Method for manufacturing high-precision spatially selective luminescent transparent glass

Abstract

This invention provides a method for manufacturing high-precision spatially selective luminescent transparent glass. The method includes the following steps: melting a base glass blank; processing the base glass; ion-exchange treating the base glass product; masking the ion-exchange glass product with ultraviolet light; and ion-exchange treatment. By employing the manufacturing method described in this invention, transparent glass with high-precision spatially selective luminescence can be obtained, which is more conducive to anti-counterfeiting, storage, and other potential photonic applications.

Description

Technical Field

[0001] This invention relates to the field of optical functional glass, and more specifically to a method for manufacturing a high-precision spatially selective luminescent transparent glass. Background Technology

[0002] Transparent glass with spatially selective luminescence refers to glass in which specific areas emit light when illuminated by excitation light. This type of glass can be used in anti-counterfeiting, decoration, and information storage applications. The property of light emission under excitation light can be provided by elements in the glass composition that possess fluorescent properties, such as Ce. 3+ 、Tb 3+ Such properties are easily achieved through conventional glass manufacturing techniques. However, glass is generally manufactured using a melting method, which often results in homogeneous glass, making it difficult to achieve spatial selectivity in light emission.

[0003] Currently, there are two main methods for achieving spatial selectivity in glass luminescence: First, 3D printing. With the components within the glass-forming region, sols containing and without fluorescent elements are prepared separately. A 3D printer is used to spray and print a preform, ensuring that only specific areas of the preform contain the fluorescent element. The preform is then sintered to obtain transparent glass with spatially selective luminescence. However, this method involves sol-gel and sintering processes. During gelation, the fluorescent element is similar to being in a viscous solution, exhibiting significant spontaneous diffusion. The sintering process is high-temperature, involving various mass transfer phenomena, making diffusion of the fluorescent element unavoidable. This results in limited and relatively low spatial resolution of the spatially selectively luminescent glass obtained through 3D printing. Second, fluorescent thin films with specific shapes are prepared on the glass surface using appropriate masks and coating processes. However, the selective luminescence effect obtained by this method is limited to the glass surface and is easily lost after scratching or washing due to the fragility of the film. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for manufacturing high-precision spatially selective luminescent transparent glass.

[0005] A method for manufacturing high-precision spatially selectively emitting transparent glass, the method comprising the following steps: Step 1: Weigh and mix the glass raw materials according to the composition of the base glass. Place the mixed raw materials in a melting device and heat and melt them to cause the raw materials to undergo physical processes of decomposition, solid-phase reaction, melting, clarification, and homogenization to form a homogeneous glass liquid. The glass liquid flows out through the glass outflow pipe and is rapidly cooled and solidified in a glass mold to obtain a base glass blank. Alternatively, the glass liquid can be poured and / or leaked into a mold and subjected to rapid cooling, solidification, and annealing processes to obtain a base glass blank. Step 2: Process the base glass blank using cutting and / or grinding and / or polishing processes, or process the base glass blank using a hot forming method to form a base glass product with any usable shape; Step 3, place the base glass product into a container containing Ag. + After being kept at a certain temperature in an ion-containing salt bath for a certain period of time, the basic glass product is taken out and cooled to room temperature to form an ion-exchange glass product. Step 4: Mask the ion-exchange glass product and irradiate it with an ultraviolet light source at a certain temperature for a certain period of time. Step 5: Place the light-treated ion-exchange glass product into an immersion chamber free of Ag. + In an ion salt bath, after being kept at a certain temperature for a certain time, silver ions that have not formed nanoparticles in the light-treated ion-exchange glass products are removed, so that silver nanoparticles are distributed in the unmasked area of ​​the glass, resulting in high-precision spatially selective luminescent transparent glass.

[0006] Furthermore, between steps 2 and 3, there is a step: placing the base glass product in an annealing furnace, heating it to a certain temperature, holding it at that temperature for a certain time, and then cooling it down to the final temperature at a certain cooling rate, followed by natural cooling; and / or between steps 3 and 4, there is a step: placing the ion-exchange glass product in an Ag-free furnace. + After being kept at a certain temperature in an ion salt bath, the ionized glass product is taken out and cooled to room temperature; and / or after step 5, there is a step: the high-precision spatially selectively luminescent transparent glass is subjected to surface polishing treatment.

[0007] Furthermore, the temperature for heat preservation in the steps between steps 2 and 3 is 460–630°C, preferably 480–600°C, and more preferably 500–580°C; the heat preservation time is 0.01–120 hours, preferably 0.02–100 hours, and more preferably 0.03–80 hours; the cooling rate is 0.2–50°C / hour, preferably 0.5–20°C / hour, and more preferably 1–10°C / hour; and the final temperature is 80–450°C, preferably 120–445°C, and more preferably 160–440°C.

[0008] Furthermore, the steps between steps 3 and 4 do not contain Ag. + The ion salt bath, by mass percentage, comprises: 20-95% exchange raw material, preferably 25-90%, more preferably 30-85%; and 5-80% filling raw material, preferably 10-75%, more preferably 15-70%. The exchange raw material is one or a mixture of lithium, sodium, and potassium salts, preferably sodium or potassium salts, more preferably potassium nitrate or sodium nitrate. The filling raw material is zinc salt and / or potassium salt and / or barium salt and / or sodium salt, preferably zinc salt and / or sodium salt and / or barium salt, more preferably zinc chloride, barium chloride, or barium nitrate. The temperature of the salt bath is 150-550℃, preferably 175-450℃, more preferably 200-400℃. The holding time is 0.01-2 hours, preferably 0.02-1 hour, more preferably 0.03-0.5 hours. The cooling rate is 0.1-30℃ / min, preferably 0.5-20℃ / min, more preferably 1-15℃ / min.

[0009] Furthermore, the melting temperature in step 1 is 1300–1600℃, preferably 1320–1580℃, and more preferably 1340–1560℃; the clarification temperature is 1350–1650℃, preferably 1380–1620℃, and more preferably 1400–1600℃; and the clarification time is 0.2–72 h, preferably 0.5–64 h, and more preferably 1–48 h.

[0010] Furthermore, step 3 describes the content containing Ag. + The salt bath for ions comprises, by mass percentage, 2-100% silver-containing raw material, preferably 10-60%, more preferably 20-50%; and 0-98% filler material, preferably 40-90%, more preferably 50-80%. The silver-containing raw material is silver chloride, silver nitrate, silver sulfate, or any mixture thereof, preferably a mixture of silver chloride and silver nitrate, more preferably silver nitrate. The filler material is potassium, barium, sodium, or magnesium nitrates or chlorides, preferably a mixture of potassium, sodium, or barium and sodium nitrates, more preferably barium nitrate or sodium nitrate. The temperature of the salt bath is 280-400℃, preferably 300-390℃, more preferably 320-380℃. The holding time is 1-720h, preferably 12-360h, more preferably 24-240h. The cooling rate is 0.1-20℃ / min, preferably 0.5-15℃ / min, more preferably 1-10℃ / min.

