CN113831015B - Cu/Mn doped color glass with luminous function, preparation method and regulation and control method thereof - Google Patents
Cu/Mn doped color glass with luminous function, preparation method and regulation and control method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 20
- 239000002019 doping agent Substances 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims description 60
- 230000005284 excitation Effects 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims 3
- 238000006467 substitution reaction Methods 0.000 claims 1
- 229910004261 CaF 2 Inorganic materials 0.000 abstract description 15
- 239000003086 colorant Substances 0.000 abstract description 9
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 49
- 239000011572 manganese Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000000295 emission spectrum Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 239000006066 glass batch Substances 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 11
- 238000000137 annealing Methods 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 8
- 229940112669 cuprous oxide Drugs 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- -1 rare earth ions Chemical class 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 6
- 235000006748 manganese carbonate Nutrition 0.000 description 6
- 229940093474 manganese carbonate Drugs 0.000 description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229940008015 lithium carbonate Drugs 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 229910003870 O—Li Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 229940095626 calcium fluoride Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 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
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229940001593 sodium carbonate Drugs 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960001296 zinc oxide Drugs 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
- 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
Abstract
The invention provides Cu/Mn doped colored glass with a luminous function, a preparation method and a regulation and control method thereof. The glass comprises the following components in parts by mole: siO (SiO) 2 :40-60 parts, B 2 O 3 :0-15 parts of Al 2 O 3 :3-20 parts of ZnO:0-12 parts of CaF 2 :12-22 parts of CaO:0-17 parts of Na 2 O:0-17 parts of Li 2 0-17 parts of O; doping agent: 0.01-5 parts of a doping agent Cu 2 O, cuO or MnO. The invention adopts transition metal ion doping, and the doping agent has the functions of a coloring agent and a luminous center, thereby realizing the coloring and luminous functions of the glass; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring, and the color and luminous performance of the glass can be adjustable and controllable by a simple method.
Description
Technical Field
The invention relates to Cu/Mn doped colored glass with a luminous function, a preparation method and a regulation and control method thereof, and belongs 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 rays 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 colorant. The common glass is generally in a solid form which is approximately colorless and transparent, and the personalized requirements of consumers on beautifying life and the like are difficult to meet. Therefore, attention has been paid to the composition design and production technology of the colored glass. The color glass can be applied to the aspects of artistic decoration, illumination, laser, light filtering and the like, and has important significance in the fields of daily life, industrial and agricultural production and science and technology of people. On the other hand, luminescent glass can be obtained by introducing luminescent centers (such as rare earth ions) into the glass composition, and the glass can generate luminescent phenomena under the action of a certain type of excitation. In recent years, luminescent glass has been used in the fields of display, illumination, and optical communication.
The colorant of the color glass and the activator (luminous center) of the luminous glass generally adopt rare earth ions, but the rare earth resources are limited in reserves and high in price, many countries in the world have limits on exploitation and export of rare earth, and most rare earth ions have narrower absorption bands and cannot absorb excitation light efficiently, so that the application of the luminous glass prepared by the rare earth ions is limited. Chinese patent document CN103803797a discloses a luminescent glass for LED and a method for preparing the same. The main component of the glass matrix of the luminous glass for the LED is SiO 2 、Al 2 O 3 、B 2 O 3 、CaF 2 CaO, znO and Na 2 O, rare earth ion Tb 3+ 、Eu 3+ 、Dy 3+ 、Ce 3+ And Sm 3+ As a luminescence center, rare earth ions are doped in a glass matrix in a double or triple mode, and an ultraviolet LED chip is matched 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, color coordinates, color temperature and the like of the luminescent glass by changing the matrix components of the glass, the concentration of rare earth ions and the excitation wavelength. However, the luminescent glass has rare earth ions in the luminescent center, is expensive and has a narrower absorption band, and the invention does not relate to the regulation and control of glass color.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides Cu/Mn doped color glass with a luminous function, a preparation method and a regulation and control method thereof. By using transition metal Cu + And Cu 2+ ，Cu + 、Cu 2+ And Mn of 2+ Or Mn of 2+ Ion doping, wherein the doping agent has the functions of a coloring agent and a luminous center, so that the coloring and luminous functions of the glass are realized; the prepared glass has good mechanical property, stable chemical property and uniform glass coloring, and the color and luminous performance of the glass can be adjustable and controllable by a simple method.
Description of the terminology:
room temperature: the temperature is 25+/-5 ℃.
