CN115140939A

CN115140939A - Cu/Eu-doped light conversion fluorescent glass and preparation method thereof

Info

Publication number: CN115140939A
Application number: CN202210696859.5A
Authority: CN
Inventors: 朱超峰; 徐留杰; 李朔
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2022-06-20
Filing date: 2022-06-20
Publication date: 2022-10-04

Abstract

The invention belongs to the technical field of optical functional glass, and relates to Cu/Eu-doped light conversion fluorescent glass and a preparation method thereof. Is prepared from SiO as active component ₂ 45-60 parts of B ₂ O ₃ :0 to 20 portions of Al ₂ O ₃ :0-20 parts of ZnO:0-10 parts of BaO:0 to 12 portions of CaF ₂ :10-20 parts of CaO:0-15 parts; na (Na) ₂ 0-15 parts of O, a dopant: 0.02-0.7 part; the dopant is CuO or Eu ₂ O ₃ At least one of (1). The Cu/Eu-doped fluorescent glass provided by the invention has a simple preparation method, has a fluorescent function, and can be applied to LED luminescent devices and display devicesThe raw materials are easy to obtain and implement, and the method has potential application prospect.

Description

Cu/Eu-doped light conversion fluorescent glass and preparation method thereof

Technical Field

The invention belongs to the technical field of optical functional glass, and relates to Cu/Eu-doped optical conversion fluorescent glass and a preparation method thereof.

Background

Environmental protection and energy saving have become the hot spot field of present scientific research, and the research of Light Emitting Diode (LED) lighting is the hot spot of attention in recent years. The LED is a semiconductor light-emitting device which converts electric energy into optical energy, is used as a third-generation lighting source following an incandescent lamp and a fluorescent lamp, has the characteristics of energy conservation, long service life, short starting time, environmental protection, low voltage safety and the like, is a high and new technical product with great development prospect and influence at present, and is expected to replace the existing incandescent lamp and the existing fluorescent lamp to become a lighting source with the greatest development potential in the twenty-first century. Research on materials for LEDs and related devices.

At present, the LED device is mainly prepared by compounding a semiconductor chip and fluorescent powder. In the field of LED, compared with a fluorescent powder material, the fluorescent glass has the advantages of low manufacturing cost, simple preparation process, good thermal stability, easy processing and capability of realizing direct packaging with a chip (epoxy resin is not adopted). Glass is a good luminescent host material.

The light conversion fluorescent glass has practical application value in LED illumination, display and some glass products. The adjustment of the performance of fluorescent glass in the prior art mainly relates to the change of the concentration of doped ions, microcrystalline glass is obtained by carrying out heat treatment on glass to separate out crystals, and the fluorescent performance of the material is rarely adjusted and controlled by cooling and spontaneous crystallization of a glass melt. Eu (Eu) ²⁺ The doped glass material generally exhibits broadband emission, and the Eu is used for preparing the Eu-doped fluorescent glass, generally ₂ O ₃ As introduction of Eu ²⁺ Or Eu ³⁺ The raw materials of (1). Therefore, to prepare Eu ²⁺ Doped phosphor, such that Eu is ³⁺ Reduction of ions to Eu ²⁺ Ions. On the other hand, currently, a reducing atmosphere is mainly used in the process of preparing the luminescent material at high temperature, such as hydrogen, carbon powder, carbon monoxide and the like, to realize Eu ³⁺ The reduction and the preparation process are relatively complex, and potential safety hazards also exist.

Disclosure of Invention

The invention provides novel Cu/Eu-doped light conversion fluorescent glass and a preparation method thereof, aiming at the problems of the traditional light conversion fluorescent glass in research, development and production.