[0011] Further, the temperature in step 4 is -196 to 300°C, preferably -40 to 250°C, and more preferably 0 to 200°C; the emission wavelength of the ultraviolet light source is 150 to 500 nm, preferably 200 to 480 nm, more preferably 350 to 460 nm, and more preferably a 365 nm laser, a 405 nm laser, a 450 nm laser, or a mercury lamp; the power density of the ultraviolet light source is 0.01 to 10 watts per square centimeter, preferably 0.1 to 2 watts per square centimeter, and more preferably 0.2 to 1.5 watts per square centimeter; the time is 0.01 to 24 h, preferably 0.02 to 10 h, and more preferably 0.1 to 2 h.

[0012] Furthermore, step 5 describes a substance that does not contain Ag. + The ion salt bath comprises, by mass percentage, 5-90% of the exchange raw material, preferably 15-85%, more preferably 30-80%; and 10-95% of the filling material, preferably 15-85%, more preferably 20-70%. The exchange raw material is sodium salt, potassium salt, or a mixture of both, preferably potassium nitrate, sodium nitrate, or a mixture of both, more preferably potassium nitrate or sodium nitrate. The filling material is zinc sulfate and / or barium chloride and / or zinc chloride and / or zinc nitrate and / or zinc metaphosphate, preferably barium chloride and / or zinc chloride, more preferably zinc chloride. The temperature is 400-600℃, preferably 420-580℃, more preferably 440-560℃. The time is 0.1-72h, preferably 0.5-48h, more preferably 2-36h.

[0013] Furthermore, the moisture resistance of the luminescent transparent glass is Class 2 or below, preferably Class 1; and / or the acid resistance is Class 4 or below, preferably Class 3 or below, more preferably Class 2 or below; and / or λ 80 The fluorescence intensity is below 460 nm, preferably below 440 nm, and more preferably below 430 nm; and / or the fluorescence integral intensity is greater than 5 × 10⁻⁶. 6 Preferably greater than 2×10 7 More preferably, it is greater than 2.5 × 10 7; and / or the color coordinate range is within the range enclosed by (0.300, 0.400), (0.300, 0.300), (0.400, 0.400), (0.400, 0.300), preferably within the range enclosed by (0.320, 0.400), (0.310, 0.330), (0.380, 0.350), (0.390, 0.400), more preferably within (0.325, 0.395), (0.315, 0.330), (0.375, 0.340), (0.390, 0.395); and / or the luminous spatial resolution is less than 0.5 mm, preferably less than 0.1 mm, more preferably less than 0.05 mm.

[0014] Furthermore, the composition of the base glass is expressed as a mole percentage, and the cations include: Mg 2+ : 0~7.5%; Al 3+ : 10~35%; B 3+ 3-20%; Si 4+ : 10~55%; P 5+ : 0~6%; Na + 5-40%; Zn 2+ : 0~5%; Ca 2+ : 0~5%; Sr 2+ : 0~10%; Ba 2+ :0~8%; La 3+ : 0~4%; Y 3+ : 0~5%; Zr 4+ : 0~3%; Yb 3+ : 0~10%; Nb 5+ +Ta 5+ +Gd 3+ : 0~5%; K + : 0~20%; Li + : 0~10%.

[0015] Furthermore, its components are expressed as mole percentages, wherein: Zn 2+ 0–3%, preferably 0–2.5%; and / or Mg 2 + : 0–5%, preferably 0.5–2.5%; and / or Ca 2+ 0-2%, preferably free of; and / or Sr 2+ 0–5%, preferably 0–2.5%; and / or Ba 2+ : 0–3%, preferably 0–1%; and / or Al 3+ : 12-32%, preferably 15-30%; and / or B 3+ : 2-18%, preferably 4-16%; and / or La3+ : 0–1%, preferably 0–0.5%; and / or Y 3+ 0–2%, preferably 0–1.5%; and / or Zr 4+ : 0–2%, preferably 0–1%; and / or Si 4+ : 15-52.5%, preferably 20-50%; and / or P 5+ : 0.2-5%, preferably 0.4-4%; and / or Yb 3+ 0–5%, preferably 0–2%; and / or Nb 5+ +Ta 5+ +Gd 3+ 0-1%, preferably free of; and / or Na + : 10-35%, preferably 15-30%; and / or K + : 0–15%, preferably 0–12%; and / or Li + : 0-2%, preferably 0-1%.

[0016] Furthermore, its components are expressed as mole percentages, wherein: (1.5×Li + +0.8×Na + +K + The content of Zn is 12-32%, preferably 13-31%, and more preferably 14-30%; and / or (Zn 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ The content of Na is 0-10%, preferably 1-6%, more preferably 2-5%; and / or (Na + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ The value is 0.125 to 2.333, preferably 0.5 to 2, and even more preferably 0.875 to 1.667.

[0017] Furthermore, its components are expressed as a mole percentage, and the anion contains O 2- 100%.

[0018] The base glass of high-precision spatially selective luminescent transparent glass has a composition expressed as a mole percentage, containing the following cations: Mg 2+ : 0~7.5%; Al 3+ : 10~35%; B3+ 3-20%; Si 4+ : 10~55%; P 5+ : 0~6%; Na + 5-40%; Zn 2+ : 0~5%; Ca 2+ : 0~5%; Sr 2+ : 0~10%; Ba 2+ :0~8%; La 3+ : 0~4%; Y 3+ : 0~5%; Zr 4+ : 0~3%; Yb 3+ : 0~10%; Nb 5+ +Ta 5+ +Gd 3+ : 0~5%; K + : 0~20%; Li + : 0~10%.

[0019] Furthermore, its components are expressed as mole percentages, wherein: Zn 2+ 0–3%, preferably 0–2.5%; and / or Mg 2 + : 0–5%, preferably 0.5–2.5%; and / or Ca 2+ 0-2%, preferably free of; and / or Sr 2+ 0–5%, preferably 0–2.5%; and / or Ba 2+ : 0–3%, preferably 0–1%; and / or Al 3+ : 12-32%, preferably 15-30%; and / or B 3+ : 2-18%, preferably 4-16%; and / or La 3+ : 0–1%, preferably 0–0.5%; and / or Y 3+ 0–2%, preferably 0–1.5%; and / or Zr 4+ : 0–2%, preferably 0–1%; and / or Si 4+ : 15-52.5%, preferably 20-50%; and / or P 5+ : 0.2-5%, preferably 0.4-4%; and / or Yb 3+ 0–5%, preferably 0–2%; and / or Nb 5+ +Ta 5+ +Gd 3+ 0-1%, preferably free of; and / or Na + : 10-35%, preferably 15-30%; and / or K + : 0–15%, preferably 0–12%; and / or Li +: 0-2%, preferably 0-1%.

[0020] Furthermore, its components are expressed as mole percentages, wherein: (1.5×Li + +0.8×Na + +K + The content of Zn is 12-32%, preferably 13-31%, and more preferably 14-30%; and / or (Zn 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ The content of Na is 0-10%, preferably 1-6%, more preferably 2-5%; and / or (Na + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ The value is 0.125 to 2.333, preferably 0.5 to 2, and even more preferably 0.875 to 1.667.