The invention is realized by the following technical scheme:
the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :40-60 parts, B 2 O 3 :0-15 parts of Al 2 O 3 :3-20 parts of ZnO:0-12 parts of CaF 2 :12-22 parts of CaO:0-17 parts of Na 2 O:0-17 parts of Li 2 0-17 parts of O; doping agent: 0.01-5 parts of a doping agent Cu 2 O, cuO or MnO.
According to the invention, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :40-60 parts, B 2 O 3 :0-15 parts of Al 2 O 3 :3-20 parts of ZnO:0-12 parts of CaF 2 :12-22 parts of CaO:0-17 parts of Na 2 O:0-17 parts of Li 2 0-17 parts of O; doping agent: 0.1-1.8 parts of a doping agent Cu 2 One or both of O, cuO or MnOCombinations of the above.
According to the invention, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :40-50 parts, B 2 O 3 :5-15 parts of Al 2 O 3 :10-20 parts of CaF 2 10-20 parts of Li 2 10-16 parts of O or CaO; dopant Cu 2 O and CuO:0.1-0.3 parts.
Preferably, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43-50 parts, B 2 O 3 :10 parts of Al 2 O 3 :10-17 parts of CaF 2 15 parts of Li 2 15 parts of O or CaO; dopant Cu 2 O and CuO:0.2 parts.
According to the invention, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :40-50 parts, B 2 O 3 :5-15 parts of Al 2 O 3 :10-20 parts of CaF 2 :10-20 parts of CaO or Li 2 O:10-15 parts of a lubricant; dopant MnO:0.2-0.6 part.
Preferably, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts, B 2 O 3 :10 parts of Al 2 O 3 :17 parts, caF 2 :15 parts of CaO or Li 2 O:15 parts; dopant MnO:0.4 parts.
According to the invention, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :40-50 parts, B 2 O 3 :5-15 parts of Al 2 O 3 :10-20 parts of CaF 2 :10-20 parts of CaO:10-15 parts of a lubricant; dopant Cu 2 O and CuO:0.1-0.3 part, mnO:0.8-1.5 parts.
Preferably, the Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts, B 2 O 3 :10 parts of Al 2 O 3 :17 parts, caF 2 ：15 parts of CaO:15 parts; dopant Cu 2 O and CuO:0.2 parts of MnO:1-1.5 parts.
According to the invention, the color and luminous performance of the glass are preferably regulated by changing the composition of the glass matrix or adjusting the type and concentration of the dopant; alternatively, the luminescence property of the glass is regulated by changing the excitation wavelength. The glass matrix is composed of components other than dopants.
The preparation method of the Cu/Mn doped color glass with the luminous 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: the glass batch obtained in the step (1) is insulated for 0.5 to 2 hours at 1400 to 1600 ℃ and melted to obtain glass liquid;
(3) And (5) forming and annealing: pouring the glass liquid obtained in the step (2) into a preheated copper mold, cooling and forming at room temperature, and then annealing at 400-550 ℃ for 1-3 hours to obtain the Cu/Mn doped color glass with a luminous function.
According to the present invention, the raw materials of silica, boric acid, alumina, zinc oxide, calcium fluoride, calcium carbonate, sodium carbonate, lithium carbonate, cuprous oxide and manganese carbonate in step (1) are used in amounts calculated according to the composition of the above glass.
According to the invention, in the 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 at the temperature for 0.5-2 hours to obtain the glass liquid. The heating mode can fully decompose raw materials, so that the obtained glass liquid has better clarifying and homogenizing effects, and is favorable for obtaining glass with uniform color, good luminous performance and other properties, structure and performance.
According to the invention, the invention adoptsCopper ions are introduced by cuprous oxide and prepared in air atmosphere, and Cu in the glass is actually finally obtained + And Cu 2+ Coexistence; therefore, the color and luminescence regulation of the glass according to the invention is practically based on Cu + And Cu 2+ ，Cu + 、Cu 2+ And Mn of 2+ Or Mn of 2+ Ions.
According to the regulating method of the Cu/Mn doped color glass with the light-emitting function, the color and the light-emitting performance of the glass are regulated by changing the composition of a glass matrix or regulating the type and the concentration of a doping agent; alternatively, the luminescence property of the glass is regulated by changing the excitation wavelength.
