CN112876073A

CN112876073A - Luminescent glass and preparation method thereof

Info

Publication number: CN112876073A
Application number: CN202110123889.2A
Authority: CN
Inventors: 姜益光; 陈春霖; 张龙; 袁新强; 李家成; 何进; 张龙飞
Original assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Current assignee: Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date: 2021-01-29
Filing date: 2021-01-29
Publication date: 2021-06-01

Abstract

A luminescent glass comprises stannous oxide, stannic fluoride, phosphorus pentoxide and sodium fluoride, wherein the stannous oxide, the stannic fluoride, the phosphorus pentoxide and the sodium fluoride are composed of (30-x): (30+ y): (30+ x): (10-y), wherein x is more than or equal to 0 and less than or equal to 5, y is more than or equal to 0.5 and less than or equal to 4, and x/y is less than or equal to 1.25. The invention can emit fluorescence under the irradiation of the ultraviolet lamp, and has the characteristics of simple preparation method, low preparation cost, high transmittance and good luminous effect.

Description

Luminescent glass and preparation method thereof

Technical Field

The application relates to the field of luminescent glass, in particular to luminescent glass and a preparation method thereof.

Background

At present, the problem of environmental pollution is more and more serious, and the photocatalysis technology is an important means which is indispensable or deficient in treating water pollution. Compared with other methods, the semiconductor photocatalysis technology has the advantages of no secondary pollution, easy large-area popularization and use, low production cost and less later maintenance. Meanwhile, the semiconductor photocatalysis technology combined with the luminescent glass is green and environment-friendly, and accords with the concept of sustainable development.

In addition, along with the increase of the concept of health and environmental protection of the public, the problem of organic volatile gas generated in home decoration and furniture is more and more emphasized. However, the existing air purification means can not completely decompose and treat the organic volatile gases, and the photocatalyst prepared by the luminescent glass can completely degrade the organic gases under the condition of applying a certain light source, so that the condition suitable for living and living of human bodies is achieved.

The luminescent glass used in the current photocatalysis technology is usually realized by adding rare earth elements and quantum dots into a glass substrate, the preparation process of the luminescent glass is complex, the production cost is high, and the luminescent glass is not environment-friendly, so that the preparation of the luminescent glass without adding the rare earth elements and the quantum dots to realize photocatalysis is very important.

Therefore, there is a need for a new luminescent glass that can emit light well without requiring harsh excitation conditions. Meanwhile, the luminescent glass has a simple and easily-controlled preparation method.

Disclosure of Invention

Aiming at the problems that the prior luminescent glass needs to be doped with rare earth elements and quantum dots and the process is complex, the invention provides oxyfluoride luminescent glass and a preparation method thereof. Under the irradiation of ultraviolet rays, the glass can emit fluorescence without requiring severe excitation conditions.

The application provides a luminescent glass, including stannous oxide, tin fluoride, phosphorus pentoxide and sodium fluoride, just the composition mole percentage of stannous oxide, tin fluoride, phosphorus pentoxide and sodium fluoride is (30-x): (30+ y): (30+ x): (10-y), wherein x is more than or equal to 0 and less than or equal to 5, y is more than or equal to 0.5 and less than or equal to 4, and x/y is less than or equal to 1.25.

Optionally, the purities of the stannous oxide, the stannic fluoride, the phosphorus pentoxide and the sodium fluoride are analytically pure.

The application provides a preparation method of luminescent glass, which comprises the following steps: according to (30-x): (30+ y): (30+ x): (10-y) providing stannous oxide, stannic fluoride, phosphorus pentoxide, and sodium fluoride in compositional molar percentages; mixing the stannous oxide, the tin fluoride, the phosphorus pentoxide and the sodium fluoride, and grinding to form a mixed ingredient; carrying out melting treatment on the mixed ingredients to form molten glass; and placing the molten glass into a mold, and condensing to form the luminescent glass.

Optionally, during the melting treatment, the mixed ingredients are placed in a platinum crucible for melting treatment.

Optionally, the melting treatment is carried out at a temperature ranging from 380 ℃ to 450 ℃ for a time ranging from 25 minutes to 35 minutes.

Optionally, the humidity of the environment is kept below a preset threshold when forming the blended ingredients.

The luminescent glass and the preparation method thereof are simple, reliable and easy to operate, have the characteristic of broadband luminescence under the excitation of ultraviolet light, and have better stability and high luminous intensity.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic XRD diffraction diagram of a low temperature oxyfluoride luminescent glass of the present invention;

FIG. 2 is a graph of Tg for a low temperature oxyfluoride luminescent glass of the present invention;

FIG. 3 is a PL diagram for a low temperature oxyfluoride luminescent glass of the present invention;

Detailed Description

In order to overcome the above problems, the inventors propose a luminescent glass and a method for preparing the same. The luminescent glass and the preparation method thereof are further described below with reference to the examples and the accompanying drawings.

And the purities of the stannous oxide, the stannic fluoride, the phosphorus pentoxide and the sodium fluoride are analytically pure.

The application provides a preparation method of luminescent glass, which comprises the following steps:

step S101: according to (30-x): (30+ y): (30+ x): (10-y) providing stannous oxide, stannic fluoride, phosphorus pentoxide, and sodium fluoride in compositional molar percentages;

step S102: and mixing the stannous oxide, the tin fluoride, the phosphorus pentoxide and the sodium fluoride to form a mixed ingredient.

Step S103: and carrying out melting treatment on the mixed ingredients to form molten glass.

In this example, the mixed ingredients were placed in a platinum crucible and melted during the melting process. In fact, the reaction vessel, such as a reaction kettle, etc., may be selected as desired, and it should be noted that the reaction vessel selected should have high temperature resistance characteristics to form the desired molten glass.