[0021] The beneficial effects of this invention are: by using the manufacturing method described in this invention, transparent glass with high-precision spatial selective luminescence effect can be obtained, which is more conducive to anti-counterfeiting, storage and other potential photonic applications. Detailed Implementation

[0022] The following is a detailed description of embodiments of the transparent glass with high-precision spatial selective luminescence effect of the present invention. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the present invention's objectives. Furthermore, while there are appropriate omissions in the repeated descriptions, this does not limit the scope of the invention. In the following text, the transparent glass with high-precision spatial selective luminescence effect of the present invention will sometimes be simply referred to as luminescent transparent glass, luminescent glass, or glass.

[0023] [A method for manufacturing transparent glass with high-precision spatial selective luminescence effect]

[0024] The manufacturing method of the luminescent transparent glass described in this invention will be described below.

[0025] Luminescent glass is prepared by utilizing the fluorescence properties of silver nanoparticles in glass, following steps 1-8 in numerical order. It should be noted that the mandatory steps described below play an irreplaceable role in achieving the functional characteristics of the luminescent glass of this invention; the optional steps described below, whether or not they are performed, do not affect the achievement of the functional characteristics of the luminescent glass of this invention.

[0026] The essential step 1 is melting the base glass blank. The glass raw materials are weighed and mixed according to the composition of the base glass. The mixed raw materials are placed in a melting device and heated and melted, causing the raw materials to undergo physical processes of decomposition, solid-phase reaction, melting, clarification, and homogenization to form a homogeneous glass melt. The glass melt flows out through a glass outlet pipe and is rapidly cooled and solidified in a glass mold to obtain the base glass blank. Alternatively, the glass melt can be poured and / or dripped into a mold, and after rapid cooling, solidification, and annealing, the base glass blank is obtained.

[0027] The essential step 2 is processing the base glass. The base glass blank described in step 1 is processed using cutting and / or grinding and / or polishing processes, or by thermoforming, to form a base glass product with any usable shape.

[0028] Optional step 3: Annealing the base glass product. The base glass product is placed in an annealing furnace, heated to a certain temperature, held at that temperature for a certain time, and then cooled to a specific temperature at a controlled rate, followed by natural cooling. The purpose of this step is to relax the thermal and processing stresses in the base glass product, and / or to change the virtual temperature of the base glass prepared using hot forming methods.

[0029] The mandatory step 4 is ion exchange treatment of the base glass product. The base glass product described in step 3 is placed in a salt bath for ion exchange, forming an ion-exchanged glass product. The salt bath in this step is characterized by containing Ag. + Ions. The purpose of this step is to introduce a specific concentration of silver ions into the glass. In the following description, the ion exchange treatment of the basic glass product in step 4 may be simply referred to as ion exchange (I) or ion exchange (I) step.

[0030] Optional step 5 involves a second ion exchange treatment of the base glass product. The ion-exchange glass product described in step 4 is placed in a salt bath for ion exchange. The salt bath in this step is characterized by being Ag-free. + Ion exchange. The purpose of this step is to remove silver ions from the glass surface while maintaining a specific concentration of silver ions in the inner layer of the glass, which is beneficial to the stability of the glass properties in humid and hot environments. In the following description, the ion exchange treatment of the basic glass product in step 5 may be simply referred to as ion exchange (II) or ion exchange (II) step.

[0031] The mandatory step 6 is mask-based ultraviolet irradiation treatment of the ion-exchange glass product. The ion-exchange glass product described in steps 4 and / or 5 is masked and treated under ultraviolet light of a certain intensity for a certain period of time to form an irradiated ion-exchange glass product. The purpose of this step is to allow the portion of the glass not covered by the mask to be irradiated with ultraviolet light, causing the silver ions therein to be excited and form silver nanoparticles, while the state of the silver ions in the portion of the glass covered by the mask remains unchanged.

[0032] The mandatory step 7 is ion exchange treatment. The ion-exchange glass product, which underwent light treatment as described in step 6, is placed in a salt bath for ion exchange. The salt bath in this step is characterized by being Ag-free. + Ions. The purpose of this step is to remove silver ions that have not formed nanoparticles in the light-treated ion-exchange glass product, so that the glass contains silver nanoparticles distributed in the unmasked region controlled by the mask in step 6, achieving a high-precision spatially selective luminescence effect, and forming the high-precision spatially selective luminescence glass described in this invention. In the following description, the ion exchange treatment of the basic glass product in step 7 may be simply referred to as ion exchange (III) or ion exchange (III) step.

[0033] Optional step 8: Surface polishing of the glass. The transparent glass with the high-precision spatial selective luminescence effect described in step 7 is then subjected to surface polishing. The purpose of this step is to polish the glass surface and avoid luminescence scattering caused by potential surface damage during steps 3-7.

[0034] The following explains the restrictions involved in each step.

[0035] [Basic Glass Composition]

[0036] The composition (components) range of the basic glass described in step 1 of the present invention constituting the luminescent glass is explained below. In this specification, unless otherwise specified, the content of a cationic component is expressed as the molar percentage (mol%) of that cationic component among all cationic components. The ratio between the contents of cationic components is the ratio of the molar percentage contents of each cationic component, and the total content is expressed as an ion molar percentage. It should be noted that the valence values ​​of each component in this invention are representative values ​​used for convenience and are not different from the valence values ​​of other ions. Some elements mentioned in the following description may have one or more possible valence states; in this specification, a representative valence state of the element is used for explanation.

[0037] The statement in this invention regarding the absence of specific components means that specific components are not actively introduced, but does not exclude their entry into the actually manufactured glass in the form of raw material impurities, impurities introduced during the manufacturing process, etc.

[0038] In this invention, the description of the relationships between the contents of each component involves multiplication and / or division. The component content is calculated using its actual percentage value. For example, when the component content percentage is 10%, it is calculated as 0.1 in multiplication and / or division relationships.

[0039] Unless otherwise specified in the specific context, the numerical ranges listed herein include upper and lower limits. "Above" and "below" include endpoint values ​​and all integers or fractions included within the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means either only A, or only B, or both A and B.

[0040] <Basic Glass Cationic Components>

[0041] The luminescent glass of this invention has a total cation content of 100% in its base glass. Impurity elements are not included in the cation content.

[0042] Na + It exists in the form of a network exterior within the glass. The base glass of the luminescent glass of this invention must contain a network exterior to enable the salt bath ion exchange process and achieve the function of the luminescent glass. + The ionic radius of Ag + Being relatively close is beneficial for Ag in subsequent steps. + -Na + The time required for the ion exchange process is reduced. Na in glass + Increased content is beneficial for improving Ag content. + -Na + Ag in glass after ion exchange process + A suitable ion concentration is beneficial for obtaining silver nanoparticles under subsequent light irradiation treatment. However, in glass, Na... + At higher concentrations, Na + Further increases in Na content lead to a decrease in the chemical stability of the glass. + If the sodium content is further increased, the glass network connectivity becomes too low, making glass formation difficult. Therefore, Na... + The content ranges from 5% to 40%, preferably from 10% to 35%, and more preferably from 15% to 30%.