In order to achieve the purpose, the invention adopts the following technical scheme:

the Cu/Eu doped fluorescent glass is prepared from the following substances containing the following effective components in parts by mole:

SiO ₂ 45-60 parts of B ₂ O ₃ :0 to 20 portions of Al ₂ O ₃ :0-20 parts of ZnO:0-10 parts of BaO:0 to 12 portions of CaF ₂ :10-20 parts of CaO:0-15 parts; na (Na) ₂ 0-15 parts of O, a dopant: 0.02-0.7 part; the dopant is CuO or Eu ₂ O ₃ At least one of (a).

The preparation method of the Cu/Eu doped fluorescent glass comprises the following steps:

(1) Batch preparation

Weighing silicon dioxide, boric acid, aluminum oxide, zinc oxide, barium carbonate, calcium fluoride, calcium carbonate, sodium carbonate, copper oxide and europium oxide (one or two of the copper oxide and the europium oxide can be respectively added according to actual requirements) according to the proportion, fully grinding and uniformly mixing to obtain a glass batch;

(2) Melting

Placing the glass batch mixture in an environment of 1400-1550 ℃ for heat preservation for 0.5-1.5 hours, and melting to obtain glass liquid;

(3) Shaping and annealing

Pouring the glass liquid into a preheated mold, cooling and molding at room temperature, and then annealing at 420-520 ℃ for 1-3 hours to obtain the Cu/Eu doped fluorescent glass.

Specifically, the temperature raising procedure in the step (2) is as follows:

room temperature 4-7 ^o Heating to 400-500 ℃ at the temperature rise rate of C/min;

5-10 ^o the temperature rises to 1000-1110 ℃ at the temperature rising rate of C/min ^o C；

3-6 ^o The temperature rises to 1400-1550 ℃ at the temperature rise rate of C/min ^o C, and melting for 0.5-1.5 hours under the condition of heat preservation. The heating mode can fully decompose the raw materials, so that the obtained glass liquid has better clarification and homogenization effects, and fluorescent glass with uniform composition, good luminescence performance and other properties, excellent structure and excellent performance can be obtained.

The scheme provided by the invention can realize the adjustment of spontaneously precipitated crystals and the content of the crystals in the cooling process of the glass liquid by adjusting the using amount of each component in the batch, thereby regulating and controlling the fluorescence property of the glass.

The invention is through Eu ³⁺ And Ba ²⁺ 、 Ca ²⁺ The negatively charged vacancy defects generated by the non-equivalent substitution of (1) Eu ³⁺ Reduction to Eu ²⁺ ，Eu ²⁺ Can be coated by alundum [ AlO ] in glass ₄ ]And boron-oxygen tetrahedron [ BO ₄ ]The three-dimensional network structure of the Eu doping agent is protected and stably exists, thereby realizing the Eu in the Eu doping glass prepared under the air atmosphere ³⁺ To Eu ²⁺ The transformation of (3).

Preferably, the specific preparation process comprises the following steps: weighing 12.8376g of silicon dioxide, 7.4074g of aluminum oxide, 2.7826g of zinc oxide, 5.0045g of calcium fluoride, 4.2774g of calcium carbonate and 0.2256g of europium oxide, fully grinding and uniformly mixing to obtain a glass batch; pouring the glass batch into a corundum crucible at room temperature of 5 DEG C ^o The temperature is raised to 400 ℃ at the temperature raising rate of C/min, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rise rate of C/min is raised to 1480 ^o C at 1480 ^o Melting for 1 hour under C to obtain glass liquid; pouring the molten glass into a copper mold preheated to 470 ℃, and cooling and molding at room temperature; annealing at 470 ℃ for 2 hours to obtain the product.

The invention provides application of the Cu/Eu doped fluorescent glass obtained by the preparation method in LED light-emitting devices, art decoration and color display.

