CN113831015A - Cu/Mn doped colored glass with luminous function, and preparation method and regulation and control method thereof - Google Patents
Cu/Mn doped colored glass with luminous function, and preparation method and regulation and control method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 159
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 32
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000002019 doping agent Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 25
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 20
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 43
- 239000011572 manganese Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 230000005284 excitation Effects 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 22
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000292 calcium oxide Substances 0.000 claims description 18
- 239000006066 glass batch Substances 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229940112669 cuprous oxide Drugs 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 7
- 239000011656 manganese carbonate Substances 0.000 claims description 7
- 235000006748 manganese carbonate Nutrition 0.000 claims description 7
- 229940093474 manganese carbonate Drugs 0.000 claims description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229940008015 lithium carbonate Drugs 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004040 coloring Methods 0.000 abstract description 3
- 238000000295 emission spectrum Methods 0.000 description 18
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 11
- 229910052761 rare earth metal Inorganic materials 0.000 description 11
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 8
- -1 rare earth ions Chemical class 0.000 description 8
- 239000010431 corundum Substances 0.000 description 7
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- 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
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides Cu/Mn doped colored glass with a light-emitting function, and a preparation method and a regulation method thereof. The glass comprises the following components in parts by mole: SiO 22: 40-60 parts of B2O3:0 to 15 portions of Al2O3: 3-20 parts of ZnO: 0 to 12 portions of CaF2: 12-22 parts of CaO: 0 to 17 portions of Na2O:0 to 17 parts of Li20-17 parts of O; doping agent: 0.01-5 parts of Cu as a dopant2One or a combination of two or more of O, CuO and MnO. The invention adopts transition metal ion doping, and the dopant has the functions of a coloring agent and a luminescence center, thereby realizing the glassColoring and light emitting functions; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring, and the color and the luminous performance of the glass can be adjusted and controlled by a simple method.
Description
Technical Field
The invention relates to Cu/Mn doped colored glass with a light-emitting function, a preparation method and a regulation and control method thereof, belonging to the technical field of novel glass.
Background
Glass generally refers to amorphous materials that have short range order and long range disorder in their structure. The colored glass is glass which can absorb, reflect and transmit light with different wavelengths so as to present different colors, and is mainly prepared by spraying organic dye on the surface of the glass or introducing a coloring agent. The common glass is generally in a solid state which is approximately colorless and transparent, and is difficult to meet the personalized requirements of consumers for beautifying life and the like. Therefore, attention is paid to composition design and production techniques of colored glass. The color glass can be applied to the aspects of art decoration, illumination, laser, light filtering and the like, and has important significance in the fields of daily life, industrial and agricultural production, science and technology of people. On the other hand, luminescent glasses can be obtained by introducing luminescent centers (e.g., rare earth ions) into the glass composition, which can produce luminescence under certain types of excitation. In recent years, luminescent glass has been used in the fields of display, lighting, and optical communication.
The colorant of the colored glass and the activator (luminescence center) of the luminescent glass generally adopt rare earth ions, but the rare earth resource reserves are limited and expensive, the exploitation and export of the rare earth are limited in many countries in the world, and most of the rare earth ions have narrow absorption bands and cannot efficiently absorb exciting light, thereby limiting the application of the luminescent glass prepared by the rare earth ions. Chinese patent document CN103803797A discloses luminescent glass for LED and luminescent glassA preparation method. The main component of the glass substrate of the luminescent glass for the LED is SiO2、Al2O3、B2O3、CaF2CaO, ZnO and Na2O, rare earth ion Tb3+、Eu3+、Dy3+、Ce3+And Sm3+The rare earth ions are double-doped or triple-doped in the glass substrate as a luminous center and are matched with the ultraviolet LED chip to emit white light; the luminescent glass is prepared by adopting a high-temperature melting method. The luminescent glass disclosed by the invention can regulate and control the emission spectrum, the color coordinate, the color temperature and the like of the luminescent glass by changing the components of the glass matrix, the concentration of rare earth ions and the excitation wavelength. However, the luminescent center of the luminescent glass is rare earth ion, the price is high, the absorption band is narrow, and the invention does not relate to the regulation and control of the color of the glass.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides Cu/Mn doped colored glass with a light-emitting function, a preparation method and a regulation and control method thereof. Using transition metals Cu+And Cu2+，Cu+、Cu2+And Mn2+Or Mn2+The ions are doped, and the dopant has the functions of a coloring agent and a luminescence center, so that the coloring and luminescence functions of the glass are realized; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring, and the color and the luminous performance of the glass can be adjusted and controlled by a simple method.
