CN101215093A - Manufacturing method of integrated color luminous high-silica glass - Google Patents

Abstract

A method for manufacturing an integrated color luminescent high-silica glass, characterized in that the method comprises the following steps: ① preparing porous glass, ② preparing a rare earth or transition metal luminescent ion solution of a certain concentration; ③ using a segmented doping method to introduce rare earth or transition metal luminescent ions into the porous glass. ④ drying the porous glass doped with rare earth or transition metal luminescent ions in air at 200-800°C; ⑤ placing the dried luminescent ion-doped porous glass in a high-temperature furnace, undergoing solid-phase sintering in air or a reducing atmosphere at 1100-1250°C to eliminate micropores and become a dense and transparent integrated color luminescent high-silica glass. The glass of the present invention has a colorless, dense and transparent appearance, and can emit light of various colors under ultraviolet light. The method has a simple manufacturing process, does not require a binder, and has a low cost. It has excellent optical properties, chemical stability and mechanical strength similar to those of quartz glass.

Description

Manufacturing method of integrated color luminous high-silica glass

technical field

The invention relates to colored luminous glass, in particular to a method for manufacturing integrated colored luminous high-silica glass.

Background technique

Glass is an excellent application material with a series of very valuable properties: transparency, hardness, good chemical stability and optical properties. Compared with crystals and phosphors, glass is easier to be processed into products of various sizes and shapes, and the price is low, and the production cost is low. Visible luminescence of various wavelengths can be obtained by doping appropriate rare earth or transition metal ions in glass, which is widely used in multi-color display, visible laser, colored lamps, advertising lighting and other fields. However, in traditional manufacturing methods, colored luminous glass mostly achieves multiple colors through the combination of multiple pieces of monochromatic luminous glass. Usually in the manufacturing process, a variety of monochromatic glass of different colors must be prepared first, and after cutting and polishing, the monochromatic glass blocks are bonded together with an adhesive. This manufacturing method is cumbersome in process, long in cycle, high in cost, and unavoidable problems such as the matching of the refractive index of the binder and the glass, and the aging of the organic binder by light.

If a manufacturing method can be developed that can emit multiple colors of light on the same piece of glass, it will greatly simplify the manufacturing process and reduce manufacturing costs, which has extremely important practical significance. In order to achieve integrated colored luminescence in glass, it is necessary to dope luminescent ions into glass in sections. Porous glass has uniform micropore distribution and large specific surface area, which can fully disperse luminescent ions in the glass. Since the luminescent ions are immersed in the porous glass by soaking, it is possible to develop a segmented doping method to prepare an integrated colored luminescent glass. In addition, the silica content in high-silica glass exceeds 96%, and its composition is close to that of pure quartz glass, which has similar optical properties, chemical stability and mechanical strength to quartz glass. The integrated luminescent high-silica glass obtained by this method has a series of potential applications in the fields of multi-color display, color barcode identification, colored lamps, advertising lighting and the like.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art, and provide a method for manufacturing an integrated color luminescent high-silica glass, so as to obtain an integrated color luminous high-silica glass with good performance. The so-called integrated colored light-emitting glass is a glass that can emit a variety of colored lights under the light of a whole piece of glass. Under the irradiation of ultraviolet light, the glass of the present invention can emit light of various colors from a single piece of high-silica glass, and the method has simple manufacturing process, no need for adhesive, and low cost. The appearance of the glass is colorless, compact and transparent, and the silicon dioxide content is close to 96%. It has excellent optical properties, chemical stability and mechanical strength similar to quartz glass.

Concrete technical solution of the present invention is as follows:

A method for manufacturing an integrated color luminescent high-silica glass, which is characterized in that the method includes the following steps:

① Preparation of porous glass, the composition of the porous glass is as follows:

Composition wt%

Silicon dioxide (SiO ₂ ) ≥96.0

Boron oxide (B ₂ O ₃ ) 1.0～3.0

Aluminum oxide (Al ₂ O ₃ ) 1.0～3.0

The pore diameter of the porous glass is 1.0-10 nanometers, and the small pores account for 25-40% of the volume of the glass;

② Prepare a certain concentration of rare earth or transition metal luminescent ion solution; by selecting the type and concentration of doped ions, control the luminous color and luminous intensity of colored luminescent glass;

③ Using a segmented doping method to introduce rare earth or transition metal luminescent ions into the porous glass.