According to the method for regulating and controlling the performance of the Cu/Eu-doped fluorescent glass, the composition of the glass matrix is designed, so that spontaneous crystallization is realized in the process of cooling the melt, the crystallization degree is controlled, or the fluorescent performance of the glass is regulated and controlled by regulating the type and concentration of a dopant; or the emission spectrum of the glass is regulated and controlled by changing the excitation wavelength. In the traditional industrial production, glass heat treatment is generally adopted to precipitate crystals in the glass, so that the fluorescence property of the glass is regulated and controlled. The invention discloses a cooling spontaneous crystallization technology of a glass melt, which changes the glass forming capacity of the melt through the precise design of glass composition, and separates out crystals in the cooling process of the meltAnd (3) a body. Compared with the crystallization by heat treatment, the crystallization technology can save energy. By designing proper glass matrix composition, eu is realized ³⁺ The ions are not substituted with divalent metal cations in the glass matrix in an equivalent manner, and Eu is substituted by using negative charges carried by generated vacancy defects ³⁺ Reduced to Eu ²⁺ ，Eu ²⁺ Can be coated by alundum [ AlO ] in glass ₄ ]And boron-oxygen tetrahedron [ BO ₄ ]The three-dimensional network structure is protected and stably exists, so that Eu in the Eu-doped glass prepared in the air atmosphere is realized ³⁺ To Eu ²⁺ The transformation of (3). The high-valence rare earth ions are reduced into low-valence state by non-equivalent substitution with metal cations, and the method realizes Eu by using hydrogen, carbon powder, carbon monoxide and the like ³⁺ Compared with reduction, the method has the advantages of low cost, safety, simple preparation process and the like.

The invention adopts transition metal ion Cu ²⁺ And rare earth ion Eu ³⁺ And Eu ²⁺ The prepared glass has excellent optical characteristics, and the photochromic quality of fluorescence generated by the glass can be realized by adjusting the composition of matrix glass, glass devitrification, the glass structure, the species and concentration of doped ions and the wavelength of exciting light. The fluorescent glass prepared by the method has uniform luminescence, easy processing and high luminous efficiency, and has potential application prospect in the fields of art decoration, LED luminescent devices and display.

Compared with the prior art, the invention has the advantages and positive effects that:

1. the Cu/Eu doped fluorescent glass provided by the invention is simple in preparation method, and the prepared glass has a fluorescent function and can be applied to the fields of LED luminescent devices, display, artistic decoration and the like.

2. The Eu can be realized without using reducing atmosphere in the preparation process of the fluorescent glass provided by the invention ³⁺ To Eu ²⁺ The reduction of (2) can reduce the cost and simplify the preparation process. The fluorescent glass raw material provided by the invention is easy to obtain and implement, and has potential application prospects.

3. The invention uses SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -ZnO-CaF ₂ -BaO-CaO-Na ₂ O system glass as matrix, transition metal ion Cu ²⁺ And rare earth ion Eu ³⁺ /Eu ²⁺ The prepared glass can efficiently absorb exciting light under the excitation of ultraviolet light to emit visible light. The invention can adjust and control the fluorescence property of the material by changing the components of the glass matrix, spontaneously crystallizing in the process of cooling the melt, changing the glass structure and adjusting the type of the doped ions and the concentration. In addition, the fluorescence performance of the glass can be regulated and controlled by changing the excitation wavelength. Various components supplement each other and exert a synergistic effect mutually so that the glass disclosed by the invention has controllable fluorescence performance.

Drawings

FIG. 1 is an emission spectrum of glasses prepared in examples 1, 2 and 3 under excitation at a wavelength of 362 nm.

FIG. 2 is an emission spectrum of glasses prepared in examples 3 and 4 under excitation at a wavelength of 330 nm.

FIG. 3 is an excitation spectrum of glass prepared in example 4 monitored at 462 and 612 nm wavelengths.

FIG. 4 shows the emission spectra of the glasses prepared in example 4 under different wavelength excitation.

FIG. 5 is an emission spectrum of glasses prepared in examples 3, 5, 6, and 7 under excitation at a wavelength of 330 nm.

FIG. 6 is an IR spectrum of glasses prepared in examples 3, 5, 6 and 7.

