Long afterglow glass-ceramics and its preparation method and application

Abstract

The present disclosure provides a long-afterglow glass-ceramic, a preparation method, and applications thereof. The glass-ceramic comprises, by mole percentage, 50-65% ZnO, 20-30% SiO2, 5-20% B2O3, 3-10% P2O5, 1-5% TeO2, and 0.1-0.5% MnO. This disclosure enables the production of a long-afterglow material with stable physical and chemical properties, a long lifespan, and a prolonged afterglow time.

Description

Technical Field

[0001] The present disclosure relates to the technical field of microcrystalline glass, and in particular to a long afterglow microcrystalline glass and a preparation method and application thereof. Background Art

[0002] Long afterglow luminescent materials, also known 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 light energy obtained. After the excitation stops, it slowly releases the energy in the form of visible light. It has important applications in many fields such as nighttime traffic emergency instructions, instrument displays, national defense and military (such as night travel maps), etc.

[0003] Traditional long-afterglow materials are primarily powders. When used outdoors in windy, sun-baked, and rainy conditions, they age quickly and have a limited service life. Chinese patent application publication number CN102765894A proposes long-afterglow luminescent glass particles and a method for preparing them. This method involves coating the long-afterglow powder with resin and surrounding the surface of transparent, colorless glass particles. However, organic materials are susceptible to aging, and their long-term weather resistance remains a concern. Furthermore, some existing solutions offer a limited afterglow duration for long-afterglow luminescent glass.

[0004] Therefore, developing a long afterglow luminescent material with stable physical and chemical properties, long afterglow time and long life is an urgent problem to be solved in current practical applications. Summary of the Invention

[0005] A technical problem to be solved by the present disclosure is that the long afterglow luminous glass in the prior art is prone to aging and has a short afterglow time.

[0006] To solve the above technical problems, an embodiment of the present disclosure provides a long afterglow glass-ceramics, which comprises, in molar percentage, 50-65% ZnO, 20-30% SiO2, 5-20% B2O3, 3-10% P2O5, 1-5% TeO2 and 0.1-0.5% MnO.

[0007] In some embodiments, the glass-ceramics comprises, by mole percentage, 55-60% ZnO, 20-25% SiO2, 10-18% B2O3, 3-5% P2O5, 1-3% TeO2, and 0.3-0.4% MnO.

[0008] In some embodiments, the main crystalline phases of the glass-ceramics are Zn2SiO4 and Zn3(PO4)2.

[0009] In some embodiments, the glass-ceramics exhibits a long orange-yellow afterglow after being excited by ultraviolet light.

[0010] In some embodiments, the glass-ceramics exhibits an orange-yellow long afterglow for at least 3 hours; preferably, the glass-ceramics exhibits an orange-yellow long afterglow for at least 5 hours; preferably, the glass-ceramics exhibits an orange-yellow long afterglow for up to 7 hours.

[0011] The embodiment of the present disclosure also provides a method for preparing the above-mentioned long-afterglow microcrystalline glass, comprising: uniformly mixing the raw materials according to a predetermined component ratio; sequentially melting, molding, and annealing the uniformly mixed raw materials to obtain a base glass; and allowing the base glass to undergo a crystallization reaction to obtain a long-afterglow microcrystalline glass.

[0012] In some embodiments, melting comprises melting at a temperature of 1250-1350° C. for 2-4 hours.

[0013] In some embodiments, the annealing comprises annealing at a temperature of 450-550° C. for 4-6 hours.

[0014] In some embodiments, causing the base glass to undergo a crystallization reaction includes heating the base glass to 600-800° C. at a heating rate of 5-10° C. / min and maintaining the temperature for 2-3 hours.

[0015] The embodiments of the present disclosure also provide applications of the long afterglow glass-ceramics described above in the fields of nighttime lighting, energy-saving indication, or anti-counterfeiting.

