Ag powder; the content of the nucleating agent is 1 to 10mol percent.
The invention also provides a preparation method of the infrared glass ceramic doped with chromium ions in various similar ways, which comprises the following specific steps:
(a) Weighing the raw materials according to a predetermined molar ratio, adding a proper amount of absolute ethyl alcohol, and grinding in an agate mortar for 0.5-5 h to obtain a uniformly mixed mixture; (b) Putting the mixture into a platinum-rhodium crucible or a quartz crucible, putting the platinum-rhodium crucible or the quartz crucible into a melting furnace, heating the mixture from room temperature to 1600-1700 ℃, preserving heat for 1-5 hours, pouring molten glass into a mold preheated to 600-800 ℃, pressing and molding the molten glass, then transferring the molten glass into an annealing furnace with the same temperature, preserving heat for 5-10 hours, and cooling the molten glass to room temperature along with the furnace; (c) Repeating the steps (a) and (b) for a plurality of times to obtain homogeneous bubble-free base glass; (d) Placing the base glass in a precision annealing furnace and keeping the temperature at the glass transition temperature T g +/-50 deg.C and crystallizing temp T c Carrying out heat treatment on the crystal in a +/-50 ℃ range by adopting processes of gradient variable speed induced nucleation and crystallization and alternating electric field induced nucleation and crystallization; (e) And after the heat treatment is finished, cooling to room temperature to obtain the chromium ion doped multiphase near infrared glass ceramic.
The preparation method of the chromium ion doped multiphase near infrared glass ceramic further comprises the following preferred scheme:
preferably, the content of the nucleating agent doped in the raw material is 2-10 mol%.
Preferably, the grinding time of the raw material in the step (a) in an agate mortar is 1-3 h.
Preferably, the stirring rate of the molten glass in the step (b) is 10 to 25r/min
Preferably, the temperature rising rate in the step (b) is 5-20 ℃/min, and the temperature reduction rate is 10-50 ℃/min.
Preferably, the number of repetition of the steps (a) and (b) in the step (c) is not less than 1.
The preparation method of the chromium ion doped multiphase near infrared glass ceramic is characterized by comprising the following steps: room temperature to T in step (d) g The temperature rise rate of the +/-50 ℃ temperature interval is 1-3 ℃/min, the heat preservation time is 5-100h g Plus or minus 50 ℃ to T c The temperature rise rate of the +/-50 ℃ temperature interval is 20-40 ℃/min, the heat preservation time is 0.5-5 h, and the frequency of the applied alternating electric field is 50Hz; the cooling rate in the step (e) is 5-40 ℃/min.
The preparation method of the chromium ion doped multiphase near infrared glass ceramic is characterized by comprising the following steps: the multiphase glass-ceramic comprises Mg 2 Al 4 Si 5 O 18 、MgAl 2 O 4 、ZnGa 2 O 4 、MgGa 2 O 4 、KZnF 3 、ZnMgSi 2 O 6 、MgSiO 3 、Mg 2 Si 2 O 6 、Mg 2 SiO 4 、Mg 3 Al 2 Si 3 O 12 2 or more of the isocrystalline phases. The valence state of the chromium ions in the crystal is +3 or +3 and +4, wherein the +3 chromium ions occupy octahedral sites in the crystal and the +4 chromium ions occupy tetrahedral sites in the crystal.
The preparation method of the chromium ion doped multiphase near infrared glass ceramic is characterized by comprising the following steps: the prepared infrared glass ceramic has the emission peak between 600nm and 1700nm, the peak value of more than 800nm, the half-peak width of 150 nm to 350nm, the luminous intensity at 150 ℃ of more than 80 percent of that at room temperature, and the internal quantum efficiency of more than 50 percent.
In summary, compared with the prior art, the invention has the following remarkable effects:
(1) The method has the advantages of low investment, high production efficiency, simple process and non-strict requirements on production conditions, and is suitable for industrial production.
(2) The glass ceramic prepared by the invention has high doping concentration and uniform distribution of chromium ions and rare earth ions.
(3) The chromium ion doped multiphase near-infrared glass ceramic obtained by the invention can be effectively excited by blue light and ultraviolet light, has the characteristics of long wavelength, wide half-peak width, high thermal stability, high quantum efficiency and the like, and can be used in the detection fields of biomedical imaging, night vision, food detection and the like.
Drawings
FIG. 1 is a graph of the emission spectrum and spectral fit of a chromium ion doped multiphase glass ceramic.
FIG. 2 is a graph of the emission spectrum and spectral fit of a chromium ion doped duplex glass ceramic.