FIG. 7 is an X-ray diffraction pattern of glasses prepared in examples 3, 5, 6 and 7.

FIG. 8 is an emission spectrum of glasses prepared in examples 7, 8 and 9 under excitation at a wavelength of 330 nm.

FIG. 9 is an IR spectrum of glasses prepared in examples 7, 8 and 9.

FIG. 10 is an X-ray diffraction pattern of glasses prepared in examples 7, 8 and 9.

Detailed Description

In order that the above objects, features and advantages of the present invention may be more clearly understood, the present invention will be further described with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the present invention is not limited to the specific embodiments disclosed in the following description.

Example 1

The embodiment provides a Cu-doped fluorescent glass and a preparation process thereof. The raw materials comprise the following effective components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :17 parts, znO:8 parts of CaF ₂ :15 parts of CaO:10 parts of CuO:0.2 part.

The preparation method of the glass comprises the following steps:

(1) According to the components of the glass, 12.8376g of silicon dioxide, 7.4074g of aluminum oxide, 2.7826g of zinc oxide, 5.0045g of calcium fluoride, 4.2774g of calcium carbonate and 0.0680g of copper oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain the glass batch.

(2) Melting: pouring the glass batch into a corundum crucible from room temperature to 5 deg.C ^o The temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rise rate of C/min is raised to 1480 ^o And C, melting for 1 hour at the temperature to obtain glass liquid.

(3) Pouring the glass liquid obtained in the step (2) into a copper mold preheated to 470 ℃, and cooling at room temperature for molding; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.

The emission spectrum of the sample prepared in this example under 362nm wavelength excitation is shown in FIG. 1, and has a broad emission band with an emission peak at 493 nm.

Example 2

The embodiment provides Eu-doped fluorescent glass and a preparation process thereof. The raw materials comprise the following effective components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :17 parts, znO:8 parts of CaF ₂ :15 parts, caO:10 parts of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) According to the components of the glass, 12.8376g of silicon dioxide, 7.4074g of aluminum oxide, 2.7826g of zinc oxide, 5.0045g of calcium fluoride, 4.2774g of calcium carbonate and 0.2256g of europium oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain the glass batch.

(2) Melting: pouring the glass batch into a corundum crucible from room temperature at 5 DEG ^o The temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rises to 1480 at the temperature rise rate of C/min ^o And C, melting for 1 hour at the temperature to obtain glass liquid.

(3) Pouring the molten glass obtained in the step (2) into a copper mold preheated to 470 ℃, and cooling and forming at room temperature; annealing treatment was carried out at 470 ℃ for 2 hours to obtain a glass.

The emission spectrum of the sample prepared in this example under 362nm excitation is shown in FIG. 1, and has a broad emission band with an emission peak at 421nm, the emission is derived from Eu ²⁺ 5d-4f electron transitions of the ions; emission peaks at 590, 613, 654 and 700nm are derived from Eu ³⁺ Of ions ⁵ D ₀ - ⁷ F ₁ 、 ⁵ D ₀ - ⁷ F ₂ 、 ⁵ D ₀ - ⁷ F ₃ 、 ⁵ D ₀ - ⁷ F ₄ And (4) electron transition. This example uses Eu ₂ O ₃ Europium ions are introduced as raw materials, and the glass is prepared in an air atmosphere without adopting a reducing atmosphere. General Eu ²⁺ Doped phosphors need to be prepared using a reducing atmosphere (e.g., H) ₂ Atmosphere, CO atmosphere), it can be seen from this example that Eu was successfully achieved by designing an appropriate glass matrix composition ³⁺ To Eu ²⁺ The reduction of (2) reduces the preparation cost and increases the safety of the preparation process.