[0016] Through the above technical solution, the long afterglow glass-ceramics provided by the present disclosure has stable physical and chemical properties, long life, and can achieve a longer afterglow time. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present disclosure or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present disclosure. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0018] Figure 1 4 is a flow chart of a method for preparing long afterglow glass-ceramics according to an exemplary embodiment of the present disclosure. DETAILED DESCRIPTION

[0019] The following embodiments of the present disclosure are further described in detail with reference to the accompanying drawings and examples. The detailed description of the following examples and the accompanying drawings are intended to illustrate the principles of the present disclosure, but are not intended to limit the scope of the present disclosure. The present disclosure can be implemented in many different forms and is not limited to the specific embodiments disclosed herein, but rather includes all technical solutions within the scope of the claims.

[0020] The present disclosure provides these embodiments in order to make this disclosure thorough and complete, and to fully convey the scope of the present disclosure to those skilled in the art. It should be noted that: unless otherwise specifically stated, the relative arrangement of parts and steps, the composition of materials, numerical expressions and numerical values ​​set forth in these embodiments should be interpreted as merely exemplary, and not as limiting.

[0021] It should be noted that, in the description of this disclosure, unless otherwise specified, "plurality" means greater than or equal to two; terms such as "upper," "lower," "left," "right," "inner," and "outer" indicating directions or positional relationships are intended solely to facilitate and simplify the description of this disclosure, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on this disclosure. When the absolute position of the object being described changes, the relative positional relationship may also change accordingly.

[0022] In addition, the terms "first," "second," and similar terms used in this disclosure do not denote any order, quantity, or importance, but are merely used to distinguish different parts. "Perpendicular" does not mean perpendicular in the strict sense, but rather means within the tolerance range. "Parallel" does not mean parallel in the strict sense, but rather means within the tolerance range. "Include" or "comprising" and similar terms mean that the elements preceding the term include the elements listed after the term, and do not exclude the possibility of also including other elements.

[0023] It should also be noted that, in the description of this disclosure, unless otherwise expressly specified or limited, the terms "installed," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to direct connections or indirect connections through an intermediary. Those skilled in the art will understand the specific meanings of the above terms in this disclosure depending on the specific circumstances. When a specific device is described as being located between a first device and a second device, there may or may not be an intervening device between the specific device and the first or second device.

[0024] All terms used in this disclosure have the same meaning as understood by one of ordinary skill in the art to which this disclosure belongs, unless otherwise specifically defined. It should also be understood that terms defined in, for example, common dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted in an idealized or highly formal sense, unless explicitly defined as such herein.

[0025] Technologies, methods, and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered part of the specification.

[0026] The embodiments of the present disclosure provide a long afterglow glass-ceramics, which comprises, in terms of molar percentage, 50-65% ZnO, 20-30% SiO2, 5-20% B2O3, 3-10% P2O5, 1-5% TeO2 and 0.1-0.5% MnO.

[0027] The inventors of the present disclosure recognize that glass-ceramics is a composite material in which micro / nano crystals are embedded in an inorganic glass matrix. It combines the advantages of crystals and glass materials, and can have optical properties similar to or even better than those of crystals, while having advantages similar to those of glass materials, such as simple preparation methods, high thermal stability and physicochemical stability, good weather resistance, and long service life. Based on this recognition, in the embodiments of the present disclosure, a long afterglow material based on glass-ceramics is prepared, so that the stability of the long afterglow material can be achieved and its service life can be improved by means of the stable physicochemical properties of the glass-ceramics itself. In addition, the present disclosure improves the afterglow performance by designing the above formula. In the embodiments of the present disclosure, Mn 2+ Doping, Mn 2+ Can partially replace Zn 2+ , and produces many defect levels, Mn 2+ As activated ions, oxygen vacancies also act as hole traps, while oxygen vacancies in this glass-ceramic system primarily serve as electron traps. The addition of TeO2 effectively increases the concentration of oxygen vacancy defects in the system, thereby improving the electron-hole recombination efficiency, improving the sample's afterglow performance, and increasing the afterglow duration. Overall, the material obtained in this disclosure exhibits excellent transparency, stable physicochemical properties, high afterglow brightness, and long lifetime, making it an excellent long-lasting afterglow material.