[0043] K + It exists in the glass as a network of external structures. K + The ionic radius is greater than that of Ag. + The base glass contains K + It has the advantage of reducing the stress generated during subsequent ion exchange processes. Therefore, K +The content ranges from 0 to 20%, preferably from 0 to 15%, and more preferably from 0 to 12%.

[0044] Li + It exists in the glass as a network of external structures. Li + Its fluxing effect is better than K + Na + In some cases, containing Li + The glass can avoid the formation of internal stones. However, in the glass system of this invention, Li... + Excessive Li content increases the glass's tendency to crystallize, and Li + Increasing the Li content is detrimental to the glass's salt bath reusability in subsequent ion exchange processes. Therefore, Li + The content ranges from 0 to 10%, preferably from 0 to 2%, and more preferably from 0 to 1%.

[0045] Li + Na + K + Both Li and Li have the function of exchanging ions with ions in a salt bath within glass. However, Li... + Na + K + When the total content of Li in the glass is too high, the tendency for glass crystallization increases, making it impossible to obtain glass with usable intrinsic quality through conventional melting. + Na + K + Regarding the crystallization tendency of the glass system of this invention, it has Na + <K + <Li + The relationship. Therefore, the present invention needs to control (1.5×Li) + +0.8×Na + +K + The range of ) is 12-32%, preferably 13-31%, and more preferably 14-30%.

[0046] Ag + In glass, it is a network exosome component. Ag + The invention provides the luminescent properties of the glass, but during the high-temperature melting process, Ag... + Ag readily forms spontaneous clusters and nanoparticles, which hinders subsequent adjustments to the spatial distribution of nanoparticles in the glass through masking and exposure processes. Therefore, Ag in glass... + The content ranges from 0 to 15%, preferably from 0 to 3%, and more preferably not contained.

[0047] Zn 2+ Relative to Mg in glass 2+ Ca 2+It is easier for Zn to enter the glass network, and when the content is appropriate, it has a good effect on improving the glass's resistance to crystallization in the glass of this invention, which is beneficial to the stability of glass properties during the secondary thermoforming process that the glass of this invention may undergo. However, Zn 2+ Excessive Zn content can easily lead to the precipitation of ZnAl2O4 crystals in the glass. Therefore, Zn 2+ The content ranges from 0 to 5%, preferably from 0 to 3%, and more preferably from 0 to 2.5%.

[0048] The glass of this invention contains an appropriate amount of Mg. 2+ This is beneficial for improving resistance to crystallization and reducing the required refining temperature of the glass. However, Mg in glass... 2+ Excessive Mg content leads to a decrease in the glass's resistance to crystallization. Therefore, Mg 2+ The content ranges from 0 to 7.5%, preferably from 0 to 5%, and more preferably from 0.5 to 2.5%.

[0049] Ca 2+ In glass, it can improve the mechanical and manufacturing properties of the glass. However, the glass of this invention requires multi-step ion exchange, and if the Ca in the glass... 2+ Entering a salt bath can easily lead to salt poisoning, significantly reducing the reusability of the salt bath. Therefore, Ca... 2+ The content ranges from 0 to 5%, preferably from 0 to 2%, and more preferably not contained.

[0050] Sr 2+ Its application effect in glass is between that of Ca 2+ Ba 2+ Between, and it will not cause salt bath poisoning. In Sr 2+ At low concentrations, Sr will not cause glass phase separation. 2+ The effect of improving the anti-crystallization properties of glass is not as good as that of Mg. 2+ Zn 2+ Therefore, Sr 2+ The content ranges from 0 to 10%, preferably from 0 to 5%, and more preferably from 0 to 2.5%.

[0051] Ba 2+ It is a network intermediate ion suitable for increasing the refractive index of silicate-based glasses. An increased refractive index allows the glass to possess a more distinctive luster, which is beneficial in the case of the luminescent glass of this invention being used for decorative purposes. However, Ba... 2+ Excessive Ba content can easily lead to glass phase separation, reducing the chemical stability and luminous spatial precision of the luminescent glass of this invention. Therefore, Ba 2+ The content ranges from 0 to 8%, preferably from 0 to 3%, and more preferably from 0 to 1%.

[0052] Zn 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ Both are glass network modifiers, capable of occupying interstitial positions within the glass network, and due to their large size and high charge, they are not easily moved within the interstitial spaces. Therefore, Zn 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ In glass, this method helps reduce the tendency of silver ions introduced through ion exchange within the glass to self-diffuse and form nanoparticles under thermal excitation during the subsequent salt bath step. The glass contains Zn. 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ In two or more of the following cases, Zn 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ It also exhibits a mixed alkaline earth effect, which slightly improves the chemical stability of the glass. Therefore, it is preferable to use glass containing Zn. 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ It may contain one, two, three, or four of the following, more preferably one or two, and most preferably two.

[0053] To achieve good anti-crystallization properties in the base glass of this invention, Zn 2+ Mg 2+ Ca 2+ Ba 2+ 、Sr 2+ Total content (Zn) 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ The content is 0-10%, preferably 1-6%, and more preferably 2-5%.

[0054] Al 3+ It is a glass network forging body and an essential component for achieving the beneficial effects of the glass of this invention. In alkali-containing silicate glasses, Al 3+ Generally, it is composed of [AlO4]. - It exists in form. [AlO4] -The Al-O bond length in the glass is longer than that of the Si-O and BO bonds, resulting in a larger network porosity. This facilitates the migration of ions outside the network and promotes the aggregation of silver ions during subsequent exposure. (Al in the glass...) 3+ The higher the content, the greater the ion diffusion coefficient of the glass, and the shorter the time required for subsequent ion exchange. Al 3+ Within a suitable range of content in glass, the glass ion diffusion coefficient is within a suitable range. However, in Al... 3+ When the content of Al is too high, glass is difficult to manufacture using conventional melting methods. This is because Al... 3+ The raw materials introduced all have high melting points and are not easy to melt, and Al 3+ The increased content of Al significantly increases the viscosity and surface tension of the molten glass, making it difficult to clarify. Therefore, Al 3+ The content ranges from 10% to 35%, preferably from 12% to 32%, and more preferably from 15% to 30%.

[0055] B 3+ It exists in the glass as a network formation and is an essential component for achieving the beneficial effects of the glass of this invention. Although the BO bond length is smaller than that of Al-O and Si-O bonds, B... 3+ This can lead to a decrease in the ion diffusion coefficient, but B 3+ Ag in glass after hindering ion exchange + Ion diffusion. In Al 3+ B 3+ When both are present, the basic units such as [AlO4], [BO3], and [BO4] mixed in the glass network have a certain distribution structure, which is conducive to the diffusion of silver ions in the glass and can prevent Ag from diffusing. + Ions spontaneously diffuse within the glass to form silver ion nanoparticles. (B) 3+ The beneficial effects are manifested within a certain range, if B 3+ If the content of B is too high, the fluorescence intensity of the luminescent glass of this invention will decrease. Therefore, B 3+ The content ranges from 3% to 20%, preferably from 2% to 18%, and more preferably from 4% to 16%.