Example 3

This example provides a Cu/Eu doped fluorescent glass and a process for making the same. The raw materials comprise the following effective components in molar portion：SiO ₂ 50 parts of Al ₂ O ₃ :17 parts of ZnO, 8 parts of CaF ₂ 15 parts, 10 parts of CaO, cuO:0.2 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) Accurately weighing 12.8376g of silicon dioxide, 7.4074g of aluminum oxide, 2.7826g of zinc oxide, 5.0045g of calcium fluoride, 4.2774g of calcium carbonate, 0.0680g of copper oxide and 0.2256g of europium oxide according to the components of the glass, fully grinding and uniformly mixing the raw materials to obtain the glass batch.

The emission spectrum of the glass prepared in this example under excitation at a wavelength of 362nm is shown in fig. 1. The emission spectrum contains a wide emission band with a peak at 500nm and is derived from Eu ²⁺ And Cu ²⁺ Electron transition of (4); emission peaks at 590, 613, 654 and 700nm are derived from Eu ³⁺ Electron transitions of the ions.

Example 4

The embodiment provides Cu/Eu doped fluorescent glass and a preparation process thereof. The raw materials comprise the following components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :17 parts, znO:8 parts of CaF ₂ :15 parts, caO:10 parts of CuO:0.1 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) According to the components of the glass, accurately weighing 4325 g of silicon dioxide zxft 4325 g, 3536 g of aluminum oxide 7.3758g, 2.7707g of zinc oxide, 4.9832g of calcium fluoride, 4.2591g of calcium carbonate, 0.0339g of copper oxide and 0.2246g of europium oxide, and fully grinding and uniformly mixing the raw materials to obtain the glass batch.

The emission spectrum of the glass prepared in this example under excitation at a wavelength of 330nm is shown in fig. 2. The emission spectrum contains a broad emission band with a peak at 474nm, and is derived from Eu ²⁺ And Cu ²⁺ Electron transition of (2); the emission peaks at 613 and 702nm are derived from Eu ³⁺ Electron transitions of the ions. For comparison, the emission spectrum of the glass prepared in example 3 is also shown in FIG. 2, and it can be seen that Cu is reduced ²⁺ Concentration, derived from Cu ²⁺ The relative intensity of the emission band of (a) decreases. This shows that the luminescent property of the prepared fluorescent glass can be adjusted and controlled by changing the concentration of the doping ions. The excitation spectra of the glasses prepared in this example, as monitored at 462 and 612 nm wavelengths, are shown in fig. 3. 612 The excitation spectrum under the monitoring of nm wavelength shows excitation peaks with peak values at 361, 381 and 393nm, which respectively correspond to Eu ³⁺ Of ions ⁷ F ₀ - ⁵ G ₄ ， ⁷ F ₀ - ⁵ G ₂ And ⁷ F ₀ - ⁵ L ₆ and (4) electron transition. The emission spectra of the glasses prepared in this example under different wavelength excitations are shown in FIG. 4, and are derived from Cu ²⁺ And Eu ²⁺ The relative intensity of the broad emission band and the emission peak position of the electron transition are varied with the excitation wavelength. This shows that the glass prepared in this example can realize the control of the luminescence property by changing the excitation wavelength.

Example 5

This example provides a Cu/Eu doped fluorescent glass and its preparationAnd (4) processing. The raw materials comprise the following components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :7 parts of, B ₂ O ₃ 10 portions of ZnO, 8 portions of CaF ₂ 15 parts of CaO, 10 parts of CaO, cuO:0.2 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) Accurately weighing 12.2612g of silicon dioxide, 2.9131g of aluminum oxide, 5.0473g of boric acid, 2.6576g of zinc oxide, 4.7798g of calcium fluoride, 4.0853g of calcium carbonate, 0.0649g of copper oxide and 0.2155g of europium oxide according to the components of the glass, and fully grinding and uniformly mixing the raw materials to obtain the glass batch.