[0028] In some embodiments, the glass-ceramics comprises, by mole percentage, 55-60% ZnO, 20-25% SiO2, 10-18% B2O3, 3-5% P2O5, 1-3% TeO2, and 0.3-0.4% MnO.

[0029] In some embodiments, the main crystalline phases of the glass-ceramics are Zn2SiO4 and Zn3(PO4)2.

[0030] In some embodiments, the glass-ceramics exhibits a long orange-yellow afterglow after being excited by ultraviolet light.

[0031] In some embodiments, the glass-ceramics exhibits an orange-yellow long afterglow for at least 3 hours; preferably, the glass-ceramics exhibits an orange-yellow long afterglow for at least 5 hours; preferably, the glass-ceramics exhibits an orange-yellow long afterglow for up to 7 hours.

[0032] refer to Figure 1 The present disclosure also provides a method for preparing the long afterglow glass-ceramics as described above, comprising:

[0033] Mix the raw materials evenly according to the predetermined ratio;

[0034] The uniformly mixed raw materials are sequentially melted, formed, and annealed to obtain basic glass;

[0035] The base glass undergoes a crystallization reaction to obtain long afterglow glass-ceramics.

[0036] In some embodiments, a predetermined amount (e.g., 20-40 grams) of raw materials are weighed according to the glass composition and molar percentages described above and ground in a mortar for 30-60 minutes to thoroughly mix the raw materials. Raw materials may include ZnO, B(OH)3 or B2O3, SiO2, P2O5, TeO2, and MnCO3.

[0037] In some embodiments, melting includes melting at a temperature of 1250-1350° C. for 2-4 hours. The uniformly mixed raw materials can be poured into a first crucible (eg, an alumina crucible), and then the first crucible containing the raw materials is placed into a second crucible containing carbon powder.

[0038] In some embodiments, the molten glass is poured into a mold to form a bulk glass, completing the molding process. The bulk glass is then annealed to eliminate internal stresses in the glass, yielding a base glass. The annealing step includes annealing at a temperature of 450-550°C for 4-6 hours. The annealing step can be performed in a muffle furnace.

[0039] In some embodiments, crystallizing the base glass includes heating the base glass to 600-800°C at a heating rate of 5-10°C / min and maintaining the temperature for 2-3 hours. This high-temperature heat treatment allows for controlled precipitation of crystals within the glass, which are then effectively encapsulated by the glass matrix, thereby improving the stability of the material.

[0040] The present disclosure also provides applications of the long-lasting glass-ceramics described above in nighttime lighting, energy-saving indicators, or anti-counterfeiting applications. The long-lasting glass-ceramics provided by the present disclosure, due to its excellent stability and long-lasting afterglow time, can be well applied in the above fields and has broad application prospects.

[0041] In summary, compared with conventional long afterglow luminescent materials, the present disclosure can achieve at least the following beneficial effects:

[0042] 1. Based on glass-ceramics, it provides good stability.

[0043] 2. Mn 2+ As hole trap centers, oxygen vacancies mainly serve as electron trap centers. The addition of TeO2 effectively increases the concentration of oxygen vacancy defects in the system, thereby increasing the electron-hole recombination efficiency and improving the afterglow performance of the sample.

[0044] 3. The preparation method is simple, low-cost, and high-yield. It can be excited by a variety of external light sources and has a long afterglow time. It can be well applied to night lighting, energy-saving indication, anti-counterfeiting and other fields, and has broad application prospects.

[0045] The following describes the specific examples and comparative examples.