[0056] B 3+ It can exist in glass as [BO4] or [BO3]. In B 3+ When present in the form of [BO3], its effect on reducing the glass ion diffusion coefficient is relatively small. This may be because [BO3] has a planar configuration, and its connection with the pyramidal structural units such as [AlO4] and [SiO4] easily creates voids. Therefore, (Na) is preferred. + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ The concentration is between 0.125 and 2.333, more preferably 0.5 to 2, and even more preferably 0.875 to 1.667. When (Na) + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ Within the preferred range, this is beneficial for improving the chromaticity of the luminescent glass of the present invention. This is because the ultraviolet and short-wave visible absorption of the luminescent glass mainly comes from silver nanoparticles. When the glass composition is within the preferred range, it is easy to achieve the excellent characteristics of uniform size distribution and small size of silver nanoparticles, which is beneficial for reducing light absorption from silver nanoparticles.

[0057] Contains a small amount of La 3+ This is beneficial for improving the stability of the glass of the present invention. Under appropriate content, La... 3+ This is beneficial for slightly improving the chromaticity of the luminescent glass of the present invention. However, La 3+ As the content increases, the glass's resistance to crystallization decreases significantly. Therefore, La... 3+ The content is 0-4%, preferably 0-1%, and more preferably 0-0.5%.

[0058] Y 3+ with La 3+ Their functions are basically the same in glass. 3+ The ionic radius is slightly smaller than that of La. 3+ Y tends to enter the glass network more readily in silicate glasses. 3+ Excessive Y content causes the glass network to tend to deagglomerate, reducing its resistance to crystallization. Therefore, Y 3+ The content is 0-5%, preferably 0-2%, and more preferably 0-1.5%.

[0059] Zr 4+ It is a glass network modifier component. It contains a small amount of Zr. 4+ Zr has an improving effect on the chemical stability of glass. However, Zr... 4+ The corresponding raw materials are generally ZrO2 and SiZrO4. These raw materials are difficult to melt, and if their content is too high, it can easily lead to the presence of stones inside the glass melted by conventional methods. Therefore, Zr 4+The content ranges from 0 to 3%, preferably from 0 to 2%, and more preferably from 0 to 1%.

[0060] Si 4+ It is the main component of the glass of this invention. If Si... 4+ Due to the high Si content, the glass of this invention is more difficult to melt. 4+ If the content of Si is further increased, the content of other necessary constituent elements will inevitably decrease, causing the glass of this invention to fail to achieve the designed effect. 4+ If the Si content is too low, the glass's resistance to crystallization decreases. Therefore, Si... 4+ The content ranges from 10% to 55%, preferably from 15% to 52.5%, and even more preferably from 20% to 50%.

[0061] P 5+ It is a glass network forming component. P 5+ With Al 3+ Similarly, it has the effect of improving the glass ion diffusion coefficient. At the same time, P 5+ It also reduces glass viscosity and prevents silver ions entering the glass in subsequent ion exchange steps from spontaneously forming silver ion clusters or silver nanoparticles. Therefore, P 5+ The content ranges from 0 to 6%, preferably from 0.2 to 5%, and more preferably from 0.4 to 4%.

[0062] Glass contains appropriate amounts of Yb 3+ This is beneficial for improving the fluorescence intensity of the glass of the present invention. However, whether or not it contains Yb 3+ The invention does not significantly affect the beneficial effects of the glass. Therefore, Yb 3+ The content ranges from 0 to 10%, preferably from 0 to 5%. More preferably from 0 to 2%.

[0063] Nb 5+ Ta 5+ Gd 3+ When the content is below a certain range, it does not affect the production performance and anti-crystallization properties of the basic glass of this invention. However, Nb 5+ Ta 5+ Gd 3+ Increasing the Nb content does not significantly improve the performance of the glass of this invention, but it does increase the raw material cost of the glass. Therefore, Nb 5+ +Ta 5+ +Gd 3+ The total content is 0-5%, preferably 0-1%, and more preferably none.

[0064] Pr 3+ 、Nd 3+ 、Sm 3+ Eu2+ 、Tb 3+ Dy 3+ Ho 3+ Er 3+ Tm 3+ Possessing a rich 4f-shell electronic structure, these elements can generate various photon-excited electronic level transitions and cross-linking transitions, among other physical processes. Introducing these elements can alter the excitation spectrum characteristics, thereby changing the emission color. The luminescence process of these elements also interacts with silver ion clusters and silver nanoparticles, potentially increasing the emission intensity of the glass under certain intensity excitation light. The base glass of this invention does not contain Pr. 3+ 、Nd 3+ 、Sm 3+ Eu 2 + 、Tb 3+ Dy 3+ Ho 3+ Er 3+ Tm 3+ However, introducing the aforementioned elements into luminescent glass to alter the excitation spectrum color and intensity of the excitation light is a glass property adjustment measure readily conceived by those skilled in the art, and does not possess any additional innovativeness. Further introducing these elements into the base glass based on the process steps described in this invention remains within the scope of protection of this invention.

[0065] The base glass described in this invention does not contain the toxic and harmful element As. + Pb + 、Tl + Cd 2+ And Bi, which may damage platinum utensils used for melting. 3+ .

[0066] <Catoid Impurities>

[0067] Fe 3+ Ni 2+ Co 2+ Mn 2+ V 5+ Cu 2+ These are transition metal coloring impurities. To achieve the luminescent glass function described in this invention, the content of these coloring impurities in the base glass needs to be strictly controlled. (Fe) 3+ Ni 2+ Co 2+ Mn 2+ V 5+ Cu 2 + The total content is less than 50 ppm, preferably less than 20 ppm, and more preferably less than 5 ppm.

[0068] Sb3+ Sn 2+ Pt 4+ W 6+ Mo 6+ Ce 4+ It belongs to the category of variable-valence elements. To achieve the luminescent glass function described in this invention, the base glass of this invention needs to control the content of the aforementioned impurities to avoid the uncontrollable formation of additional silver ion clusters and nano-silver particles due to redox reactions between silver ions and the aforementioned variable-valence element ions. However, due to factors such as possible corrosion of the smelting vessel and electrodes during the melting process, the content of the aforementioned impurities is sometimes difficult to strictly control. Sb 3+ Sn 2+ Pt 4+ W 6+ Mo 6+ Ce 4+ The total content is less than 100 ppm, preferably less than 50 ppm, and more preferably less than 10 ppm.

[0069] <Anionic components>

[0070] The luminescent glass of this invention has a base glass anion content of 100%, and impurity elements are not included in the anion content.

[0071] In this invention, O 2- The content is 100%.

[0072] F - Cl - SO4 2- S 2- The presence of fluorine in glass makes it prone to devitrification during subsequent processes. Therefore, the glass of this invention does not contain fluorine. - Cl - SO4 2- S 2- However, the glass of this invention contains F. - Cl - SO4 2- S 2- The possibility of impurities.