Description of terms:
room temperature: the temperature is 25 ℃. + -. 5 ℃.
The invention is realized by the following technical scheme:
a Cu/Mn doped color glass with a light-emitting function comprises the following components in parts by mole: SiO 22: 40-60 parts of B2O3:0 to 15 portions of Al2O3: 3-20 parts of ZnO: 0 to 12 portions of CaF2: 12-22 parts of CaO: 0 to 17 portions of Na2O:0 to 17 parts of Li20-17 parts of O; doping agent: 0.01-5 parts of Cu as a dopant2One or a combination of two or more of O, CuO and MnO.
According to the invention, the preferable Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 40-60 parts of B2O3:0 to 15 portions of Al2O3: 3-20 parts of ZnO: 0 to 12 portions of CaF2: 12-22 parts of CaO: 0 to 17 portions of Na2O:0 to 17 parts of Li20-17 parts of O; doping agent: 0.1 to 1.8 portions of Cu as the dopant2One or a combination of two or more of O, CuO and MnO.
According to the invention, the preferable Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF210-20 parts of Li210-16 parts of O or CaO; dopant Cu2O and CuO: 0.1 to 0.3 portion.
Preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43-50 parts of B2O3:10 parts of Al2O3: 10-17 parts of CaF215 parts of Li215 parts of O or CaO; dopant Cu2O and CuO: 0.2 part.
According to the invention, the preferable Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF2:10-20 parts of CaO or Li2O: 10-15 parts; dopant MnO: 0.2 to 0.6 portion.
Preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of, B2O3:10 parts of Al2O3: 17 parts of CaF2:15 parts of CaO or Li2O:15 parts of (1); dopant MnO: 0.4 part.
According to the invention, the preferable Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF2:10-20 parts of CaO: 10-15 parts; dopant Cu2O and CuO: 0.1-0.3 parts, MnO: 0.8 to 1.5 portions.
Preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of, B2O3:10 parts of Al2O3: 17 parts of CaF2:15 parts, CaO:15 parts of (1); dopant Cu2O and CuO: 0.2 part, MnO: 1-1.5 parts.
According to the invention, the color and the luminous performance of the glass are preferably regulated and controlled by changing the composition of the glass matrix or adjusting the type and the concentration of the dopant; or, the luminous performance of the glass is regulated and controlled by changing the excitation wavelength. The glass matrix is composed of components other than the dopant.
The preparation method of the Cu/Mn doped color glass with the luminescent function comprises the following steps:
(1) fully grinding and uniformly mixing raw materials of silicon dioxide, boric acid, aluminum oxide, zinc oxide, calcium fluoride, calcium carbonate, sodium carbonate, lithium carbonate, cuprous oxide and manganese carbonate to obtain a glass batch;
(2) melting: preserving the temperature of the glass batch mixture obtained in the step (1) at 1400-1600 ℃ for 0.5-2 hours, and melting to obtain glass liquid;
(3) forming and annealing: and (3) pouring the glass liquid obtained in the step (2) into a preheated copper mold, cooling and molding at room temperature, and then annealing at 400-550 ℃ for 1-3 hours to obtain the Cu/Mn doped colored glass with the light-emitting function.
According to the invention, the raw materials of silicon dioxide, boric acid, aluminum oxide, zinc oxide, calcium fluoride, calcium carbonate, sodium carbonate, lithium carbonate, cuprous oxide and manganese carbonate in the step (1) can be used in amounts calculated according to the composition of the glass.
Preferably, according to the present invention, in step (2), the temperature is raised to 1400-1600 ℃ at a temperature-raising rate of 4-8 ℃/min.
According to the invention, in the step (2), the melting mode is as follows: heating from room temperature to 350-450 ℃ at a heating rate of 5 ℃/min, then heating to 950-1050 ℃ at a heating rate of 6 ℃/min, and then heating to 1400-1600 ℃ at a heating rate of 4.8 ℃/min, and melting for 0.5-2 hours at the temperature to obtain the glass liquid. The temperature rising mode can fully decompose the raw materials, so that the obtained molten glass has better clarification and homogenization effects, and is beneficial to obtaining glass with uniform color, good luminescence performance and other characteristics, excellent structure and excellent performance.
According to the invention, cuprous oxide is adopted to introduce copper ions, the preparation is carried out in the air atmosphere, and actually Cu in the finally obtained glass+And Cu2+Coexistence; thus, the present invention relates to glass color and luminescence modulation based on Cu+And Cu2+，Cu+、Cu2+And Mn2+Or Mn2+Ions.
