CN117185664A - Long afterglow microcrystalline glass and preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of long afterglow materials and discloses a method for preparing long afterglow glass-ceramics. The method includes: (1) sequentially carrying out melting treatment, shaping treatment and annealing treatment on a mixture containing a composition for long afterglow glass-ceramics. , to obtain base glass; (2) perform nucleation treatment and crystallization treatment on the base glass in sequence to obtain the long afterglow crystallized glass; the long afterglow crystallized glass provided by the present invention has a long afterglow time and good stability.

Description

Long afterglow crystallized glass and its preparation method and application

Technical field

The invention relates to the field of long afterglow materials, and in particular to a long afterglow crystallized glass and its preparation method and application.

Background technique

Long afterglow luminescent materials, referred to as long afterglow materials, are a type of photoluminescent material that emits visible light when excited by a light source and can store part of the obtained light energy. After the excitation stops, the energy is slowly released in the form of visible light. Luminescent materials have important applications in many fields such as nighttime traffic emergency instructions, instrument displays, national defense and military (such as night travel maps), and are also expected to be used in cutting-edge scientific and technological fields such as solar cells and life sciences.

Traditional long-afterglow materials are mainly powders, which age quickly and have a limited service life when used in outdoor environments exposed to wind, sun and rain.

For example, Qiu Zhihai, Zheng Zhiqiang and others publicly used a high-temperature solid-phase method to prepare phosphor Ca ₂ MgSi ₂ O ₇ : Ce ³⁺ , Eu ²⁺ under reducing atmosphere conditions, and studied its energy transfer and light color. (Study on energy transfer and light color of new WLED phosphors Ca ₂ MgSi ₂ O ₇ : Ce ³⁺ , Eu ²⁺ , Chinese Journal of Rare Earths, Volume 29, Issue 5,). The active elements in the powder materials prepared by this prior art are easily deactivated by environmental influences, and have the disadvantages of being inconvenient to use and easily causing environmental pollution.

CN102765894A discloses long afterglow luminescent glass particles and a preparation method thereof. In this method, long afterglow powder is wrapped with resin on the surface of transparent colorless glass particles. However, organic matter is prone to aging, and its long-term weather resistance is still a problem.

Therefore, developing a long-afterglow luminescent material with stable physical and chemical properties, high afterglow brightness, and long life is an urgent problem in current practical applications.

Contents of the invention

The object of the present invention is to provide a long afterglow crystallized glass with long afterglow time and good stability.

In order to achieve the above objects, a first aspect of the present invention provides a method for preparing long afterglow crystallized glass, which method includes:

(1) The mixture containing the composition for long afterglow glass-ceramics is sequentially subjected to melting treatment, molding treatment and annealing treatment to obtain base glass;

(2) The base glass is sequentially subjected to nucleation treatment and crystallization treatment to obtain the long afterglow crystallized glass; the conditions for the nucleation treatment include: a temperature of 550-750°C and a time of 2-4 hours; The conditions for the crystallization treatment include: temperature 750-1000°C, time 1-3h;

Based on the total molar amount of the composition, the composition contains 15-20 mol% CaO, 7-10 mol% MgO, 52-66 mol% SiO ₂ , and 3-5.5 mol% Al ₂ O ₃ , 0.5-1mol% B ₂ O ₃ , 0.5-1.5mol% Na ₂ O , 0.2-2mol% ZrO ₂ , 0.05-2mol% Eu ₂ O ₃ , 0-1mol% Ce ₂ O ₃ ; and The molar ratio of the MgO and the CaO is 1:1.8-2.5.

Preferably, the molar ratio of the Eu ₂ O ₃ and the Ce ₂ O ₃ is 1:0.9-1.1.

More preferably, based on the total molar amount of the composition, the composition contains 18-20 mol% CaO, 9-10 mol% MgO, 60-64 mol% SiO ₂ , 3-5.5 mol% Al ₂ O ₃ , 0.5-1mol% B ₂ O ₃ , 0.5-1.5mol% Na ₂ O , 0.5-2mol% ZrO ₂ , 0.5-1mol% Eu ₂ O ₃ , 0.5-1mol% Ce ₂ O ₃ .