Example 6

This example provides a Cu/Eu co-doped fluorescent glass and a preparation process thereof. The raw materials comprise the following effective components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :7 portions of BaO, 10 portions of ZnO, 8 portions of CaF ₂ 15 parts, 10 parts of CaO, cuO:0.2 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) According to the components of the glass, accurately weighing 4325 g of silicon dioxide zxft 4325 g, 3536 g of aluminum oxide 2.6933g, 7.4468g of barium carbonate, 2.4571g of zinc oxide, 4.4191g of calcium fluoride, 3.7770g of calcium carbonate, 0.0600g of copper oxide and 3534 g of europium oxide, and fully grinding and uniformly mixing the raw materials to obtain the glass batch.

Example 7

This example provides a Cu/Eu ion doped fluorescent glass and a manufacturing process thereof. The raw materials comprise the following effective components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :7 portions of BaO, 10 portions of ZnO, 8 portions of CaF ₂ 15 portions of Na ₂ 10 parts of O, cuO:0.2 part by weight of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) Accurately weighing 11.1259g of silicon dioxide, 2.6434g of aluminum oxide, 7.3089g of barium carbonate, 2.4116g of zinc oxide, 4.3372g of calcium fluoride, 3.9256g of sodium carbonate, 0.0589g of copper oxide and 0.1955g of europium oxide according to the components of the glass, and fully grinding and uniformly mixing the raw materials to obtain the glass batch.

(2) Melting: pouring the glass batch into a corundum crucible from room temperature to 5 deg.C ^o The temperature is raised to 400 ℃ at the temperature raising rate of C/min, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rise rate of C/min is raised to 1480 ^o And C, melting for 1 hour at the temperature to obtain glass liquid.

The emission spectra of the glasses prepared in examples 3, 5, 6 and 7 under excitation at a wavelength of 330nm are shown in FIG. 5. Emission spectrum containing Eu ²⁺ ，Cu ²⁺ And Eu ³⁺ The emission peak of the broadband emission is shifted along with the change of the composition of the glass matrix. Example 7 in comparison to examples 3, 5, 6, appearsThe peak values are at the emission peaks at 574 and 631 nm.

The IR spectra of the glasses prepared in examples 3, 5, 6 and 7 are shown in FIG. 6. The infrared spectrum contains mainly 4 absorption bands. The absorption band 1 corresponds to B-O stretching vibration, the absorption band 2 corresponds to Si-O stretching vibration, the absorption band 3 corresponds to Al-O bending vibration, and the absorption band 4 corresponds to Si-O-Si and Si-O-Al bending vibration. As can be seen from fig. 6, as the composition of the matrix glass changes, the position and intensity of each absorption band changes, indicating that the glass structure changes, thereby causing a change in the luminescent properties of the material.

The X-ray diffraction patterns of the glasses prepared in examples 3, 5, 6 and 7 are shown in fig. 7.

The spectra of examples 3, 5, and 6 have no diffraction peaks, indicating that the materials prepared in these examples are glassy, whereas the material prepared in example 7 has distinct diffraction peaks, corresponding to CaF ₂ Crystal (PDF 70-2049). Generally, devitrification occurs in glass, and it is necessary to subject the glass to a microcrystallization heat treatment. As can be seen from the X-ray diffraction results of example 7, by precisely designing the composition of the glass matrix, precipitation of crystals during cooling of the glass melt can be achieved. As can be seen from the emission spectrum of FIG. 5, the precipitation of crystals of example 7 induced emission peaks with peaks at 574 and 631 nm.

Example 8

The embodiment provides Cu/Eu-doped fluorescent glass and a preparation method thereof. The raw materials comprise the following components in parts by mole: siO 2 ₂ 50 parts of Al ₂ O ₃ :17 parts, znO:8 parts of CaF ₂ :15 parts of Na ₂ O:10 parts of CuO:0.2 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) According to the components of the glass, 12.5690g of silicon dioxide, 7.2524g of aluminum oxide, 2.7244g of zinc oxide, 4.8998g of calcium fluoride, 4.4347g of sodium carbonate, 0.0666g of copper oxide and 0.2209g of europium oxide are accurately weighed, and the raw materials are fully ground and uniformly mixed to obtain the glass batch.