According to the regulating method of the Cu/Mn doped colored glass with the luminous function, the color and the luminous performance of the glass are regulated and controlled by changing the composition of the glass substrate or regulating the type and the concentration of the dopant; or, the luminous performance of the glass is regulated and controlled by changing the excitation wavelength.
The invention has the following technical characteristics and beneficial effects:
1. the invention uses SiO2-B2O3-Al2O3-ZnO-CaF2-CaO-Na2O-Li2O system glass as matrix, transition metal Cu+And Cu2+，Cu+、Cu2+And Mn2+Or Mn2+The prepared glass is a colorant and a luminous center, has a color, and can efficiently absorb exciting light under the excitation of ultraviolet light, thereby stably emitting visible light. The invention introduces transition metal Cu/Mn into the glass composition, and the selective absorption of transition metal ions to visible light wave bands can make the glass show specific color; on the other hand, the transition metal ions can generate electronic transition under the excitation of ultraviolet wavelength to emit visible light, and the transition metal ions have wider absorption band, so that the high-efficiency absorption of exciting light can be realized. The invention can change the glass structure and adjust the type and concentration of doped ions by changing the components of the glass matrixRegulating and controlling the color and the luminous performance of the material. In addition, the regulation and control of the glass luminescence property can be realized by changing the excitation wavelength. Various components supplement each other, and the synergistic effect is mutually exerted, so that the glass disclosed by the invention has different colors and different luminous properties, is adjustable and controllable in color and luminous property, and has the characteristics of good mechanical property and stable chemical property.
2. The preparation method is simple, and the prepared glass has good mechanical property and stable chemical property, has color and luminous function, and can be applied to LED luminous devices, artistic decoration and the like. The glass colorant and the luminescent center adopt transition metal ions and do not adopt rare earth elements, so that the glass manufacturing cost is low.
Drawings
FIG. 1 is an emission spectrum of glasses prepared in examples 1 to 3 under excitation at a wavelength of 296 nm;
FIG. 2 is an emission spectrum of glasses prepared in examples 4 and 5 under excitation at a wavelength of 414 nm;
FIG. 3 is an emission spectrum of glasses prepared in examples 6 and 7 under excitation at a wavelength of 352 nm;
FIG. 4 shows emission spectra of glasses prepared in example 6 under different wavelength excitation.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
Example 1
A Cu-doped color glass with a light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts of Li2O:15 parts of Cu2O: 0.2 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.3338g of silicon dioxide, 6.9333g of aluminum oxide, 4.9464g of boric acid, 4.6842g of calcium fluoride, 4.4334g of lithium carbonate and 0.1145g of cuprous oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in the example is dark cyan in appearance color, the glass prepared in the example is subjected to a fluorescence test, an emission spectrum under the excitation of a wavelength of 296nm is shown in figure 1, and luminescence is broadband emission with an emission peak of 489 nm.
Example 2
The copper ion doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts, CaO:15 parts of Cu2O: 0.2 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 8.9953g of silicon dioxide, 6.0352g of aluminum oxide, 4.3057g of boric acid, 4.0775g of calcium fluoride, 5.2275g of calcium carbonate and 0.0996g of cuprous oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example was blue in appearance and the emission spectrum under 296nm wavelength excitation is shown in FIG. 1.
As can be seen from FIG. 1, the emission peak of 489nm for example 1 and 455nm for example 2 are shown by comprehensive analysis, which shows that Li in the glass composition2When O (example 1) was replaced with CaO (example 2), the emission peak was blue-shifted. From the above, Li2The replacement of O and CaO can regulate the luminous color.
Example 3
The copper ion doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 50 parts of Al2O3:10 parts of, B2O3:10 parts of CaF2:15 parts of Li2O:15 parts of Cu2O: 0.2 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 12.2612g of silicon dioxide, 4.1616g of aluminum oxide, 5.0473g of boric acid, 4.7798g of calcium fluoride, 4.5239g of lithium carbonate and 0.1168g of cuprous oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example was pale cyan in appearance and had an emission spectrum under 296nm excitation as shown in FIG. 1.
From the comprehensive analysis, as can be seen from FIG. 1, the emission peak of example 3 is 481 nm. A reduction in Al in the glass composition is demonstrated in comparison with example 1 (emission peak at 489nm)2O3Increasing SiO2In an amount to shift the emission peak to a short wavelengthAnd (6) moving.