[0046] Example 1

[0047] According to the following composition and molar fractions: 60ZnO—10B2O3—25SiO2—3P2O5—2TeO2—0.1MnO, the raw materials ZnO, B(OH)3, SiO2, P2O5, TeO2, and MnCO3 were weighed and ground in an agate mortar for 30 minutes to thoroughly mix. The mixed raw materials were placed in an alumina crucible, transferred to a larger crucible filled with carbon powder, and melted in a 1300°C elevator furnace for 3 hours. The molten glass was poured into a mold and cooled to form a bulk glass. The bulk glass was then quickly transferred to a 500°C muffle furnace and annealed for 6 hours to eliminate internal stress. The temperature was then raised to 750°C at a rate of 5°C / min and held for 2 hours for crystallization, resulting in an orange-yellow long-lasting glass-ceramic that can be excited by ultraviolet light.

[0048] In this embodiment, the main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2. After being irradiated by ultraviolet light for 15 minutes, the product exhibits an orange-yellow long afterglow, and the long afterglow time is about 3 hours.

[0049] Example 2

[0050] According to the following composition and molar fractions: 60ZnO—15B2O3—20SiO2—3P2O5—2TeO2—0.2MnO, the raw materials ZnO, B(OH)3, SiO2, P2O5, TeO2, and MnCO3 were weighed and ground in an agate mortar for 30 minutes to thoroughly mix. The mixed raw materials were placed in an alumina crucible, transferred to a larger crucible filled with carbon powder, and melted in a 1300°C elevator furnace for 3 hours. The molten glass was poured into a mold and cooled to form a bulk glass. The bulk glass was then quickly transferred to a 500°C muffle furnace and annealed for 6 hours to eliminate internal stress. The temperature was then raised to 750°C at a rate of 5°C / min and held for 2 hours for crystallization, resulting in an orange-yellow long-lasting glass-ceramic that can be excited by ultraviolet light.

[0051] In this embodiment, the main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2. After being irradiated by ultraviolet light for 15 minutes, the product exhibits an orange-yellow long afterglow, and the long afterglow time can reach 4 hours.

[0052] Example 3

[0053] According to the following composition and molar fractions: 55ZnO—18B2O3—22SiO2—4P2O5—1TeO2—0.3MnO, the raw materials ZnO, B(OH)3, SiO2, P2O5, TeO2, and MnCO3 were weighed and ground in an agate mortar for 30 minutes to thoroughly mix. The mixed raw materials were placed in an alumina crucible, transferred to a larger crucible filled with carbon powder, and melted in a 1300°C elevator furnace for 3 hours. The molten glass was poured into a mold and cooled to form a bulk glass. The bulk glass was then quickly transferred to a 500°C muffle furnace and annealed for 6 hours to eliminate internal stress. The temperature was then raised to 750°C at a rate of 5°C / min and held for 2 hours for crystallization, resulting in an orange-yellow long-lasting glass-ceramic that can be excited by ultraviolet light.

[0054] In this embodiment, the main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2. After being irradiated by ultraviolet light for 15 minutes, the product exhibits an orange-yellow long afterglow, and the long afterglow time can reach 7 hours.

[0055] Example 4

[0056] According to the following composition and molar fractions: 58ZnO—12B2O3—23SiO2—5P2O5—2TeO2—0.4MnO, the raw materials ZnO, B(OH)3, SiO2, P2O5, TeO2, and MnCO3 were weighed and ground in an agate mortar for 30 minutes to thoroughly mix. The mixed raw materials were placed in an alumina crucible, then transferred to a larger crucible filled with carbon powder and melted in a 1300°C elevator furnace for 3 hours. The molten glass was poured into a mold and cooled to form a bulk glass. The bulk glass was then quickly transferred to a 500°C muffle furnace and annealed for 6 hours to eliminate internal stress. The temperature was then raised to 750°C at a rate of 5°C / min and held for 2 hours for crystallization, resulting in an orange-yellow long-lasting glass-ceramic that can be excited by ultraviolet light.