Detailed Description
Example 1
A chromium ion doped multiphase near infrared glass ceramic is prepared by the following steps:
(a) Weighing raw materials of MgO:6.1386g; ga 2 O 3 ：3.7526g；Al 2 O 3 ：16.0664g；SiO 2 ：33.3833g；H 3 BO 3 ：2.4856g；Na 2 CO 3 ：2.1412g；Li 2 CO 3 ：0.7464g；AlF 3 ：4.2032g；ZrO 2 ：1.8670g；TiO 2 ：0.4034g；Cr 2 O 3 ：0.6083g；Sb 2 O 3 :0.7252g. Pouring the raw materials and a proper amount of absolute ethyl alcohol into an agate mortar together, and grinding for 1.5h to obtain a uniformly mixed mixture;
(b) Putting the obtained uniform mixture into a platinum-rhodium crucible, putting the platinum-rhodium crucible into a melting furnace, heating the platinum-rhodium crucible to 1600 ℃ from room temperature at the heating rate of 8 ℃/min, keeping the temperature for 1.5h, and stirring the molten liquid at the stirring rate of 15r/min; pouring the molten glass liquid onto a mold preheated to 650 ℃ for press molding, then moving the mold into an annealing furnace at 650 ℃ for annealing for 6 hours, and then cooling the mold to room temperature at the speed of 20 ℃/min to obtain base glass;
(c) Repeating the steps (a) and (b) for 2 times to obtain homogeneous bubble-free base glass;
(d) Placing the obtained basic glass in a precision annealing furnace, heating to the nucleation temperature of 780 ℃ at the speed of 2 ℃/min, preserving heat for 12h, then heating to 960 ℃ at the speed of 30 ℃/min, preserving heat for 1h, and applying an alternating electric field with the frequency of 50Hz all the time in the whole heat treatment process.
(e) After the heat treatment process is finished, the furnace is cooled to room temperature at the speed of 10 ℃/min to obtain Cr 3+ Doped Mg 2 Al 4 Si 5 O 18 、MgSiO 3 A multiphase glass-ceramic.
The chromium ion doped multiphase near infrared glass ceramic obtained in the embodiment has an emission peak between 660 and 1500nm under the excitation of 468nm blue light, the peak value of the emission peak is 815nm, the half-peak width is 235nm, the luminous intensity at 150 ℃ is 82.5 percent of that at room temperature, and the internal quantum efficiency is 52.5 percent.
Example 2
A chromium ion doped multiphase near infrared glass ceramic is prepared by the following steps:
(a) Weighing raw materials of MgO:4.9109g; znO:5.2245g; ga 2 O 3 ：14.6350g；Al 2 O 3 ：6.1794g；SiO 2 ：32.1694g；H 3 BO 3 ：0.6214g；Na 2 CO 3 ：3.2118g；Li 2 CO 3 ：0.3732g；AlF 3 ：5.0438g；Yb 2 O 3 :0.3912g; ag powder: 1.6181g; zrO (ZrO) 2 ：1.2446g；TiO 2 ：0.4034g；Cr 2 O 3 ：0.3041g；Sb 2 O 3 :0.8069g. Pouring the raw materials and a proper amount of absolute ethyl alcohol into an agate mortar together for grinding for 2 hours to obtain a uniformly mixed mixture;
(b) Putting the obtained uniform mixture into a platinum-rhodium crucible, putting the platinum-rhodium crucible into a melting furnace, heating the platinum-rhodium crucible to 1620 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 2 hours, and stirring the molten liquid at a stirring rate of 20r/min; pouring the molten glass into a mold preheated to 680 ℃ for press molding, then moving the mold into an annealing furnace at 680 ℃ for annealing for 7 hours, and then cooling the mold to room temperature at the speed of 30 ℃/min to obtain base glass;
(c) Repeating the steps (a) and (b) for 3 times to obtain homogeneous bubble-free base glass;
(d) Placing the obtained basic glass in a precision annealing furnace, heating to the nucleation temperature of 800 ℃ at the speed of 2 ℃/min, preserving heat for 24h, then heating to 960 ℃ at the speed of 30 ℃/min, preserving heat for 1h, and applying an alternating electric field with the frequency of 50Hz all the time in the whole heat treatment process.
(e) After the heat treatment process is finished, the furnace is cooled to room temperature at the speed of 15 ℃/min to obtain Cr 3+ Doped MgAl 2 O 4 、ZnGa 2 O 4 、Mg 3 Al 2 Si 3 O 12 A multiphase glass-ceramic.