(2) Melting: pouring the glass batch into a corundum crucible from room temperature5 ^o The temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rise rate of C/min is raised to 1480 ^o And C, melting for 1 hour at the temperature to obtain glass liquid.

Example 9

The embodiment provides Cu/Eu doped fluorescent glass and a preparation process thereof. The raw materials comprise the following components in parts by mole: siO 2 ₂ 50 parts by weight of B ₂ O ₃ :17 parts, znO:8 parts of CaF ₂ :15 parts of Na ₂ O:10 parts of CuO:0.2 part of Eu ₂ O ₃ :0.15 part.

The preparation method of the glass comprises the following steps:

(1) Accurately weighing 12.2612g of silicon dioxide, 8.5805g of boric acid, 2.6576g of zinc oxide, 4.7798g of calcium fluoride, 4.3261g of sodium carbonate, 0.0649g of copper oxide and 0.2155g of europium oxide according to the components of the glass, fully grinding and uniformly mixing the raw materials to obtain the glass batch.

The emission spectra of the glasses prepared in examples 8 and 9 under excitation at a wavelength of 330nm are shown in FIG. 8, and for comparison, the emission spectrum of example 7 is also shown. Spectrum shows Eu ²⁺ 、Cu ²⁺ Broadband emission and Eu ³⁺ The emission peak of (2). The emission peak position of the broadband emission shifts with the change of the glass matrix composition, and the peak valueThere was a change in the relative intensities of the emission peaks at 574 and 631 nm.

The IR spectra of examples 7, 8 and 9 are shown in FIG. 9. It can be seen from FIG. 9 that the position and intensity of the absorption bands change with the composition of the matrix glass, indicating a change in the glass structure. FIG. 10 is an X-ray diffraction chart of examples 7, 8 and 9, from which it can be seen that the materials prepared in all three examples have crystal precipitates and the diffraction peak intensities are gradually decreased in the order of examples 7, 8 and 9, indicating that the crystal contents are gradually decreased in the three samples. As can be seen from FIG. 8, the emission spectra of examples 7, 8 and 9 show a gradual decrease in the relative intensities of the emission peaks with peaks at 574 and 631 nm.

Comprehensive analysis, through the accurate design of matrix glass composition, the precipitation and precipitation content of crystals in the material can be controlled, and then the microstructure of the material is changed, so that the regulation and control of the material luminescence performance are realized.

On the basis of comprehensive analysis, the color coordinates of the glasses prepared in examples 3 to 9 are shown in Table 1.

TABLE 1 glass color coordinates

Table 1 illustrates that the color coordinates of the glass of the present invention can be adjusted by the glass matrix composition, devitrification, glass structure and excitation wavelength, thereby adapting the fluorescent glass to different application environments.

Example 10

The present embodiment is different from embodiment 1 in that the temperature raising program is: room temperature 4 ^o Heating to 400 ℃ at the temperature rise rate of C/min; 10 ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C； 6 ^o The temperature rises to 1400 ℃ at the temperature rising rate of C/min ^o And C, preserving heat and melting for 1.5 hours, pouring the molten glass into a preheated mold, cooling and molding at room temperature, and then annealing at 520 ℃ for 1 hour to obtain a product which is not much different from that of the product in the example 1.

Example 11

The difference between this embodiment and embodiment 1The temperature rise procedure is as follows: room temperature 7 ^o Heating to 500 ℃ at the temperature rise rate of C/min; 5 ^o The temperature rises to 1110 ℃ at the temperature rising rate of C/min ^o C；3 ^o The temperature rises to 1550 ℃ at the temperature rise rate of C/min ^o And C, preserving heat and melting for 0.5 hour, pouring the molten glass into a preheated mold, cooling at room temperature for molding, and then annealing at 420 ℃ for 3 hours to obtain a product which is not much different from the product obtained in the embodiment 1.