④ Dry the porous glass doped with rare earth or transition metal luminescent ions in the air at 200-800°C;

⑤Put the dried luminescent ion-doped porous glass into a high-temperature furnace, and undergo solid-phase sintering in air or reducing atmosphere at 1100-1250°C to eliminate micropores and become a dense and transparent integrated color luminescent high-silica glass;

The preparation of the luminescent ion solution described in the above step ② can be an aqueous solution, an organic solution or an acid solution.

The luminescent ion species described in the above step ② include single doping or co-doping of rare earth ions and transition metal ions, including europium (Eu), terbium (Tb), cerium (Ce), samarium (Sm), yttrium (Y), Single doping or co-doping of copper (Cu), tin (Sn), vanadium (V), silver (Ag) plasma. The luminescence of different colors of the glass under the ultraviolet lamp is realized by changing the doping ion species.

The concentration of the luminescent ions described in the above step ② is 0.01-0.2 mol/L.

Two methods can be adopted for the segmental doping described in the above step ③:

a) Segmented soaking doping method. Segmented immersion doping refers to dividing the porous glass into several segments (A, B, C...), and each segment is soaked in different luminescent ions.

b) Segmented coating doping method. Segmented coating and doping refers to immersing paper strips or cloth strips in the luminescent ion solution, and quickly wrapping absorbent paper strips or cloth strips on each section of porous glass after taking them out, and the porous glass absorbs paper or cloth strips. Doping is achieved by the luminescent ions on the surface.

Technical effect of the present invention is:

The invention uses a physical method to dope rare earth or transition metal luminescent ions into porous glass. Different luminescent ions are introduced into the porous glass by segmental doping, and an integrated color luminescent high-silica glass is obtained after sintering.

The integrated colored luminescent high-silica glass obtained by the invention can emit light of different colors under the irradiation of ultraviolet lamps.

The invention adopts porous glass with large specific surface and strong surface activity as the original matrix doping material, and rare earth or transition metal ions can be fully and uniformly dispersed in the glass. And because the sintering process does not require high-temperature melting, the concentration quenching of luminescent ions can be effectively suppressed, and the luminous intensity of the glass is enhanced.

The silicon dioxide content in the integrated color luminescent high-silica glass produced by the invention is close to that of quartz glass, so it has optical properties, chemical stability and mechanical strength similar to quartz. There are a series of potential applications in multi-color display, color barcode recognition, colored lamps, advertising lighting and other fields.

Description of drawings

Figure 1 is a schematic diagram of the segmental soaking doping method. In the figure: 1-solution; 4-porous glass.

Fig. 2 is a schematic diagram of a segmented encapsulation doping method. In the figure: 1-solution; 2-absorbing paper; 3-absorbing paper soaked with luminescent ions; 4-porous glass.

Figure 3 shows the blue luminescence spectrum of segment A and the green luminescence spectrum of segment B of europium and copper respectively doped into the integrated colored high-silica glass.

Detailed ways

Table 1 lists the main dopant ion species, sintering atmosphere, and luminescent color under the irradiation of ultraviolet lamps in the integrated color luminous high-silica glass of the present invention. Through the combined doping of luminescent ions in Table 1 (comprising the combination of any two or more different color luminescent ions in Table 1), the examples are given to further illustrate the present invention, but the protection of the present invention should not be limited thereby scope.