The chromium ion doped multiphase near infrared glass ceramic obtained in the embodiment has an emission peak between 680 nm and 1600nm under the excitation of 450nm blue light, the peak value of the emission peak is 985nm, the half-peak width is 250nm, the luminous intensity at 150 ℃ is 86.3% of that at room temperature, and the internal quantum efficiency is 56.6%.
Example 3
A chromium ion doped multiphase near infrared glass ceramic is prepared by the following steps:
(a) Weighing raw materials of MgO:4.0924g; znO:4.4782g; ga 2 O 3 ：11.2577g；Al 2 O 3 ：5.6644g；SiO 2 ：30.3485g；H 3 BO 3 ：4.9713g；Na 2 CO 3 ：1.0706g；Li 2 CO 3 ：0.7464g；AlF 3 ：4.6235g；K 2 CO 3 ：6.9174g；Yb 2 O 3 ：3.9412g；Nd 2 O 3 ：3.3817g；Ce 2 O 3 :3.2839g; ag powder: 1.0787g; zrO (ZrO) 2 ：1.2446g；TiO 2 ：0.4034g；CrO 2 ：0.1261g；Cr 2 O 3 ：0.5322g；Sb 2 O 3 :0.8905g. Pouring the raw materials and a proper amount of absolute ethyl alcohol into an agate mortar together for grinding for 2 hours to obtain a uniformly mixed mixture;
(b) Putting the obtained uniform mixture into a platinum-rhodium crucible, heating the mixture to 1630 ℃ from room temperature at a heating rate of 15 ℃/min in a melting furnace, preserving the heat for 3 hours, and stirring the molten liquid at a stirring rate of 25r/min; pouring the molten glass liquid onto a mold preheated to 700 ℃ for press molding, then moving the mold into an annealing furnace at 700 ℃ for annealing for 8 hours, and then cooling the mold to room temperature at the speed of 30 ℃/min to obtain base glass;
(c) Repeating the steps (a) and (b) for 3 times to obtain homogeneous bubble-free base glass;
(d) And (3) placing the obtained basic glass in a precise annealing furnace, heating to the nucleation temperature of 850 ℃ at the speed of 2.5 ℃/min, preserving heat for 48 hours, then heating to the temperature of 1000 ℃ at the speed of 25 ℃/min, preserving heat for 1.5 hours, and applying an alternating electric field with the frequency of 50Hz in the whole heat treatment process.
(e) After the heat treatment process is finished, the furnace is cooled to room temperature at the speed of 20 ℃/min to obtain Cr 3+ And Cr 4+ Doped Mg 2 Al 4 Si 5 O 18 、MgGa 2 O 4 、KZnF 3 A multiphase glass-ceramic.
The chromium ion doped multiphase near infrared glass ceramic obtained in the embodiment has an emission peak between 650 nm and 1580nm under the excitation of 405nm light, the peak value of the emission peak is 985nm, the half-peak width is 242nm, the luminous intensity at 150 ℃ is 83.9 percent of that at room temperature, and the internal quantum efficiency is 68.8 percent.
Example 4
A chromium ion doped multiphase near infrared glass ceramic is prepared by the following steps:
(a) Weighing raw materials of MgO:4.0924g; znO:3.7318g; ga 2 O 3 ：9.3814g；Al 2 O 3 ：6.1794g；SiO 2 ：31.8659g；Li 2 CO 3 ：4.4782g；AlF 3 ：4.8337g；K 2 CO 3 ：6.9174g；Nd 2 O 3 ：3.3817g；Ce 2 O 3 ：3.2839g；TiO 2 ：1.6135g；CrO 2 ：0.1681g；Cr 2 O 3 ：0.8364g；Sb 2 O 3 :0.8158g. Pouring the raw materials and a proper amount of absolute ethyl alcohol into an agate mortar together for grinding for 2 hours to obtain a uniformly mixed mixture;
(b) Putting the obtained uniform mixture into a platinum-rhodium crucible, putting the platinum-rhodium crucible into a melting furnace, heating the platinum-rhodium crucible to 1680 ℃ from room temperature at the heating rate of 12 ℃/min, keeping the temperature for 2 hours, and stirring the molten liquid at the stirring rate of 20r/min; then pouring the molten glass liquid onto a mold preheated to 620 ℃ for press molding, then moving the mold into an annealing furnace at 620 ℃ for annealing for 9 hours, and then cooling the mold to room temperature at the speed of 30 ℃/min to obtain base glass;
(c) Repeating the steps (a) and (b) for 3 times to obtain homogeneous bubble-free base glass;
(d) And (3) placing the obtained basic glass in a precision annealing furnace, heating to the nucleation temperature of 760 ℃ at the speed of 3 ℃/min, preserving heat for 60 hours, then heating to 980 ℃ at the speed of 25 ℃/min, preserving heat for 2 hours, and applying an alternating electric field with the frequency of 50Hz all the time in the whole heat treatment process.