Example 12

The present embodiment is different from embodiment 1 in that the temperature raising program is: room temperature 6 ^o Heating to 480 ℃ at the temperature rise rate of C/min; 7.5 ^o The temperature rises to 1050 at a C/min temperature rise rate ^o C；3.6 ^o The temperature rises to 1500 ℃ at the temperature rise rate of C/min ^o And C, preserving heat and melting for 0.8 hour, pouring the molten glass into a preheated mold, cooling at room temperature for molding, and then annealing at 460 ℃ for 2 hours to obtain a product which is not much different from the product obtained in the embodiment 1.

The Cu/Eu doped fluorescent glass is prepared by a high-temperature melt cooling method, and can show sufficient color fluorescence through ultraviolet irradiation. The photochromic quality of the fluorescence generated by the glass can be realized by adjusting the composition of the matrix glass, the devitrification of the glass, the structure of the glass, the species and the concentration of the doped ions and the wavelength of the exciting light. The fluorescent glass prepared by the method has uniform luminescence, easy processing and high luminous efficiency, and has potential application prospect in the fields of art decoration, LED luminescent devices, color display and the like.

The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.

Claims

1. The Cu/Eu doped fluorescent glass is characterized by being prepared from the following substances containing the following effective components in parts by mole:

SiO ₂ 45-60 parts of B ₂ O ₃ :0 to 20 portions of Al ₂ O ₃ :0-20 parts of ZnO:0-10 parts of BaO:0 to 12 portions of CaF ₂ :10-20 parts of CaO:0-15 parts; na (Na) ₂ 0-15 parts of O, a dopant: 0.02-0.7 part; the dopant is CuO or Eu ₂ O ₃ At least one of (1).

2. The method of making the Cu/Eu doped fluorescent glass of claim 1, characterized by the steps of:

(1) Batch preparation

Weighing silicon dioxide, boric acid, aluminum oxide, zinc oxide, barium carbonate, calcium fluoride, calcium carbonate, sodium carbonate, copper oxide and europium oxide according to the proportion of claim 1, fully grinding and uniformly mixing to obtain a glass batch;

(2) Melting

(3) Shaping and annealing

And pouring the glass liquid into a preheated mold, cooling at room temperature for molding, and then annealing at 420-520 ℃ for 1-3 hours to obtain the Cu/Eu-doped fluorescent glass.

3. The method for preparing a Cu/Eu-doped fluorescent glass according to claim 2, wherein the temperature raising procedure in step (2) is:

3-6 ^o The temperature rises to 1400-1550 ℃ at the temperature rising rate of C/min ^o C, and melting for 0.5-1.5 hours under the condition of heat preservation.

4. The method for preparing Cu/Eu-doped fluorescent glass according to claim 2, wherein silica 12.8376g, alumina 7.4074g and zinc oxide 2 are weighed.7826g, 5.0045g of calcium fluoride, 4.2774g of calcium carbonate and 0.2256g of europium oxide, and fully grinding and uniformly mixing to obtain a glass batch; pouring the glass batch into a corundum crucible at room temperature of 5 DEG C ^o The temperature is raised to 400 ℃ at a C/min temperature rise rate, and then the temperature is raised to 6 DEG C ^o The temperature rises to 1000 at a temperature rise rate of C/min ^o C, then 4.8 ^o The temperature rise rate of C/min is raised to 1480 ^o C at 1480 ^o Melting for 1 hour under C to obtain glass liquid; pouring the molten glass into a copper mold preheated to 470 ℃, and cooling and molding at room temperature; annealing at 470 deg.C for 2 hr to obtain the final product.

5. The use of the Cu/Eu doped fluorescent glass obtained by the preparation method of claims 2-4 in LED light-emitting devices, art decoration and color display.