Preferably, in step (1), the melting treatment is performed in the presence of carbon powder.

More preferably, the amount of carbon powder is not less than 5 wt% based on the total weight of the mixture.

Preferably, in step (1), the melting treatment conditions include: a temperature of 1350-1550°C and a time of 3-4 hours.

Preferably, the annealing treatment conditions include: a temperature of 450-600°C and a time of 4-6 hours.

Preferably, in step (2), the nucleation treatment conditions include: a temperature of 620-680°C and a time of 2-3 hours.

More preferably, in step (2), the crystallization treatment conditions include: a temperature of 850-950°C and a time of 1-2 hours.

A second aspect of the present invention provides long-afterglow crystallized glass prepared by the method described in the first aspect.

A third aspect of the present invention provides the application of the long-afterglow crystallized glass described in the second aspect in the fields of energy-saving indication and/or anti-counterfeiting.

The long-afterglow crystallized glass provided by the present invention is a composite material in which micron crystals and/or nanocrystals are evenly embedded in an inorganic glass matrix. It combines the advantages of crystals and glass materials and has optical properties similar to or even better than those of crystals. performance and simple preparation method. The long afterglow crystallized glass provided by the invention has a long afterglow time, good thermal stability and physical and chemical stability, good weather resistance and long service life.

Compared with the existing technology, the technical solution provided by the present invention also has the following advantages:

(1) In the long-afterglow crystallized glass of the present invention, the incorporation of Eu ²⁺ as an activator and Ce ³⁺ as a sensitizer can effectively absorb sunlight, and can emit light for up to 23 hours after the illumination stops. green afterglow light;

(2) The present invention preferably adopts high-temperature heat treatment, which can controllably precipitate crystals in the glass, and the glass matrix can well cover the crystals, thereby improving the stability of the material;

(3) The preparation method provided by the present invention is simple, low-cost, high-yield, can be excited by a variety of external light sources, has a long afterglow, and has broad application prospects in the fields of night lighting, energy-saving indication, anti-counterfeiting and other fields.

Description of the drawings

Figure 1 is a process route diagram for the preparation of long-afterglow glass-ceramics according to a preferred specific embodiment provided by the present invention;

Figure 2 is a typical XRD diffraction pattern of the long-afterglow crystallized glass provided in Example 1 of the present invention.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.

As mentioned above, the first aspect of the present invention provides a method for preparing long-afterglow glass-ceramics, which method includes:

(1) The mixture containing the composition for long afterglow glass-ceramics is sequentially subjected to melting treatment, molding treatment and annealing treatment to obtain base glass;

(2) The base glass is sequentially subjected to nucleation treatment and crystallization treatment to obtain the long afterglow crystallized glass; the conditions for the nucleation treatment include: a temperature of 550-750°C and a time of 2-4 hours; The conditions for the crystallization treatment include: temperature 750-1000°C, time 1-3h;

Based on the total molar amount of the composition, the composition contains 15-20 mol% CaO, 7-10 mol% MgO, 52-66 mol% SiO ₂ , and 3-5.5 mol% Al ₂ O ₃ , 0.5-1mol% B ₂ O ₃ , 0.5-1.5mol% Na ₂ O , 0.2-2mol% ZrO ₂ , 0.05-2mol% Eu ₂ O ₃ , 0-1mol% Ce ₂ O ₃ ; and The molar ratio of the MgO and the CaO is 1:1.8-2.5.

Preferably, the molar ratio of the Eu ₂ O ₃ and the Ce ₂ O ₃ is 1:0.9-1.1. The inventor found that in this preferred embodiment, the long afterglow glass-ceramics prepared by the method of the present invention has a longer afterglow and better stability.

More preferably, based on the total molar amount of the composition, the composition contains 18-20 mol% CaO, 9-10 mol% MgO, 60-64 mol% SiO ₂ , 3-5.5 mol% Al ₂ O ₃ , 0.5-1mol% B ₂ O ₃ , 0.5-1.5mol% Na ₂ O , 0.5-2mol% ZrO ₂ , 0.5-1mol% Eu ₂ O ₃ , 0.5-1mol% Ce ₂ O ₃ . The inventor found that in this preferred embodiment, the long afterglow crystallized glass prepared by the method of the present invention has a longer afterglow and better stability.