(e) After the heat treatment process is finished, the furnace is cooled to room temperature at the speed of 30 ℃/min to obtain Cr 3+ And Cr 4+ Doped Mg 2 Al 4 Si 5 O 18 、ZnGa 2 O 4 A multiphase glass-ceramic.
The chromium ion doped multiphase near infrared glass ceramic obtained in the embodiment has an emission peak between 650 nm and 1400nm under the excitation of 450nm blue light, the peak value of the emission peak is 820nm, the half-peak width is 195nm, the luminous intensity at 150 ℃ is 85.6 percent of that at room temperature, and the internal quantum efficiency is 71.6 percent.
Example 5
A chromium ion doped multiphase near infrared glass ceramic is prepared by the following steps:
(a) Weighing raw materials of MgO:6.1386g; ga 2 O 3 ：18.7628g；Al 2 O 3 ：8.2392g；SiO 2 ：30.3485g；Na 2 CO 3 ：4.2824g；AlF 3 ：6.1367g；Ce 2 O 3 :6.5679g; ag powder: 3.2361g; crO 2 ：0.1681g；Cr 2 O 3 ：0.7603g；Sb 2 O 3 :0.8550g. Pouring the raw materials and a proper amount of absolute ethyl alcohol into an agate mortar together for grinding for 2 hours to obtain a uniformly mixed mixture;
(b) Putting the obtained uniform mixture into a platinum-rhodium crucible, putting the crucible into a melting furnace, heating the crucible to 1660 ℃ from room temperature at the heating rate of 10 ℃/min, preserving the heat for 2 hours, and stirring the molten liquid at the stirring rate of 15r/min; then pouring the molten glass liquid onto a mold preheated to 720 ℃ for press molding, then moving the mold into an annealing furnace at 720 ℃ for annealing for 10 hours, and then cooling the mold to room temperature at the speed of 35 ℃/min to obtain base glass;
(c) Repeating the steps (a) and (b) for 3 times to obtain homogeneous bubble-free base glass;
(d) And (3) placing the obtained basic glass in a precision annealing furnace, heating to the nucleation temperature of 850 ℃ at the speed of 1 ℃/min, preserving heat for 72 hours, heating to the nucleation temperature of 980 ℃ at the speed of 25 ℃/min, preserving heat for 2 hours, and applying an alternating electric field with the frequency of 50Hz in the whole heat treatment process.
(e) After the heat treatment process is finished, the furnace is cooled to room temperature at the speed of 35 ℃/min to obtain Cr 3+ And Cr 4+ Doped Mg 2 Al 4 Si 5 O 18 、MgAl 2 O 4 、MgGa 2 O 4 A multiphase glass-ceramic.
In the embodiment, the emission peak of the obtained chromium ion doped multiphase near-infrared glass ceramic is between 680 and 1580nm under the excitation of 405nm light, the peak value of the emission peak is 860nm, the half-peak width is 219nm, the luminous intensity at 150 ℃ is 85.3 percent of that at room temperature, and the internal quantum efficiency is 65.5 percent.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. The chromium ion doped multiphase near infrared glass ceramic is characterized in that the basic glass comprises the following components in percentage by mole: mgO:5 to 20 percent; siO 2 2 ：20～60％；Al 2 O 3 ：5～25％；Ga 2 O 3 ：0～15％；ZnO：0～15％；AlF 3 ：5～25％；K 2 CO 3 ：0～10％；RE 2 O 3 ：0～5％；Cr 2 O 3 ：0.05～5％；CrO 2 ：0～5％；B 2 O 3 、Na 2 O and Li 2 Total content of O: 1 to 20 percent; clarifying agent Sb 2 O 3 The content of (A) is 0.5-2 wt.% of the total mass of other raw materials; the nucleating agent is ZrO 2 、TiO 2 And one or more of nano Ag powder with the content of 1-15 mol percent.
2. The chromium ion-doped multiphase near infrared glass-ceramic according to claim 1, wherein the source of chromium ions in the raw material is Cr 2 O 3 Or Cr 2 O 3 And CrO 2 Combinations of (a) and (b); RE 2 O 3 Is Yb 2 O 3 、Nd 2 O 3 、Ce 2 O 3 One or more combinations thereof.