The invention has the technical characteristics and beneficial effects that:
1. the invention uses SiO 2 -B 2 O 3 -Al 2 O 3 -ZnO-CaF 2 -CaO-Na 2 O-Li 2 O system glass as matrix, transition metal Cu + And Cu 2+ ，Cu + 、Cu 2+ And Mn of 2+ Or Mn of 2+ The prepared glass is colored for the colorant and the luminous center, and can efficiently absorb the excitation light under the excitation of ultraviolet light, so that the visible light can be stably emitted. According to the invention, transition metal Cu/Mn is introduced into the glass composition, and the glass can be made to present a specific color by selective absorption of transition metal ions to a visible light wave band; on the other hand, the transition metal ions can generate electron transition under the excitation of ultraviolet wavelength to emit visible light, and the transition metal ions have wider absorption bands, so that the high-efficiency absorption of the excitation light can be realized. The invention can change the glass structure by changing the components of the glass matrix, and adjust the color and the luminous performance of the doping ion type and concentration regulating material. In addition, the regulation and control of the luminous performance of the glass can be realized by changing the excitation wavelength. The glass of the invention has the characteristics of good mechanical property and stable chemical property, and the various components complement each other and mutually play a synergistic effect so that the glass of the invention has different colors and different luminous properties, and the colors and luminous properties are adjustable and controllable.
2. The preparation method is simple, and the prepared glass has good mechanical property, stable chemical property, color and luminous function, and can be applied to LED luminous devices, artistic decorations and the like. The glass coloring agent and the luminous center adopt transition metal ions, rare earth elements are not adopted, and the glass manufacturing cost is low.
Drawings
FIG. 1 is an emission spectrum of the glass prepared in examples 1-3 under excitation at 296 nm;
FIG. 2 is an emission spectrum of the glass prepared in examples 4 and 5 under excitation at a wavelength of 414 nm;
FIG. 3 is an emission spectrum of the glasses prepared in examples 6 and 7 under excitation at 352 nm;
FIG. 4 is an emission spectrum of the glass prepared in example 6 under excitation at different wavelengths.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, and apparatus, unless otherwise specified, are all commercially available.
Example 1
The Cu doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of Li 2 O:15 parts of Cu 2 O:0.2 parts.
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 precisely 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 to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example was dark green in appearance, and fluorescence test was performed on the glass prepared in this example, and the emission spectrum under excitation at 296nm wavelength is shown in fig. 1, and luminescence is broadband emission with an emission peak at 489 nm.
Example 2
The copper ion doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of CaO:15 parts of Cu 2 O:0.2 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 and 0.0996g of cuprous oxide are precisely 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 to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example was blue in appearance and the emission spectrum at 296nm excitation was as shown in FIG. 1.
As can be seen from FIG. 1, the emission peak of example 1 is 489nm, the emission peak of example 2 is 455nm, and it is explained that Li in the glass composition 2 When O (example 1) is replaced by CaO (example 2), the emission peak shifts blue. From the above, li 2 Replacement of O and CaO can regulate and control luminescenceColor.
Example 3
The copper ion doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :50 parts of Al 2 O 3 :10 parts, B 2 O 3 :10 parts, caF 2 :15 parts of Li 2 O:15 parts of Cu 2 O:0.2 parts.
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 precisely 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 to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example was light bluish green in appearance and its emission spectrum at 296nm excitation is shown in FIG. 1.
From the comprehensive analysis, it is understood from FIG. 1 that the emission peak of example 3 was 481nm. Compared with example 1 (emission peak at 489 nm), it is demonstrated that Al is reduced in the glass composition 2 O 3 Increase SiO 2 The amount of (3) may shift the emission peak to a short wavelength.
Comprehensive analysis shows that the change of the composition of the glass matrix has obvious influence on the luminescence spectrum of the Cu doped glass. A change in the composition of the glass, causing a change in the structure of the glass, affecting Cu + And Cu 2+ The electron transition behavior of the ions further regulates the luminescence properties of the glass.
Example 4
A Mn-doped colored glass with a light-emitting function comprises, for exampleThe following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of CaO:15 parts of MnO:0.4 parts.
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 precisely weighed, and fully ground and uniformly mixed to obtain a glass batch;
(2) Melting: pouring the glass batch into a corundum crucible, heating to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example is light brown in appearance, and the emission spectrum at 414nm is shown in FIG. 2, and as can be seen from FIG. 2, the emission spectrum is a broadband spectrum with a peak at 618 nm.
Example 5
The manganese ion doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of Li 2 O:15 parts of MnO:0.4 parts.
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 precisely 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 to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example is brown in appearance and has an emission spectrum at 414nm excitation as shown in FIG. 2. The emission peak was 627nm.
As can be seen from FIG. 2, according to the comprehensive analysis, li is used in the glass matrix composition in comparison with example 4 2 O replaces CaO, and the emission wavelength of the glass can be shifted to the long wave direction (from 618nm to 627 nm).