The present invention has no special restrictions on the specific mixing method of the mixture in step (1), as long as the purpose of uniform mixing can be achieved, and those skilled in the art can make a selection based on technical means known in the art. For example, Place each component in the composition into a mortar and grind for 30-60 minutes to mix evenly. The present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.

Preferably, in step (1), the melting treatment is performed in the presence of carbon powder.

More preferably, the amount of carbon powder is not less than 5 wt% based on the total weight of the mixture.

Preferably, in step (1), the melting treatment conditions include: a temperature of 1350-1550°C and a time of 3-4 hours.

The present invention has no special restrictions on the method of the molding process. Those skilled in the art can choose according to the technical means known in the art. For example, the glass liquid obtained after the melting process is poured into the mold and then cooled. Shaping to obtain bulk glass. The present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.

Preferably, the annealing treatment conditions include: a temperature of 450-600°C and a time of 4-6 hours.

Preferably, in step (2), the nucleation treatment conditions include: a temperature of 620-680°C and a time of 2-3 hours. The inventor found that in this preferred embodiment, the long afterglow crystallized glass prepared by the method of the present invention has a longer afterglow.

More preferably, in step (2), the crystallization treatment conditions include: a temperature of 850-950°C and a time of 1-2 hours. The inventor found that in this preferred embodiment, the long afterglow crystallized glass prepared by the method of the present invention has a longer afterglow.

It should be noted that the nucleation treatment and the crystallization treatment each independently include a heating stage and a constant temperature stage, and the temperature of the nucleation treatment and the temperature of the crystallization treatment both refer to the temperature of the constant temperature stage, so The time of the nucleation treatment and the time of the crystallization treatment both refer to the temperature maintenance time of the constant temperature stage. The present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.

Preferably, the temperature rise rate of the nucleation treatment is 5-10°C/min.

Preferably, the temperature rise rate of the crystallization treatment is 3-5°C/min.

Figure 1 is a process flow diagram for the preparation of long-afterglow glass-ceramics according to a preferred specific embodiment of the present invention.

Preferred specific embodiments of the present invention will be described in detail below with reference to Figure 1 , but the present invention is not limited thereto.

S1, ingredients: Place each component in the composition for preparing long-afterglow glass-ceramics in a mortar and grind for 30-60 minutes to obtain a mixture;

S2, melting: In the presence of carbon powder, the mixture is melted at 1350-1550°C for 3-4 hours to obtain a glass melt; based on the total weight of the mixture, the amount of carbon powder is not Less than 5wt%;

S3, molding and annealing: Pour the glass melt into a mold, and then cool and shape it to obtain a block glass. The block glass is kept at 450-600°C for 4-6 hours and annealed to obtain a base glass. ;

S4, nucleation: nucleate the base glass to obtain an intermediate product; the conditions for the nucleation treatment include: temperature of 550-750°C, time of 2-4h, and heating rate of 5-10°C/min ;

S5, crystallization: crystallize the intermediate product to obtain the long-afterglow crystallized glass; the conditions for the crystallization include: a temperature of 750-1000°C, a time of 1-3h, and a heating rate of 3 -5℃/min.

As mentioned above, a second aspect of the present invention provides long-afterglow crystallized glass prepared by the method described in the first aspect.

Preferably, the main crystal phase of the long-afterglow glass-ceramic is Ca ₂ MgSi ₂ O ₇ .

As mentioned above, the third aspect of the present invention provides the application of the long-afterglow crystallized glass described in the second aspect in the fields of energy-saving indication and/or anti-counterfeiting.

The invention provides Eu ²⁺ and Ce ³⁺ co-doped crystallized glass. The main crystal phase of the crystallized glass is Ca ₂ MgSi ₂ O ₇ and belongs to the feldspar structure. Eu ²⁺ is the activator and Ce ³⁺ It is a sensitizer; when it is excited by sunlight, ultraviolet light or irradiated by a fluorescent lamp, Eu ²⁺ undergoes a transition from 4f to 5d. After stopping the excitation, under the combined action of thermal motion and trap energy levels, Eu ²⁺ undergoes a transition from 5d to 4f. Afterglow luminescence occurs during the transition; the incorporation of Ce ³⁺ introduces a new trap energy level, thereby greatly improving the afterglow luminescence effect of Eu ²⁺ . This material has broad application prospects in night lighting, energy-saving indication, anti-counterfeiting and other fields.