3. The chromium ion-doped multiphase near infrared glass-ceramic according to claim 1, characterized in that the sintering aid is B 2 O 3 、Na 2 O or Li 2 One or more combinations of O, introduced from the corresponding borate or carbonate or fluoride.
4. A chromium ion doped multiphase near infrared glass-ceramic according to any of claims 1 to 3, characterized in that the base glass is prepared by the following steps:
(a) Weighing the raw materials according to a predetermined molar ratio, adding a proper amount of absolute ethyl alcohol, and grinding in an agate mortar for 1-5 hours to obtain a uniformly mixed mixture;
(b) Putting the mixture into a platinum-rhodium crucible or a quartz crucible, putting the platinum-rhodium crucible or the quartz crucible into a melting furnace, heating the mixture from room temperature to 1600-1700 ℃, preserving heat for 1-5 hours, pouring molten glass into a mold preheated to 600-800 ℃, pressing and molding the molten glass, then transferring the molten glass into an annealing furnace with the same temperature, preserving heat for 5-10 hours, and cooling the molten glass to room temperature along with the furnace;
(c) Repeating the steps (a) and (b) for a plurality of times to obtain the base glass which is homogeneous and has no bubbles.
5. A chromium ion-doped base glass according to claim 4, characterized in that the molten glass in step (b) is mechanically stirred while it is molten, at a stirring rate of 5 to 30r/min.
6. The method for preparing chromium ion doped multiphase near infrared glass ceramic according to any one of claims 1 to 5, which is characterized by comprising the following specific preparation steps:
(a) Placing the base glass in a precision annealing furnace and keeping the temperature at the glass transition temperature T g Plus or minus 50 ℃ and crystallization temperature T c Performing heat treatment on the crystal in the range of +/-50 ℃ by adopting a process of gradient variable speed induced nucleation and crystallization and an alternating electric field induced nucleation and crystallization;
(b) After the crystallization treatment is finished, the annealing furnace is cooled to room temperature at the speed of 5-20 ℃/min, and the chromium ion doped multiphase near infrared glass ceramic is obtained;
the step (a) of gradient speed change induced nucleation and crystallization refers to that the temperature is increased from room temperature to T through a small temperature increase rate g A temperature of 50 ℃ and a time sufficient to ensure that the base glass has acquired sufficient energy to nucleate, and then is raised to T at a very rapid ramp rate c Plus or minus 50 ℃ for a suitable time to ensure that the nuclei in the base glass grow completely without excessively growing, and to achieve both high crystallization and high transparency of the glass ceramic. The 'alternating electric field induced nucleation and crystallization' means that an alternating electric field is applied to the basic glass in the heat treatment process of the basic glass to promote the fluctuation of the concentration of nucleation points in the glass, so that the effective migration of ions in the glass is caused, the effective phase separation and the full crystallization of the basic glass are realized, and the aim of preparing the high-crystallinity chromium ion doped multiphase near infrared glass ceramic is fulfilled.
7. The method for preparing chromium ion doped multiple near infrared glass ceramic according to claim 6, wherein the method comprises the following steps: room temperature to T g The temperature rise rate of the +/-50 ℃ temperature interval is 1-3 ℃/min, the heat preservation time is 5-100h g Plus or minus 50 ℃ to T c The temperature rise rate of the +/-50 ℃ temperature interval is 20-40 ℃/min, and the heat preservation time is 0.5About 5h; the cooling rate is 5-20 ℃/min, and the frequency of the applied alternating electric field is 50Hz.
8. The chromium ion doped multiphase near infrared glass-ceramic of claim 7, wherein the multiphase glass-ceramic comprises Mg 2 Al 4 Si 5 O 18 、MgAl 2 O 4 、ZnGa 2 O 4 、MgGa 2 O 4 、KZnF 3 、ZnMgSi 2 O 6 、MgSiO 3 、Mg 2 Si 2 O 6 、Mg 2 SiO 4 、Mg 3 Al 2 Si 3 O 12 2 or more of the isocrystalline phases.
9. The chromium ion doped multiphase near infrared glass-ceramic of claim 8, wherein the chromium ions have a valence state in the crystal of +3 or coexistence of +3 and +4, wherein the +3 chromium ions occupy octahedral sites in the crystal and the +4 chromium ions occupy tetrahedral sites in the crystal.
10. The chromium ion-doped multiphase near infrared glass-ceramic according to any one of claims 7 to 9, characterized in that: the prepared infrared glass ceramic has the emission peak between 600-1700 nm, peak value over 800nm, half-peak width of 150-350nm, luminous intensity at 150 deg.c over 80% of that at room temperature, and internal quantum efficiency over 50%.
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