Preparation method of rare earth europium ion doped black talc-based high-performance luminescent glass

Abstract

The invention discloses a preparation method of Eu < 3 + >-doped black talc-based high-performance luminescent glass, and the prepared luminescent glass is a novel photoluminescent material matrix and can provide a new expansion space for a rare earth photoluminescent material. The luminescent glass is characterized by comprising the following chemical components in percentage by weight: 90wt% of black talc, 10wt% of CaO and 1-13wt% of Eu2O3. The preparation method comprises the following steps: weighing the three raw materials according to the mass ratio, uniformly mixing in a ceramic mortar, putting into an Al2O3 crucible, putting into a high-temperature muffle furnace, carrying out high-temperature melting at the melting temperature of 1600 DEG C, and keeping the temperature for 2 hours. Pouring the glass melt on a preheated stainless steel mold, placing the mold in a low-temperature muffle furnace for annealing treatment at the annealing temperature of 680 DEG C, and keeping the temperature for 10 hours; and cooling the annealing furnace to room temperature to obtain the black talc-based luminescent glass. According to the invention, a black talc high-value utilization technology is successfully developed, and the prepared luminescent glass can be excited by a 394 nm light source to emit red fluorescence with a fluorescence range of 520-750 nm and a main emission peak of 615 nm, and can be used as a red fluorescent material of a warm white light LED.

Description

Technical Field

[0001] The invention belongs to the field of inorganic luminescent glass materials, relates to the high-value utilization of black talc, and specifically relates to a Eu 3+ Preparation method of high-performance luminescent glass based on doped black talc. Background Art

[0002] Inorganic luminescent glass has been widely reported in recent years. On the one hand, thanks to the melting preparation process of glass materials, rare earth ions can be evenly dispersed in the network structure of the glass to obtain uniform and good luminescent effects; on the other hand, compared with phosphors, glass has better thermal and chemical stability and lower light loss, which can effectively solve the problem of reduced service life and lighting quality of LED devices, and has become an effective substitute for phosphors for the new generation of LEDs.

[0003] The main chemical composition of black talc in Guangfeng District, Shangrao City, Jiangxi Province is silicon dioxide / magnesium oxide (SiO 2 / MgO), a small amount of chemical composition is alkali / alkaline earth metal oxides (K 2 O / CaO), which has the potential to prepare silicate glass. Therefore, this application uses black talc as a matrix to prepare luminescent glass materials. Rare earth ion-activated fluorescent glass can be excited by ultraviolet light, near-ultraviolet light or blue light wavelengths, and has the characteristics of high stability and good high-temperature properties. Therefore, it has been widely used in many industries such as luminescence, display, information storage, biomarkers, and medical treatment. Among the common red, blue, and green primary color phosphors, Eu 3+ Ion-activated red luminescent glass has received widespread attention. It has the characteristics of high luminous efficiency, pure chromaticity, and good temperature performance. In addition, the matrix materials of fluorescent glass activated by rare earth ions are abundant, and the common ones are phosphates, silicates, borates, aluminates, and aluminosilicates. Compared with these matrix materials, fluorescent glass with Guangfeng District black talc as the matrix is ​​rarely reported. It is a new type of photoluminescent material matrix, which can provide new development space for rare earth photoluminescent materials. Therefore, the present invention studies Eu by fluorescence spectrometer 2 O 3 The optical properties of the black talc-doped luminescent glass are as follows: the fluorescence emission spectrum of this material is in the red light region, and it is an inorganic luminescent glass material with potential application value, and is expected to be used in the field of luminescent materials for LEDs. Summary of the invention

[0004] The purpose of the present invention is to provide a black talc-based luminescent glass material. The luminescent glass is a type of red light luminescent material with excellent performance and is expected to be applied in the field of luminescent glass for LEDs.

[0005] Another object of the present invention is to provide a Eu 3+The preparation method of doped black talc-based luminescent glass solves the problem of low-value utilization of black talc in Guangfeng District, Shangrao City.

[0006] In order to achieve the above-mentioned invention object, the present invention is specifically implemented by the following technical solutions:

[0007] (1) black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3 (1-13%);

[0008] (2) placing the batch material in a high-temperature muffle furnace and melting it at 1600° C. for 2 hours to obtain a uniform glass melt;

[0009] (3) Pour the glass melt onto a preheated stainless steel mold and place it in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain rare earth Eu. 3+ Doped black talc-based luminescent glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] (1) Figure 1 Eu prepared in the present invention 3+ XRD spectrum of high-performance luminescent glass based on doped black talc;

[0011] (2) Figure 2 Eu prepared in the present invention 3+ Actual picture of doped black talc-based high-performance luminescent glass under UV light / natural light;

[0012] (3) Figure 3 Eu prepared in the present invention 3+ Fluorescence excitation and emission spectra of high-performance luminescent glass based on doped black talc;

[0013] (4) Figure 4 Eu prepared in the present invention 3+ Fluorescence emission intensity of high-performance luminescent glass based on doped black talc varies with Eu 3+ Doping concentration variation diagram;

[0014] (5) Figure 5 Eu prepared in the present invention 3+ Fluorescence lifetime spectrum of high-performance luminescent glass based on doped black talc and its relationship with Eu 3+ Doping concentration variation diagram. DETAILED DESCRIPTION

[0015] The present invention is further described below with reference to the embodiments, but the protection scope of the present invention should not be limited thereto.