[0073] [Basic Glass Manufacturing Methods]

[0074] The manufacturing method of the basic glass of this invention is as follows: Common glass raw materials (such as oxides, carbonates, nitrates, etc.) are weighed and mixed according to the glass composition. The mixed raw materials are placed in a melting device and heated and melted. The melting process of the glass raw materials of this invention is generally completed in a platinum chamber. The melting temperature (melting temperature) of the raw materials for the glass of this invention is preferably 1300–1600°C, more preferably 1320–1580°C, and even more preferably 1340–1560°C. After the above raw materials are completely melted and vitrified, the glass temperature is raised or lowered to its clarification temperature and maintained for a certain period of time to clarify the molten glass. The clarification temperature of the glass of this invention is preferably 1350–1650°C, more preferably 1380–1620°C, and even more preferably 1400–1600°C. The clarification time is preferably 0.2–72 h, more preferably 0.5–64 h, and even more preferably 1–48 h. The molten glass after the clarification process is homogenized by stirring, or continuously supplied to a glass outflow pipe for rapid cooling and solidification in a glass mold to obtain base glass; or it is poured and / or poured from a molten container into a mold of a specific shape, and after rapid cooling, solidification, and annealing, base glass is obtained.

[0075] During the melting and refining process of the basic glass of this invention, appropriate equipment and processes should be used to minimize the volatilization of glass components; suitable technical means should be adopted to ensure the consistency of glass composition and optical homogeneity. During the mixing, weighing, and melting of raw materials for the glass of this invention, appropriate equipment and processes should be used to prevent moisture absorption of the raw materials. Within the above principles and process parameter range, those skilled in the art can appropriately select raw materials, process methods, and process parameters according to equipment characteristics and actual needs.

[0076] [Annealing heat treatment method]

[0077] The following describes the annealing heat treatment method described in step 3 of the luminescent glass preparation process of the present invention.

[0078] The glass product is placed in a heat treatment furnace and heated to a specific holding temperature. After holding at that temperature for a specific time, it is slowly cooled down to a specific temperature at a specific cooling rate, and then allowed to cool naturally.

[0079] The selection of a specific heat treatment temperature should follow these principles: First, the heat treatment temperature should be higher than the strain point temperature of the glass. Heat treatment below the strain point temperature cannot achieve the effect of eliminating internal stress in the glass or changing its virtual temperature. Second, the heat treatment temperature should be lower than the sag temperature of the glass. Heat treatment above the sag temperature causes the glass to fail to maintain its useful shape after heat treatment. The specific heat treatment temperature in this invention is 460–630°C, preferably 480–600°C, and more preferably 500–580°C.

[0080] The specific heat treatment time ranges from 0.01 to 120 hours, preferably from 0.02 to 100 hours, and more preferably from 0.03 to 80 hours. Those skilled in the art can select a suitable specific heat treatment time within the range described in this invention, based on the characteristics of the heat treatment equipment used, the dimensions of the glass product, and the glass product forming method.

[0081] The specific cooling rate ranges from 0.2 to 50°C / hour, preferably from 0.5 to 20°C / hour, and more preferably from 1 to 10°C / hour. Those skilled in the art can select a suitable specific cooling rate based on the dimensions of the glass product and the characteristics of the heat treatment equipment.

[0082] The selection of a specific end temperature should follow these principles: First, ensure the glass does not experience excessively rapid cooling. If the specific end temperature is too high, the glass product will cool too quickly during natural cooling, potentially leading to surface micro-cracks. Second, minimize equipment downtime. If the specific end temperature is too low, the heat treatment equipment will operate for too long, reducing production efficiency. The specific end temperature range is 80–450℃, preferably 120–445℃, and more preferably 160–440℃. Those skilled in the art can select a suitable specific end temperature based on the glass product's dimensions and the characteristics of the heat treatment equipment.

[0083] During the annealing heat treatment process, appropriate technical means should be adopted to avoid temperature inhomogeneity in the heat treatment equipment; when annealing more than one sample at a time, appropriate technical means should be adopted to avoid temperature inconsistency between samples and stress inconsistency caused by stacking methods.

[0084] [Ion Exchange (I) Method]

[0085] The following describes the ion exchange method described in step 4 of the luminescent glass preparation process of the present invention.

[0086] <Composition of Salt Bath>

[0087] In this invention, the composition of the salt bath is expressed as a percentage by mass.

[0088] The ion exchange (I) salt bath contains silver-containing raw materials and filler materials.

[0089] Silver-containing raw materials are essential components of ion exchange (I) salt baths to achieve the purpose of introducing silver ions into the glass through ion exchange. The silver-containing raw materials can be silver chloride, silver nitrate, silver sulfate, or any mixture thereof, preferably a mixture of silver chloride and silver nitrate, and more preferably silver nitrate. The higher the content of the silver-containing raw material, the better the effect of introducing silver ions into the glass through ion exchange; however, when the content of the silver-containing raw material exceeds a certain limit, further increasing its content does not significantly improve the effect of introducing silver ions through ion exchange. At the same time, increasing the content of the silver-containing raw material increases the cost of the salt bath preparation, especially in the case of large-scale preparation. If the content of the silver-containing raw material is too low, on the one hand, the ion exchange effect is poor, and on the other hand, the number of times the salt bath can be reused is low. Therefore, the content of the silver-containing raw material introduced into the salt bath is 2-100%, preferably 10-60%, and more preferably 20-50%. The purpose of the filler material is to reduce the proportion of silver-containing raw material in the salt bath, thereby reducing the cost of the salt bath while ensuring the ion exchange effect. Using the filler material also has the beneficial effects of reducing the decomposition rate of the silver-containing raw material in the salt bath and preventing elemental silver from adhering to the glass products. The packing material can be nitrates or chlorides of potassium, barium, sodium, or magnesium, preferably a mixture of potassium, sodium, or barium and sodium nitrates, and more preferably barium nitrate or sodium nitrate. The content of the packing material in the salt bath is 0-98%, preferably 40-90%, and more preferably 50-80%.

[0090] <Salt Bath Process>

[0091] The glassware is placed in a salt bath and kept at a specific salt bath temperature for a certain period of time. Then, the glassware is removed and cooled to room temperature at a specific rate.

[0092] The salt bath temperature should be within an appropriate range. Too high a temperature leads to excessively rapid decomposition of the silver-containing raw materials, reducing the reusability of the salt bath and increasing its cost. Too low a temperature makes it difficult to exchange samples with significant thickness. Therefore, the salt bath temperature range is 280–400℃, preferably 300–390℃, and more preferably 320–380℃.

[0093] The value of the salt bath (heat preservation) time is mainly related to the shape and size of the glass product, the composition of the base glass, and the salt bath temperature. Those skilled in the art can select a salt bath time range of 1 to 720 hours based on the above factors, preferably 12 to 360 hours, and more preferably 24 to 240 hours.

[0094] The cooling rate after the salt bath should be within an appropriate range. If the cooling rate is too fast, the glass removed from the salt bath is prone to cracking due to uneven cooling rates inside and outside the glass, solidification of the molten salt adhering to the sample, and the mismatch between the thermal expansion coefficients of the solidified molten salt and the glass, resulting in subsurface cracks that are detrimental to subsequent processing. If the cooling rate is too slow, silver ions that have entered the glass through ion exchange are prone to agglomeration due to high-temperature insulation, which is also detrimental to subsequent processing. Therefore, the cooling rate should be in the range of 0.1–20°C / min, preferably 0.5–15°C / min, and more preferably 1–10°C / min. Appropriate technical means should be adopted to control the cooling rate of the glass within the range described in this invention. Those skilled in the art can add solid salt bath additives that are insoluble in the salt bath according to actual needs.