Table 1

dopant ions Sintering atmosphere luminous color Eu-Y-VSmMnTbCuVEuSnAgCe Air or Redox Reduction Reduction Reduction Reduction Reduction Reduction Reduction Reduction Reduction Reduction Reduction Reduction or Air Reduction Reduction Reduction   Red red red green green yellow blue blue blue blue purple

Example 1

0.50g of analytically pure europium nitrate (Eu(NO ₃ ) ₃ .9H ₂ O) was completely dissolved in 20ml of distilled water to prepare a 0.05mol/L Eu ³⁺ solution; 0.135g of analytically pure copper chloride (CuCl ₂ ) Completely dissolved in 20ml of distilled water to prepare a 0.05mol/L Cu2 ⁺ solution. Divide the selected porous glass strip into two sections, A and B, and immerse the Eu ³⁺ solution into the A section by using the segmental immersion doping method, and then immerse the Cu ²⁺ solution into the B section. The porous glass impregnated with luminescent ions is fully dried in air at 200°C and put into a corundum crucible with a cover, and 10g of graphite or carbon powder is placed around the glass, and then put into a high-temperature furnace for sintering. During the sintering process, the temperature rises from room temperature to 900°C at a rate of 10°C/min, and then from 900 to 1150°C at a rate of 5°C/min, and is kept at 1150°C for 30 minutes, and then the glass is cooled to room temperature with the high-temperature furnace . After solid-phase sintering at 1150°C in a reducing atmosphere, it becomes a dense and transparent integrated color luminous high-silica glass. When the transparent glass is irradiated by an ultraviolet lamp with a wavelength of 254nm, the A section emits blue light with a wavelength near 425nm, and the B section emits green light with a wavelength near 475nm. Figure 3 shows the blue light emission spectrum curve of section A and the green light emission spectrum curve of section B.

Example 2

0.10g of analytically pure Eu(NO ₃ ) ₃ 9H ₂ O, 0.70g of analytically pure yttrium nitrate (Y(NO ₃ ) ₃ 9H ₂ O) and 0.27g of 97% (vanadyl sulfate) VOSO ₄ Completely dissolved in 20ml of distilled water to prepare a mixed solution, the concentration of Eu ³⁺ in the solution is 0.01mol/L, the concentration of Y ³⁺ is 0.08mol/L, and the concentration of V ⁴⁺ is 0.08mol/L. Make solution 1; Dissolve 0.43g of analytically pure cerium nitrate (Ce(NO ₃ ) ₃ 6H ₂ O) completely in 20ml of distilled water, and prepare 0.05mol/L Ce ³⁺ solution, which is designated as solution 2; 0.30 g of analytically pure terbium nitrate (Tb(NO ₃ ) ₃ ·9H ₂ O) was completely dissolved in 20 ml of distilled water to prepare a 0.30 mol/L Tb ³⁺ solution, which was designated as solution 3. Divide the selected porous glass strip into three sections A, B, and C, and use the segmental coating and doping method to immerse solution 1 into section A, immerse solution 2 into section B, and immerse solution 3 into section C. The porous glass impregnated with luminescent ions is fully dried in air at 300°C and put into a corundum crucible with a cover, and then put into a high-temperature furnace for sintering. During the sintering process, the temperature rises from room temperature to 900°C at a rate of 10°C/min, and then from 900 to 1150°C at a rate of 5°C/min, and is kept at 1150°C for 30 minutes, and then the glass is cooled to room temperature with the high-temperature furnace . After solid-state sintering at 1150°C, it becomes a dense and transparent integrated color luminous high-silica glass. When the transparent glass is irradiated by an ultraviolet lamp with a wavelength of 254nm, the A section emits red light with a wavelength of 613nm, the B section emits blue light with a wavelength of 405nm, and the C section emits green light with a wavelength of 542nm.