[0016] Eu 3+ The method for preparing high-performance luminescent glass based on doped black talc comprises the following steps:

[0017] (1) black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed raw material mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3 (1-13%);

[0018] (2) placing the batch material in a high-temperature muffle furnace and melting it at 1600° C. for 2 hours to obtain a uniform glass melt;

[0019] (3) Pour the glass melt onto a preheated stainless steel mold and place it in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain rare earth Eu. 3+ Doped black talc-based luminescent glass.

[0020] Example 1

[0021] Black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed raw material mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3 (1%). The batch material is placed in a high-temperature muffle furnace and melted at 1600°C for 2 hours to obtain a uniform glass melt. The glass melt is poured onto a preheated stainless steel mold and placed in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain rare earth Eu. 3+ The relative value of the integrated intensity of fluorescence emission of the doped black talc-based luminescent glass is 17.5%, and the value of the fluorescence lifetime is 2.072 ms. Figure 3 For Eu 3+Excitation and emission spectra of ion-activated black talc fluorescent glass. In the excitation spectrum at a detection wavelength of 615 nm, the absorption peak in the range of 200 to 300 nm belongs to the charge transfer band of Eu-O, and the other absorption peaks are at 318 nm, 362 nm, 381 nm, 395 nm and 415 nm, which are attributed to Eu 3+ Ions from 7 F 0 The intrinsic transition from the ground state to the excited state is 7 F 0 → 5 H 3,6 , 7 F 0 → 5 D 4 , 7 F 0 → 5 L 7 , 7 F 0 → 5 L 6 ,and 7 F 0 → 5 D 3 The electron energy level transition, among which the strongest excitation peak is located at 395nm. 3+ The black talc-doped fluorescent glass was excited by 395nm near-ultraviolet light, and Eu was observed in the range of 520-750nm. 3+ The transition of an ion from an excited state to a ground state is 5 D 0 → 7 F J (J=0, 1, 2, 3, 4) energy level transitions correspond to characteristic peaks at 535nm, 589nm, 615nm, 654nm and 705nm, respectively, with the red light emission at 615nm being the strongest emission peak. In the field of solid-state lighting and display, it can be used as red fluorescent glass for warm white light LEDs, or directly as luminescent glass for color light sources.

[0022] Example 2

[0023] Black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed raw material mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3(5%). The batch material is placed in a high-temperature muffle furnace and melted at 1600°C for 2 hours to obtain a uniform glass melt. The glass melt is poured onto a preheated stainless steel mold and placed in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain Eu 3+ The relative value of the integrated intensity of fluorescence emission of the doped black talc-based luminescent glass is 63.3%, and the value of the fluorescence lifetime is 2.025 ms.

[0024] Example 3

[0025] Black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed raw material mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3 (10%). The batch material is placed in a high-temperature muffle furnace and melted at 1600°C for 2 hours to obtain a uniform glass melt. The glass melt is poured onto a preheated stainless steel mold and placed in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain Eu 3+ The relative value of the integrated intensity of fluorescence emission of the doped black talc-based luminescent glass is 100%, and the value of the fluorescence lifetime is 1.945 ms.

[0026] Example 4

[0027] Black talc, CaO and Eu 2 O 3 The three raw materials were mixed evenly in a ceramic mortar according to the pre-designed raw material mass ratio and loaded into Al 2 O 3 The mass percentage of each component is: black talc (90%), CaO (10%), Eu 2 O 3 (13%). The batch material is placed in a high-temperature muffle furnace and melted at 1600°C for 2 hours to obtain a uniform glass melt. The glass melt is poured onto a preheated stainless steel mold and placed in a low-temperature muffle furnace for annealing at 680°C for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain Eu 3+ The relative value of the integrated intensity of fluorescence emission of the doped black talc-based luminescent glass is 97.5%, and the value of the fluorescence lifetime is 1.888 ms. Table 1 Eu prepared in Examples 1-4 3+Fluorescence emission integrated relative intensity and fluorescence lifetime data of high performance luminescent glass based on doped black talc

[0028]

Claims

1. Eu 3+ A method for preparing high-performance luminescent glass based on doped black talc, characterized in that: The steps are as follows: (1) Mix black talc, CaO and Eu2O3 in a ceramic mortar according to a pre-designed mass ratio, and put them into an Al2O3 crucible to obtain a batch material. The mass percentage of each component is: black talc (90%), CaO (10%), Eu2O3 (1-13%); (2) placing the batch material in a high-temperature muffle furnace and melting it at 1600° C. for 2 hours to obtain a uniform glass melt; (3) The glass melt is poured onto a preheated stainless steel mold and placed in a low-temperature muffle furnace for annealing at 680° C. for 10 hours to release the stress in the melt. The annealing furnace is cooled to room temperature to obtain a black talc-based luminescent glass.

2. Eu according to claim 1 3+ A method for preparing high-performance luminescent glass based on doped black talc, characterized in that: The raw materials include black talc, CaO and Eu2O3.

3. Eu according to claim 2 3+ A method for preparing high-performance luminescent glass based on doped black talc, characterized in that: The melting temperature is 1600℃ / 2h.

4. Eu according to claim 2 3+ A method for preparing high-performance luminescent glass based on doped black talc, characterized in that: The annealing system is 680℃ / 10h.

5. Eu according to claim 1 3+ Doped black talc-based high-performance luminescent glass has potential applications in lighting or display devices using near-ultraviolet light as the excitation light source.

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