[0095] [Ion Exchange (II) Method]

[0096] The following describes the ion exchange method described in step 5 of the luminescent glass preparation process of the present invention.

[0097] <Composition of Salt Bath>

[0098] In this invention, the composition of the salt bath is expressed as a percentage by mass.

[0099] Ion exchange (II) salt baths contain exchange raw materials and filling raw materials.

[0100] The exchange raw material is an essential component of the ion exchange (II) salt bath. Its function is to replace the silver ions on the surface of the glass, which contains silver ions after the ion exchange (I) step, preventing the silver ions on the glass surface from dissociating with OH groups released from water vapor in the air. - The ionic phase reaction increases the possibility of reducing silver ions on the glass surface, which has the beneficial effect of enhancing the environmental stability of the glass.

[0101] The exchange raw material may consist of one or a mixture of lithium, sodium, and potassium salts, preferably sodium or potassium salts, and more preferably potassium nitrate or sodium nitrate. Potassium nitrate, as an exchange raw material, introduces compressive stress into the glass and has a relatively slow diffusion rate. Therefore, when the product size is small or the shape is special, using potassium nitrate as the exchange raw material has the advantages of a wide usable range of ion exchange time, easy and precise control, and less damage to the glass after ion exchange. Sodium nitrate, as an exchange raw material, introduces tensile stress into the glass and has a relatively high diffusion rate. In some cases, it has the advantage of relatively shorter ion exchange time. The content of the exchange raw material ranges from 20% to 95%, preferably 25% to 90%, and more preferably 30% to 85%.

[0102] The filler material is an essential component of the ion exchange (II) salt bath. The functions of the filler material include: First, adjusting the overall melting point of the salt bath to match its process temperature. Second, reducing the activity of silver ion impurities introduced during the ion exchange process, preventing the shift of the ion exchange equilibrium and thus ensuring the elimination of surface silver ions. Third, the filler material may also contain monovalent ions to assist the ion exchange function of the exchange material. The main components of the filler material are zinc salts and / or potassium salts and / or barium salts and / or sodium salts, preferably zinc salts and / or sodium salts and / or barium salts, and more preferably zinc chloride, barium chloride, or barium nitrate. The content of the filler material ranges from 5% to 80%, preferably 10% to 75%, and more preferably 15% to 70%.

[0103] <Salt Bath Process>

[0104] The glassware is placed in a salt bath and kept at a specific salt bath temperature for a certain period of time. Then, the glassware is removed and cooled to room temperature at a specific rate.

[0105] The salt bath temperature is determined according to the following principles. First, the salt bath temperature should not be too high, to avoid the formation of silver ion clusters due to spontaneous diffusion of silver atoms entering the glass in the previous steps, which would prevent the spatial selective luminescence effect of the luminescent glass of this invention from being achieved. Second, in some cases, the salt bath temperature should not be too low, to avoid surface microcracks in the glass product due to excessive ion exchange stress. A moderate salt bath temperature helps maintain the salt bath time within an appropriate range, saving operating time of the salt bath furnace and increasing the precision of salt bath time control. The salt bath temperature range is 150–550℃, preferably 175–450℃, and more preferably 200–400℃.

[0106] The determination of the salt bath time is mainly related to the composition of the base glass, the salt bath temperature, and the salt bath composition. The salt bath time ranges from 0.01 to 2 hours, preferably from 0.02 to 1 hour, and more preferably from 0.03 to 0.5 hours. Those skilled in the art can select a salt bath time with better implementation effect within the above range.

[0107] The cooling rate after the salt bath should be within an appropriate range. If the cooling rate is too fast, the glass removed from the salt bath is prone to cracking due to uneven cooling rates inside and outside the glass, solidification of the molten salt adhering to the sample, and the mismatch between the thermal expansion coefficients of the solidified molten salt and the glass, resulting in subsurface cracks that are detrimental to subsequent processing. If the cooling rate is too slow, the silver ions that have entered the glass through ion exchange are prone to agglomeration due to high-temperature insulation, which is also detrimental to subsequent processing. Therefore, the cooling rate should be in the range of 0.1–30℃ / min, preferably 0.5–20℃ / min, and more preferably 1–15℃ / min.

[0108] Those skilled in the art should take appropriate technical measures, including but not limited to installing water-cooled baffles at the opening of the salt bath and sealing the salt bath, to reduce the volatilization of the salt bath and ensure that the above-mentioned technical effects can be achieved. Those skilled in the art may add solid salt bath additives that are insoluble in the salt bath to the salt bath according to actual needs.

[0109] [Mask and UV Exposure]

[0110] The masking and ultraviolet (UV) exposure steps are essential for achieving the high-precision spatially selective luminescence glass described in this invention. The principle is that the silver ions entering the glass after the preceding steps are essentially in a metastable state. During UV exposure, the photosensitive silver ions in the glass absorb photon energy, possessing sufficient energy to overcome the displacement barrier, thereby forming silver nanoparticles within the glass. The region where silver nanoparticles are formed in the glass is highly correlated with the region exposed. The silver ions that have formed silver nanoparticles exhibit fluorescence properties and do not participate in subsequent ion exchange steps, which is the source of the spatially selective luminescence performance described in this invention. The following describes the implementation method of the masking and UV exposure process.

[0111] <Mask Process>

[0112] Specific areas of a glass article can be selectively shielded using known and commonly used methods such as coating and / or shielding and / or masking and / or deposition, achieving any usable shielding shape.

[0113] <Ultraviolet Exposure Process>

[0114] The masked glass product is irradiated for a specific time at a specific temperature using a specific ultraviolet light source with a specific power.

[0115] The selection of ultraviolet (UV) exposure temperature should be based on the following principles: If the UV exposure temperature is too low, the required UV exposure power and time to achieve the desired technical effect will be too high; if the UV exposure temperature is too high, the size of the silver nanoparticles will be difficult to control, easily leading to colloidal coloring in the glass. Therefore, the UV exposure temperature is -196 to 300°C, preferably -40 to 250°C, and more preferably 0 to 200°C. The UV exposure temperature refers to the temperature of the glass product or the temperature of the enclosed space containing the glass product during UV exposure, measured using a thermocouple and / or an infrared thermometer.

[0116] The longer the emission wavelength of the ultraviolet light source, the lower the photon energy, and the more difficult it is to induce the movement of silver ions in the glass to form silver nanoparticles. Conversely, the shorter the emission wavelength, the higher the intrinsic absorption of the glass, and the faster the intensity of the light attenuates within the glass, making it difficult to achieve a consistent ultraviolet exposure effect along the glass thickness direction. Therefore, the emission wavelength of the ultraviolet light source is 150–500 nm, preferably 200–480 nm, more preferably 350–460 nm, and even more preferably a 365 nm laser, a 405 nm laser, a 450 nm laser, or a mercury lamp. Those skilled in the art can rationally select other types of ultraviolet light sources based on this, such as pulsed excimer lasers.