Example 3

0.17g of analytically pure silver nitrate (Ag(NO ₃ ) ₃ ) was completely dissolved in 20ml of 1mol/L dilute nitric acid to prepare a 0.05mol/L Ag ⁺ solution, which was referred to as solution 1; 0.17g of 97% silver nitrate Vanadyl sulfate (VOSO ₄ ) was completely dissolved in 20 ml of distilled water to prepare a 0.05 mol/L V ⁴⁺ solution, referred to as solution 2; 0.26 g of analytically pure tin chloride (SnCl ₄ ) was completely dissolved in 20 ml of ethanol A 0.05mol/L Sn ⁴⁺ solution was prepared in the solution, which was referred to as solution 3. Divide the selected porous glass strip into three sections A, B, and C, and use the segmental coating and doping method to immerse solution 1 into section A, immerse solution 2 into section B, and immerse solution 3 into section C. The porous glass impregnated with luminescent ions is fully dried in air at 400°C and put into a corundum crucible with a cover, and 15g of graphite or carbon powder is placed around the glass, and then put into a high-temperature furnace for sintering. During the sintering process, the temperature rises from room temperature to 900°C at a rate of 10°C/min, and then from 900 to 1100°C at a rate of 5°C/min, and is kept at 1100°C for 30 minutes, and then the glass is cooled to room temperature with the high-temperature furnace . After solid-phase sintering at 1100°C in a reducing atmosphere, it becomes a dense and transparent integrated color luminous high-silica glass. When the transparent glass is irradiated by an ultraviolet lamp with a wavelength of 254nm, segment A emits blue-violet light with a wavelength of 372nm, segment B emits yellow light with a wavelength of 514nm, and segment C emits blue light with a wavelength of 400nm.

Example 4

0.25g of analytically pure Eu(NO ₃ ) ₃ 9H ₂ O, 0.44g of analytically pure Y(NO ₃ ) ₃ 9H ₂ O and 0.27g of 97% VOSO ₄ were completely dissolved in 20ml of distilled water to prepare Mixed solution, the concentration of Eu ³⁺ in the solution is 0.025mol/L, the concentration of Y ³⁺ is 0.05mol/L, the concentration of V ⁴⁺ is 0.08mol/L, this solution is recorded as solution 1; 0.20g analytically pure Tb(NO ₃ ) ₃ ·9H ₂ O was completely dissolved in 20ml of distilled water to prepare a 0.20mol/L Tb ³⁺ solution, which was referred to as solution 2; 0.25g of analytically pure Eu(NO ₃ ) ₃ ·6H ₂ O was completely dissolved in 20ml of distilled water to prepare a 0.025mol/L Eu ³⁺ solution, which was referred to as solution 3;. Divide the selected porous glass strip into three sections A, B, and C, and use the segmental coating and doping method to immerse solution 1 into section A, immerse solution 2 into section B, and immerse solution 3 into section C. The porous glass impregnated with luminescent ions is fully dried in air at 300°C and put into a corundum crucible with a cover, and then put into a high-temperature furnace for sintering. During the sintering process, the temperature rises from room temperature to 900°C at a rate of 10°C/min, then from 900 to 1250°C at a rate of 5°C/min, and is kept at 1150°C for 30 minutes, and then the glass is cooled to room temperature with the high-temperature furnace . After solid-state sintering at 1250°C, it becomes a dense and transparent integrated color luminous high-silica glass. When the transparent glass is irradiated by an ultraviolet lamp with a wavelength of 254nm, the section A emits red light with a wavelength of 613nm, the section B emits green light with a wavelength of 542nm, and the section C emits blue light with a wavelength of 425nm.