In the present example, the melting treatment was carried out at a treatment temperature in the range of 380 ℃ to 450 ℃ for a treatment time of 25 to 35 minutes. In fact, the treatment temperature and the treatment time period at the time of the melting treatment can be set as desired.

Step S104: and placing the molten glass into a mold, and condensing to form the luminescent glass.

In this embodiment, the mold comprises a copper mold. The shape of the mold can be changed according to the needs, such as being arranged in a template shape, or other shapes, so as to obtain the luminescent glass with the needed shape.

Maintaining the ambient humidity below a preset threshold while forming the blended batch. By setting the preset threshold value, the components can be kept dry and do not absorb moisture during the process of mixing and grinding to form the mixed ingredient. In some embodiments, the preset threshold may be set to 15% -30%. Humidity here refers to relative humidity, which refers to the ratio between the water vapor pressure and the water vapor saturation pressure at the prevailing temperature and pressure, and is therefore expressed in percentages.

In fact, the preset threshold value can also be set as required, and the smaller the preset threshold value is, the drier the environment is, and the better the luminous energy efficiency of the finally obtained luminescent glass is.

The luminescent glass obtained by the invention is different from the common luminescent glass which comprises aluminum oxide and zinc oxide, the oxyfluoride is adopted to prepare the luminescent glass, the luminescent glass is simple, reliable and easy to operate, and the luminescent glass has the characteristic of broadband luminescence under the excitation of ultraviolet light, and has better stability and high luminous intensity.

Example 1:

selecting the components with the mole percentage of 30: 30.5: 30: 9.5 stannous oxide, stannic fluoride, phosphorus pentoxide and sodium fluoride, wherein x/y is 0, the raw materials used are analytically pure.

The raw materials are fully and uniformly mixed to form the mixed ingredients.

And (3) placing the mixed ingredients in a platinum crucible, and melting for 25min at the temperature of 380 ℃ to obtain glass liquid.

And pouring the molten glass on a copper mold, and cooling for a period of time to obtain the low-temperature oxyfluoride luminescent glass with good transparency and high stability. And after annealing heat treatment, cutting and polishing to prepare a block-shaped luminescent glass sample.

Example 2:

the preparation method of the oxyfluoride luminescent glass comprises the following steps:

selecting the components with the mole percentage of 29: 30.8: 31: 9.2 stannous oxide, tin fluoride, phosphorus pentoxide, and sodium fluoride, wherein x/y is 1.25. 20g of starting material were weighed out and used as analytical grade.

The raw materials are fully and uniformly mixed to form the mixed ingredients.

And (3) placing the mixed ingredients in a platinum crucible, and melting for 35min at the temperature of 390 ℃ to obtain glass liquid.

Example 3:

the selected components have the mole percentage of 28: 33: 32: 7 stannous oxide, stannic fluoride, phosphorus pentoxide, and sodium fluoride, wherein x/y is 2/3. 20g of raw material was weighed out and used as analytically pure.

The raw materials are fully and uniformly mixed to form the mixed ingredients.

And (3) placing the mixed ingredients in a platinum crucible, and melting for 30min at the temperature of 450 ℃ to obtain glass liquid.

Referring to fig. 1 to 3, there are shown diagrams of luminescent glasses prepared by the method of example 1, wherein fig. 1 is a schematic XRD diffraction diagram of the low temperature oxyfluoride luminescent glass of the present invention, fig. 2 is a Tg diagram of the low temperature oxyfluoride luminescent glass of the present invention, and fig. 3 is a PL diagram of the low temperature oxyfluoride luminescent glass of the present invention.

The XRD diffraction diagram can be used for detecting whether a precipitated crystal phase exists in the luminescent glass, the Tg diagram can be used for indicating that the glass transition temperature of the luminescent glass is low, and the PL diagram can be used for indicating that broadband luminescence is realized under the excitation of ultraviolet light.

The luminescent glass and the preparation method thereof are simple, reliable and easy to operate, can emit fluorescence under ultraviolet rays, have good fluorescence effect and good glass stability, emit light in a broad band different from that of doped rare earth ions, and have high luminous intensity.

The above description is only an embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes performed by the contents of the specification and the drawings, such as the combination of technical features between various embodiments, or the direct or indirect application to other related technical fields, are also included in the scope of the present application.

Claims

1. The luminescent glass is characterized by comprising stannous oxide, tin fluoride, phosphorus pentoxide and sodium fluoride, wherein the stannous oxide, the tin fluoride, the phosphorus pentoxide and the sodium fluoride are composed of (30-x): (30+ y): (30+ x): (10-y), wherein x is more than or equal to 0 and less than or equal to 5, y is more than or equal to 0.5 and less than or equal to 4, and x/y is less than or equal to 1.25.

2. The luminescent glass according to claim 1, wherein the purity of the stannous oxide, stannic fluoride, phosphorus pentoxide, and sodium fluoride is analytical grade.

3. The preparation method of the luminescent glass is characterized by comprising the following steps of:

according to (30-x): (30+ y): (30+ x): (10-y) providing stannous oxide, stannic fluoride, phosphorus pentoxide, and sodium fluoride in compositional molar percentages;

mixing the stannous oxide, the tin fluoride, the phosphorus pentoxide and the sodium fluoride to form a mixed ingredient;

carrying out melting treatment on the mixed ingredients to form molten glass;

and placing the molten glass into a mold, and condensing to form the luminescent glass.

4. The production method according to claim 3, wherein the mixed ingredients are placed in a platinum crucible for melting treatment when the melting treatment is performed.

5. The method according to claim 3, wherein the melt-processing is carried out at a temperature in the range of 380 to 450 ℃ for a period of 25 to 35 minutes.

6. The method of claim 3, wherein the blended formulation is formed while maintaining an ambient humidity below a predetermined threshold.