The present invention will be described in detail below through examples. Unless otherwise specified, the raw materials used in the following examples are all commercially available products.

In the following examples, the amount of carbon powder is based on the total weight of the mixture.

Unless otherwise specified, in the following examples, it is determined that the sum of the molar amounts of each component in the composition used to prepare long-afterglow glass-ceramics is 10 mol for testing, and the corresponding molar amounts of each component are calculated based on the formula of the glass composition. The mass of the component and weigh it accurately (accurate to two decimal places).

Example 1

This example is used to illustrate that the long-afterglow crystallized glass according to the present invention is prepared according to the formula in Table 1 and as follows.

The method for preparing long-afterglow glass-ceramics includes the following steps:

Step 1: Place each component in the composition for preparing long-afterglow glass-ceramics in a mortar and grind for 40 minutes to obtain a mixture;

Step 2: Place the mixture in an alumina crucible, then place the alumina crucible containing the mixture into a crucible containing carbon powder, and perform melting treatment to obtain a glass melt; the conditions for the melting treatment are: The temperature is 1400℃ and the time is 4h;

Step 3: Pour the glass melt into a mold, then cool and shape it to obtain block glass, and then anneal the block glass to obtain base glass. The conditions for the annealing process are: the temperature is 500°C. , time is 5h;

Step 4: Nucleate the base glass to obtain an intermediate product;

Step 5: Crystallize the intermediate product to obtain the long-afterglow crystallized glass.

Unless otherwise specified, the remaining examples are carried out using a process similar to Example 1. The difference is that the formula used in each example is different. See Table 1 and Table 2 for details.

Table 1

Example 8

This embodiment adopts a similar process to that of Embodiment 1, except that in step (4), the temperature of the nucleation treatment in this embodiment is 750°C.

The rest are the same as Example 1.

Long afterglow glass-ceramic S8 was prepared.

Example 9

This embodiment is carried out using a process similar to that of Embodiment 1, except that in step (5), the temperature of the crystallization treatment in this embodiment is 1000°C.

The rest are the same as Example 1.

Long afterglow glass-ceramic S9 was prepared.

Table 2

Comparative example 4

This comparative example is carried out using a process similar to that of Example 1, except that in step (4), the temperature of the nucleation treatment in this comparative example is 800°C.

The rest are the same as Example 1.

Long afterglow glass-ceramic DS4 was prepared.

Comparative example 5

This comparative example is carried out using a process similar to that of Example 1, except that in step (4), the temperature of the crystallization treatment of this comparative example is 1030°C.

The rest are the same as Example 1.

Long afterglow glass-ceramic DS5 was prepared.

test case

Test method for the main crystal phase: crush and grind the long-afterglow glass-ceramics prepared in the Examples and Comparative Examples of the present invention, and then conduct X-ray powder diffraction analysis. The X-ray diffractometer model used is D8 Advance, purchased from Germany. Bruker Company.

Afterglow time test method: After the glass-ceramics prepared in the above-mentioned examples and comparative examples were irradiated with 365nm ultraviolet rays for 15 minutes, the afterglow luminescence of the glass-ceramics was observed after stopping the irradiation. The results are shown in Table 3;

Stability test of glass-ceramics: The afterglow time of glass-ceramics was tested after being soaked in water for 365 days. The results are shown in Table 3.