Comprehensive analysis shows that the change of the glass matrix composition has obvious influence on the luminescence spectrum of the Cu-doped glass. The change of glass composition causes the change of glass structure, and affects Cu+And Cu2+The electron transition behavior of the ions further regulates and controls the luminescent property of the glass.
Example 4
The Mn-doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts, CaO:15 parts, MnO: 0.4 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 9.5683g of silicon dioxide, 6.4197g of aluminum oxide, 4.5800g of boric acid, 4.3372g of calcium fluoride, 5.5605g of calcium carbonate and 0.1703g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example was light brown in appearance, and the emission spectrum under 414nm excitation was shown in FIG. 2, and it can be seen from FIG. 2 that the emission spectrum is a broad band spectrum with a peak at 618 nm.
Example 5
The manganese ion doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts of Li2O:15 parts, MnO: 0.4 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 10.3338g of silicon dioxide, 6.9333g of aluminum oxide, 4.9464g of boric acid, 4.6842g of calcium fluoride, 4.4334g of lithium carbonate and 0.1839g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example was brown in appearance and the emission spectrum at 414nm excitation is shown in FIG. 2. The emission peak is 627 nm.
From the comprehensive analysis, it can be seen from FIG. 2 that Li is used in the composition of the matrix glass, as compared with example 42O replaces CaO, and can shift the emission wavelength of the glass to a long wave direction (from 618nm to 627 nm).
Example 6
A Cu/Mn doped color glass with a light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts, CaO:15 parts of Cu2O: 0.2 part, MnO: 1 part.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 8.9953g of silicon dioxide, 6.0352g of aluminum oxide, 4.3057g of boric acid, 4.0775g of calcium fluoride, 5.2275g of calcium carbonate, 0.0996g of cuprous oxide and 0.4002g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example was cyan in appearance and had an emission spectrum under 352nm excitation as shown in FIG. 3. As can be seen from FIG. 3, the emission spectrum peaks at 487nm and 582nm, which are derived from Cu+，Cu2+Ions and Mn2+Electron transitions of the ions.
The emission spectra of the glasses prepared in this example under different wavelength excitations are shown in FIG. 4, the color coordinates and the color temperature are shown in Table 1, and the luminescence comes from Cu+，Cu2+Ions and Mn2+Electron transitions of the ions. It can be seen that the change of the excitation wavelength can obviously change the shape of the emission spectrum, the color coordinate and the color temperature of the glass, so that the regulation and control of the luminescence property of the glass can be realized by changing the excitation wavelength.
TABLE 1 color coordinates and color temperature data sheet
Example 7
The color glass co-doped with copper and manganese ions and having the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of Al2O3: 17 parts of, B2O310 parts of CaF2:15 parts, CaO:15 parts of Cu2O: 0.2 part, MnO: 1.5 parts.
The preparation method of the glass comprises the following steps:
(1) according to the components of the glass, 8.9953g of silicon dioxide, 6.0352g of aluminum oxide, 4.3057g of boric acid, 4.0775g of calcium fluoride, 5.2275g of calcium carbonate, 0.0996g of cuprous oxide and 0.6004g of manganese carbonate are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain a glass batch;
(2) melting: pouring the glass batch into a corundum crucible, heating the mixture to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating the mixture to 1000 ℃ at a heating rate of 6 ℃/min, heating the mixture to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting the mixture for 1 hour at the temperature to obtain glass liquid;
(3) pouring the molten glass obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.
The glass prepared in this example had a light cyan appearance, an emission spectrum under 352nm excitation as shown in FIG. 3, and color coordinates and color temperature as shown in Table 1.
As can be seen from FIG. 3, the emission spectrum peaks at 487nm and 599nm, which are derived from Cu+，Cu2+Ions and Mn2+Electron transitions of the ions. Comprehensive analysis shows that Mn can be increased by increasing the content of manganese ions relative to example 62+The emission wavelength of the ions produces a red shift (from 582nm to 599 nm). In addition, by changing the content of manganese ions, the relative intensity ratios, color coordinates, and color temperatures corresponding to the emission peaks of copper ions and manganese ions were also changed (table 1). Therefore, the emission spectrum shape of the glass can be changed by changing the content of the doped manganese ions, so that the regulation and control of the luminescence property of the prepared material are realized.
Claims (10)
1. The Cu/Mn doped color glass with the light-emitting function is characterized by comprising the following components in parts by mole: SiO 22: 40-60 parts of B2O3:0 to 15 portions of Al2O3: 3-20 parts of ZnO: 0 to 12 portions of CaF2: 12-22 parts of CaO: 0 to 17 portions of Na2O:0 to 17 parts of Li20-17 parts of O; doping agent: 0.01-5 parts of Cu as a dopant2One or a combination of two or more of O, CuO and MnO.