Example 5

0.35g of analytically pure samarium oxide (Sm ₂ O ₃ ) was completely dissolved in 20ml of 1mol/L dilute nitric acid to prepare a ^0.10mol /L Sm solution, which was referred to as solution 1; 0.22g of analytically pure Ce( NO ₃ ) ₃ 6H ₂ O was completely dissolved in 20ml of distilled water to prepare a 0.025 mol/L Ce ³⁺ solution, which was referred to as solution 2; 0.72g of 50% manganese nitrate (Mn(NO ₃ ) ₃ ) Completely dissolve in 20ml of distilled water to prepare 0.1mol/L Mn ²⁺ solution, which is referred to as solution 3; completely dissolve 0.07g of analytically pure CuCl ₂ in 20ml of distilled water to prepare 0.025mol/L Cu ²⁺ The solution is referred to as solution 4; 0.67 g of VOSO ₄ with a content of 97% is completely dissolved in 20 ml of distilled water to prepare a 0.20 mol/L V ⁴⁺ solution, which is referred to as solution 5. Divide the selected porous glass strip into five sections A, B, C, D, and E, and use the segmental coating and doping method to immerse the solution 1 in the A section, immerse the solution 2 in the B section, and immerse the solution in the C section 3. Immerse solution 4 into section D and solution 5 into section E. The porous glass impregnated with luminescent ions is fully dried in air at 800°C and put into a corundum crucible with a cover, and 20g of graphite or carbon powder is placed around the glass, and then put into a high-temperature furnace for sintering. During the sintering process, the temperature rises from room temperature to 900°C at a rate of 10°C/min, and then from 900 to 1150°C at a rate of 5°C/min, and is kept at 1150°C for 30 minutes, and then the glass is cooled to room temperature with the high-temperature furnace . After solid-phase sintering at 1150°C in a reducing atmosphere, it becomes a dense and transparent integrated color luminous high-silica glass. When the transparent glass is irradiated by an ultraviolet lamp with a wavelength of 254nm, the five sections A, B, C, D, and E emit five different colors of light, namely orange-red, blue-purple, red, green, and yellow, respectively.

Claims (5)

1. the manufacture method of an integrated color luminous vycor glass is characterized in that this method comprises the following steps:

1. prepare sintered glass, the composition of this sintered glass is as follows:

Ingredient w t%

SiO ₂ ≥96.0

B ₂O ₃ 1.0～3.0

Al ₂O ₃ 1.0～3.0

The aperture of this sintered glass is 1.0～10 nanometers, and aperture accounts for 25～40% of glass volume;

2. according to the glow color of colorful light-emitting glass and the requirement of luminous intensity, select the kind and the concentration of Doped Rare Earth or transition metal light emitting ionic, and be mixed with corresponding rare earth or transition metal light emitting ionic solution;

3. choose the 1. the sintered glass of step preparation be raw material, adopt sectional doped method, described rare earth or transition metal light emitting ionic solution middle-weight rare earths or transition metal light emitting ionic are incorporated in the described sintered glass;

4. will be mixed with the sintered glass of rare earth or transition metal light emitting ionic, in 200～800 ℃ air, carry out drying;

5. dried light emitting ionic doped porous glass is put into High Temperature Furnaces Heating Apparatus, solid state sintering under 1100～1250 ℃ air or reducing atmosphere, eliminating micropore becomes closely knit transparent integrated color luminous vycor glass.

2. the manufacture method of integrated color luminous vycor glass according to claim 1 is characterized in that the preparation light emitting ionic solution described in described step 2. is the aqueous solution, organic solution or acid solution.

3. the manufacture method of integrated color luminous vycor glass according to claim 1 is characterized in that described light emitting ionic kind comprises singly mixing of rare earth ion and transition metal ion or mixes altogether, comprises Eu, Tb, Ce, Cu, V, Ag, Sm or Y ionic list are mixed or are mixed altogether.

4. the manufacture method of integrated color luminous vycor glass according to claim 1, the strength of solution that it is characterized in that described light emitting ionic is 0.01-0.2mol/L.

5. the manufacture method of integrated color luminous vycor glass according to claim 1 is characterized in that describedly sectional dopedly can taking two kinds of methods:

A) doping method is soaked in segmentation, and this segmentation immersion doping is meant sintered glass is divided into plurality of sections (A, C ...), each section is soaked in respectively in the different light emitting ionic solution;

B) segmentation coats doping method, this segmentation coating-doping is meant paper slip or cloth is dipped in the light emitting ionic solution, rapidly this paper slip or cloth are coated to respectively on each section of sintered glass after the taking-up, so that the light emitting ionic on sintered glass absorption paper slip or the cloth is realized mixing.

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