table 3

Main crystal phase afterglow color Afterglow time (h) Stability inspection Example 1 Ca ₂ MgSi ₂ O ₇ green twenty three 22.5 Example 2 Ca ₂ MgSi ₂ O ₇ green 21.5 twenty one Example 3 Ca ₂ MgSi ₂ O ₇ green twenty two 21.4 Example 4 Ca ₂ MgSi ₂ O ₇ green twenty two 21.6 Example 5 Ca ₂ MgSi ₂ O ₇ green 21.5 twenty one Example 6 Ca ₂ MgSi ₂ O ₇ green 20 19.6 Example 7 Ca ₂ MgSi ₂ O ₇ green 20.5 20 Example 8 Ca ₂ MgSi ₂ O ₇ green 20.8 20.3 Example 9 Ca ₂ MgSi ₂ O ₇ green 20.6 20.1 Comparative example 1 Ca ₂ MgSi ₂ O ₇ green 5 4.5 Comparative example 2 Ca ₂ MgSi ₂ O ₇ green 10 9.5 Comparative example 3 Ca ₂ MgSi ₂ O ₇ green 5 4.5 Comparative example 4 Ca ₂ MgSi ₂ O ₇ green 5 4.5 Comparative example 5 Ca ₂ MgSi ₂ O ₇ green 4 3.5

It can be seen from the results in Table 3 that the afterglow time and stability of the long-afterglow crystallized glass prepared using the technical solution provided by the present invention are significantly better than those of the comparative example, and it has broad applications in the fields of night lighting, energy-saving indication, anti-counterfeiting, etc. prospect.

The present invention exemplarily provides the X-ray diffraction pattern of the crystal phase of Example 1, as shown in Figure 2. It can be seen from the figure that the main crystal phase is Ca ₂ MgSi ₂ O ₇ .

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, many simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (10)

1. A method for preparing long-afterglow glass-ceramics, characterized in that the method includes: (1) The mixture containing the composition for long afterglow glass-ceramics is sequentially subjected to melting treatment, molding treatment and annealing treatment to obtain base glass; (2) The base glass is sequentially subjected to nucleation treatment and crystallization treatment to obtain the long afterglow crystallized glass; the conditions for the nucleation treatment include: a temperature of 550-750°C and a time of 2-4 hours; The conditions for the crystallization treatment include: temperature 750-1000°C, time 1-3h; Based on the total molar amount of the composition, the composition contains 15-20 mol% CaO, 7-10 mol% MgO, 52-66 mol% SiO ₂ , and 3-5.5 mol% Al ₂ O ₃ , 0.5-1mol% B ₂ O ₃ , 0.5-1.5mol% Na ₂ O , 0.2-2mol% ZrO ₂ , 0.05-2mol% Eu ₂ O ₃ , 0-1mol% Ce ₂ O ₃ ; and The molar ratio of the MgO and the CaO is 1:1.8-2.5. 2. The method according to claim 1, characterized in that the molar ratio of the Eu ₂ O ₃ and the Ce ₂ O ₃ is 1:0.9-1.1. 3. The method according to claim 1 or 2, characterized in that, based on the total molar amount of the composition, the composition contains 18-20 mol% CaO, 9-10 mol% MgO, 60 -64 mol% SiO ₂ , 3-5.5 mol% Al ₂ O ₃ , 0.5-1 mol% B ₂ O ₃ , 0.5-1.5 mol% Na ₂ O, 0.5-2 mol% ZrO ₂ , 0.5-1 mol% Eu ₂ O ₃ , 0.5-1 mol% Ce ₂ O ₃ . 4. The method according to any one of claims 1 to 3, characterized in that in step (1), the melting treatment is performed in the presence of carbon powder. 5. The method according to claim 4, characterized in that in step (1), the amount of carbon powder is not less than 5 wt% based on the total weight of the mixture. 6. The method according to any one of claims 1 to 5, characterized in that, in step (1), the melting treatment conditions include: a temperature of 1350-1550°C and a time of 3-4 hours; And/or, the conditions of the annealing treatment include: the temperature is 450-600°C and the time is 4-6 hours. 7. The method according to any one of claims 1 to 6, characterized in that in step (2), the conditions for the nucleation treatment include: a temperature of 620-680°C and a time of 2-3 hours. 8. The method according to any one of claims 1 to 7, characterized in that in step (2), the conditions for the crystallization treatment include: a temperature of 850-950°C and a time of 1-2 hours. 9. Long-afterglow crystallized glass prepared by the method of any one of claims 1-8. 10. Application of the long-afterglow crystallized glass according to claim 9 in the fields of energy-saving indication and/or anti-counterfeiting.