2. The Cu/Mn doped color glass with the luminescent function according to claim 1, wherein the Cu/Mn doped color glass with the luminescent function comprises the following components in parts by mole: SiO 22: 40-60 parts of B2O3：0-15 parts of, Al2O3: 3-20 parts of ZnO: 0 to 12 portions of CaF2: 12-22 parts of CaO: 0 to 17 portions of Na2O:0 to 17 parts of Li20-17 parts of O; doping agent: 0.1 to 1.8 portions of Cu as the dopant2One or a combination of two or more of O, CuO and MnO.
3. The Cu/Mn doped color glass with the luminescent function according to claim 1, wherein the Cu/Mn doped color glass with the luminescent function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF210-20 parts of Li210-16 parts of O or CaO; dopant Cu2O and CuO: 0.1-0.3 part;
preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43-50 parts of B2O3:10 parts of Al2O3: 10-17 parts of CaF215 parts of Li215 parts of O or CaO; dopant Cu2O and CuO: 0.2 part.
4. The Cu/Mn doped color glass with the luminescent function according to claim 1, wherein the Cu/Mn doped color glass with the luminescent function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF2:10-20 parts of CaO or Li2O: 10-15 parts; dopant MnO: 0.2-0.6 part;
preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of, B2O3:10 parts of Al2O3: 17 parts of CaF2:15 parts of CaO or Li2O:15 parts of (1); dopant MnO: 0.4 part.
5. The Cu/Mn doped pigment with luminescent function of claim 1The colored glass is characterized in that the Cu/Mn doped colored glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 40-50 parts of B2O3: 5-15 parts of Al2O3:10-20 parts of CaF2:10-20 parts of CaO: 10-15 parts; dopant Cu2O and CuO: 0.1-0.3 parts, MnO: 0.8-1.5 parts;
preferably, the Cu/Mn doped color glass with the light-emitting function comprises the following components in parts by mole: SiO 22: 43 parts of, B2O3:10 parts of Al2O3: 17 parts of CaF2:15 parts, CaO:15 parts of (1); dopant Cu2O and CuO: 0.2 part, MnO: 1-1.5 parts.
6. The Cu/Mn doped color glass with the luminescent function according to claim 1, wherein the color and the luminescent property of the glass are regulated and controlled by changing the composition of a glass matrix or adjusting the type and the concentration of a dopant; or, the luminous performance of the glass is regulated and controlled by changing the excitation wavelength.
7. A process for the preparation of a Cu/Mn doped color glass with luminescent function as claimed in any of claims 1 to 6, comprising the steps of:
(1) fully grinding and uniformly mixing raw materials of silicon dioxide, boric acid, aluminum oxide, zinc oxide, calcium fluoride, calcium carbonate, sodium carbonate, lithium carbonate, cuprous oxide and manganese carbonate to obtain a glass batch;
(2) melting: preserving the temperature of the glass batch mixture obtained in the step (1) at 1400-1600 ℃ for 0.5-2 hours, and melting to obtain glass liquid;
(3) forming and annealing: and (3) pouring the glass liquid obtained in the step (2) into a preheated copper mold, cooling and molding at room temperature, and then annealing at 400-550 ℃ for 1-3 hours to obtain the Cu/Mn doped colored glass with the light-emitting function.
8. The method as claimed in claim 7, wherein the temperature of step (2) is increased to 1400-1600 ℃ at a temperature increase rate of 4-8 ℃/min.
9. The method for preparing Cu/Mn doped color glass with luminescent function according to claim 7, wherein in the step (2), the melting mode is as follows: heating from room temperature to 350-450 ℃ at a heating rate of 5 ℃/min, then heating to 950-1050 ℃ at a heating rate of 6 ℃/min, and then heating to 1400-1600 ℃ at a heating rate of 4.8 ℃/min, and melting for 0.5-2 hours at the temperature to obtain the glass liquid.
10. The method for regulating and controlling the color glass with the light-emitting function doped with Cu/Mn as claimed in any one of claims 1 to 6, wherein the color and the light-emitting property of the glass are regulated and controlled by changing the composition of a glass matrix or adjusting the type and the concentration of a dopant; or, the luminous performance of the glass is regulated and controlled by changing the excitation wavelength.
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| CN115583792B (en) * | 2022-09-13 | 2023-12-22 | 昆明理工大学 | Coordinated luminous color-changing glass and preparation method and application thereof |
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