Example 6
The Cu/Mn doped colored glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of CaO:15 parts of Cu 2 O:0.2 parts of 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 precisely weighed, and fully and uniformly ground and mixed to obtain a glass batch;
(2) Melting: pouring the glass batch into a corundum crucible, heating to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example is cyan in appearance and the emission spectrum at 352nm excitation is shown in FIG. 3. As can be seen from fig. 3, the emission spectrum peaks are at 487nm and 582nm,derived from Cu respectively + ，Cu 2+ Ion and Mn 2+ Electron transitions of ions.
The emission spectra of the glass prepared in the example under excitation of different wavelengths are shown in FIG. 4, the color coordinates and the color temperature are shown in Table 1, and the luminescence is derived from Cu + ，Cu 2+ Ion and Mn 2+ Electron transitions of ions. It can be seen that the excitation wavelength is changed, and the shape, color coordinates and color temperature of the emission spectrum of the glass are obviously changed, so that the regulation and control of the luminous performance of the glass can be realized by changing the excitation wavelength.
TABLE 1 color coordinates and color temperature data sheet
Example 7
The copper-manganese ion co-doped color glass with the luminous function comprises the following components in parts by mole: siO (SiO) 2 :43 parts of Al 2 O 3 :17 parts, B 2 O 3 10 parts of CaF 2 :15 parts of CaO:15 parts of Cu 2 O:0.2 parts of 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 precisely weighed, and fully and uniformly ground and mixed to obtain a glass batch;
(2) Melting: pouring the glass batch into a corundum crucible, heating to 400 ℃ from room temperature at a heating rate of 5 ℃/min, then heating to 1000 ℃ at a heating rate of 6 ℃/min, and then heating to 1480 ℃ at a heating rate of 4.8 ℃/min, and melting for 1 hour at the temperature to obtain glass liquid;
(3) Pouring the glass liquid obtained in the step (2) into a preheated copper mold, and cooling and forming at room temperature; annealing at 470 ℃ for 2 hours to obtain glass.
The glass prepared in this example has a light cyan appearance, and the emission spectrum at 352nm excitation is shown in FIG. 3, and the color coordinates and color temperature are shown in Table 1.
As can be seen from FIG. 3, the emission spectra peak at 487nm and 599nm, respectively, are derived from Cu + ，Cu 2+ Ion and Mn 2+ Electron transitions of ions. Comprehensive analysis, relative to example 6, mn can be achieved by increasing the Mn ion content 2+ The emission wavelength of the ions is red shifted (from 582nm to 599 nm). In addition, changing the content of manganese ions also resulted in changes in the relative intensity ratio, color coordinates and color temperature corresponding to the copper ion and manganese ion emission peaks (table 1). Therefore, by changing the content of doped manganese ions, the emission spectrum shape of the glass can be changed, and the regulation and control of the luminous performance of the prepared material are realized.
Claims (2)
1. The regulation and control method of the copper ion doped color glass with the light emitting function is characterized by comprising the following components in parts by mole: siO (SiO) 2 :43 parts, B 2 O 3 :10 parts of Al 2 O 3 :17 parts, caF 2 15 parts of Li 2 15 parts of O or CaO; dopant Cu 2 O:0.2 parts;
by incorporating Li into the glass composition 2 O, making the appearance color of the glass be dark green; the CaO is introduced into the glass composition to make the appearance color of the glass blue; thereby by regulating and controlling Li 2 The introduction of O or CaO realizes the regulation and control of the appearance color of the glass;
li in glass matrix composition 2 O is replaced by CaO, and under excitation of 296nm wavelength, the emission peak is blue-shifted from 489nm to 455nm; thereby by combining Li in glass matrix 2 O and CaO are exchanged to realize the regulation and control of emission peak and emission light color.
2. The method for regulating and controlling the manganese ion doped color glass with the luminous function is characterized by comprising the following components in parts by mole: siO (SiO) 2 :43 parts of，B 2 O 3 :10 parts of Al 2 O 3 :17 parts, caF 2 :15 parts of CaO or Li 2 O:15 parts; dopant MnO:0.4 parts;
by incorporating Li into the glass composition 2 O, the appearance color of the glass is brown; the CaO is introduced into the glass composition to make the appearance color of the glass light brown; thereby by regulating and controlling Li 2 The introduction of O or CaO realizes the regulation and control of the appearance color of the glass;
substitution of CaO in the glass matrix composition for Li 2 O, under the excitation of 414nm wavelength, the emission peak moves from 618nm to 627nm of long wavelength; thereby by combining Li in glass 2 O and CaO are exchanged to realize the regulation and control of emission peak and emission light color.
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