[0057] In this embodiment, the main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2. After being irradiated by ultraviolet light for 15 minutes, the product exhibits an orange-yellow long afterglow, and the long afterglow time is about 5 hours.

[0058] Comparative Example 1

[0059] According to the following composition and molar fractions: 60ZnO—15B2O3—20SiO2—3P2O5—2TeO2, weigh the raw materials ZnO, B(OH)3, SiO2, P2O5, and TeO2 and grind them in an agate mortar for 30 minutes to thoroughly mix them. The mixed raw materials are placed in an alumina crucible, transferred to a larger crucible filled with carbon powder, and melted in a 1300°C elevator furnace for 3 hours. The molten glass is poured into a mold and cooled to form a bulk glass. The bulk glass is then quickly transferred to a 500°C muffle furnace and annealed for 6 hours to eliminate internal stresses. The temperature is then raised to 750°C at a rate of 5°C / min and held for 2 hours to allow crystallization to occur, resulting in glass-ceramics.

[0060] In this comparative example, the main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2, and the product does not exhibit long afterglow luminescence after being irradiated by ultraviolet light for 15 minutes.

[0061] Thus far, various embodiments of the present disclosure have been described in detail. To avoid obscuring the concept of the present disclosure, some details well known in the art have not been described. Based on the above description, those skilled in the art can fully understand how to implement the technical solutions disclosed herein.

[0062] Although some specific embodiments of the present disclosure have been described in detail through examples, those skilled in the art will understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. Those skilled in the art will understand that the above embodiments may be modified or some technical features may be replaced with equivalents without departing from the scope and spirit of the present disclosure. In particular, as long as there are no structural conflicts, the various technical features mentioned in the various embodiments may be combined in any manner.

Claims

1. A long afterglow glass-ceramic, characterized in that: In terms of molar percentage, it contains: 55-65% ZnO, 20-25% SiO2, 5-20% B2O3, 3-10% P2O5, 1-5% TeO2 and 0.1-0.5% MnO.

2. The glass-ceramic according to claim 1, characterized in that In terms of molar percentage, the glass-ceramics contains: 55-60% ZnO, 20-25% SiO2, 10-18% B2O3, 3-5% P2O5, 1-3% TeO2 and 0.3-0.4% MnO.

3. The glass-ceramic according to claim 1, characterized in that The main crystalline phases of the microcrystalline glass are Zn2SiO4 and Zn3(PO4)2.

4. The glass-ceramic according to claim 1, characterized in that The microcrystalline glass exhibits a long orange-yellow afterglow after being excited by ultraviolet light.

5. The glass-ceramic according to claim 4, characterized in that: The glass-ceramics exhibits an orange-yellow long afterglow for at least 3 hours.

6. The glass-ceramic according to claim 4, characterized in that: The glass-ceramics exhibits an orange-yellow long afterglow for at least 5 hours.

7. The glass-ceramics according to claim 4, characterized in that: The glass-ceramics exhibits an orange-yellow long afterglow for up to 7 hours.

8. A method for preparing the long afterglow glass-ceramics according to any one of claims 1 to 7, characterized in that: include: Mix the raw materials evenly according to the predetermined ratio; The uniformly mixed raw materials are sequentially melted, formed, and annealed to obtain basic glass; The base glass is subjected to a crystallization reaction to obtain the long afterglow glass-ceramics.

9. The method according to claim 8, characterized in that The melting process includes melting at a temperature of 1250-1350° C. for 2-4 hours.

10. The method according to claim 8, characterized in that The annealing step includes annealing at a temperature of 450-550° C. for 4-6 hours.

11. The method according to claim 8, characterized in that The step of causing the base glass to undergo a crystallization reaction comprises heating the base glass to 600-800° C. at a heating rate of 5-10° C. / min and keeping the temperature for 2-3 hours.

12. Application of the long afterglow glass-ceramics according to any one of claims 1 to 7 in the fields of nighttime lighting, energy-saving indication or anti-counterfeiting.

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