[0117] The power density of the ultraviolet light source needs to be adjusted according to the following principles. If the power density of the ultraviolet light source is too low, the exposure time required to achieve the design effect of this invention will be longer. Below a certain power density, the required time becomes too long, making it impractical. If the power density is too high, it can easily lead to excessive growth of silver ion nanoparticles, resulting in increased glass color. Therefore, the power density of the ultraviolet light source is 0.01–10 W / cm², preferably 0.1–2 W / cm², and more preferably 0.2–1.5 W / cm². The exposure time is 0.01–24 h, preferably 0.02–10 h, and more preferably 0.1–2 h.

[0118] [Ion Exchange (III) Method]

[0119] The following describes the ion exchange method described in step 7 of the luminescent glass preparation process of the present invention.

[0120] <Composition of Salt Bath>

[0121] In this invention, the composition of the salt bath is expressed as a percentage by mass.

[0122] The ion exchange (III) salt bath contains exchange raw materials and filling raw materials.

[0123] The exchange feedstock is an essential component of the molten salt in the salt bath used in the ion exchange (III) step. Its function is to contain monovalent element ions, which, after sufficient ion exchange time, allows the silver ions that have not yet formed silver nanoparticles in the glass to reach an equilibrium concentration with the exchanged monovalent element ions. The exchange feedstock is composed of sodium salts, potassium salts, or a mixture of both, preferably potassium nitrate, sodium nitrate, or a mixture of both, and more preferably potassium nitrate or sodium nitrate. The content of the exchange feedstock ranges from 5% to 90%, preferably 15% to 85%, and more preferably 30% to 80%.

[0124] The filler material is an essential component of the ion exchange (III) molten salt. Its function is to reduce the activity of silver ions in the salt bath, thereby lowering the ion exchange equilibrium concentration of silver ions in the glass and effectively removing silver ions that have not polymerized into silver nanoparticles. The filler material consists of zinc sulfate and / or barium chloride and / or zinc chloride and / or zinc nitrate and / or zinc metaphosphate, preferably barium chloride and / or zinc chloride, and more preferably zinc chloride. Excessive filler material content increases the volatility of the salt bath, which is detrimental to the health of operators and the stability of the salt bath composition. Therefore, the filler material content ranges from 10% to 95%, preferably 15% to 85%, and more preferably 20% to 70%.

[0125] Those skilled in the art should take appropriate technical measures to prevent the salt bath from evaporating.

[0126] <Salt Bath Process>

[0127] The glassware is placed in a salt bath and kept at a specific salt bath temperature for a certain period of time before being removed.

[0128] The salt bath temperature is determined based on the following principles: First, the salt bath temperature should be as high as possible to avoid excessively long ion exchange processes, which could cause the silver nanoparticles already present in the glass to grow and increase the glass's color. Second, excessively high salt bath temperatures could cause silver ions in the glass to spontaneously diffuse and form additional silver nanoparticles, reducing the glass's luminescence spatial precision. Therefore, the salt bath temperature range is 400–600℃, preferably 420–580℃, and more preferably 440–560℃.

[0129] The salt bath time ranges from 0.1 to 72 hours, with a preferred range of 0.5 to 48 hours and an optimal range of 2 to 36 hours. Those skilled in the art can determine the salt bath time based on the dimensions of the glass product, the salt bath temperature, and the glass composition.

[0130] [Luminescent Glass Composition]

[0131] The composition and content range of the luminescent glass obtained by the present invention are described below.

[0132] The luminescent glass of this invention, based on a base glass, undergoes only ion exchange treatment that alters its composition. During ion exchange treatment, the content of divalent, trivalent, tetravalent, and pentavalent cations in the glass remains unchanged. Therefore, the composition of the luminescent glass of this invention is expressed as a mole percentage (mol%), containing: Zn 2+ The content is 0-5%, preferably 0-3%, and more preferably 0-2.5%; Mg 2+ The content is 0-7.5%, preferably 0-5%, and more preferably 0.5-2.5%; Ca 2+ The content is 0-5%, preferably 0-2%, and more preferably none; Sr 2+ The content is 0-10%, preferably 0-5%, and more preferably 0-2.5%; Ba 2+ The content is 0-8%, preferably 0-3%, and more preferably 0-1%; Al 3+ The content is 10-35%, preferably 12-32%, and more preferably 15-30%; B 3+ The content is 3-20%, preferably 2-18%, and more preferably 4-16%; La 3+ The content is 0-4%, preferably 0-1%, and more preferably 0-0.5%; Y 3+ The content is 0-5%, preferably 0-2%, and more preferably 0-1.5%; Zr 4+ The content is 0-3%, preferably 0-2%, and more preferably 0-1%; Si 4+ The content is 10-55%, preferably 15-52.5%, and more preferably 20-50%; P 5+ The content is 0-6%, preferably 0.2-5%, and more preferably 0.4-4%; Yb 3+ The content is 0-10%, preferably 0-5%. More preferably 0-2%; Nb 5+ +Ta 5+ +Gd 3+ The total content is 0-5%, preferably 0-1%, and even more preferably none.

[0133] The luminescent glass of this invention is based on a base glass and undergoes ion exchange treatment. Because the glass appears as a hard and brittle solid during ion exchange, the various components within the glass do not possess the ability to thermally migrate; therefore, the composition range of the luminescent glass can be outside the crystallization range of the glass. Thus, the glass of this invention contains: Na + The content is 1-40%, preferably 5-30%, and more preferably 10-25%; K + The content is 0-40%, preferably 0-30%, and more preferably 0-25%; Li +The ionic radius of Li is too small to belong to the molten salt component of ion exchange (III), therefore Li + The content is 0-5%, preferably 0-2%, and more preferably 0-0.2%; Ag + The content is 0.01-36%, preferably 0.1-20%, and more preferably 2-10%.

[0134] In the luminescent glass of this invention, when Ag + / (Na + +Li + +K + +Ag + If the size is too small, the luminous intensity of the glass is low, and the luminous area occupies too small a proportion of the whole, making it difficult to have a usable function; when Ag + / (Na + +Li + +K + +Ag + Increased silver content in glass leads to an increase in silver nanoparticles, affecting glass color; Ag + / (Na + +Li + +K + +Ag + The size is too large to be achieved using the technology of this invention. + / (Na + +Li + +K + +Ag + Within the preferred range, glass exhibits optimal performance. Therefore, this invention limits Ag... + / (Na + +Li + +K + +Ag + The value is 0.0001 to 0.9, preferably 0.001 to 0.5, and more preferably 0.005 to 0.25.

[0135] O in the luminescent glass of this invention 2- The content is 100%.

[0136] [Testing and Characterization Methods]

[0137] <Moisture resistance stability Rc>

[0138] The moisture resistance stability of the luminescent glass of this invention was tested according to the surface method of GB / T 7962.15-2010. Moisture resistance stability can be classified into four categories based on comparison with H-BaK7 and H-ZK9 glasses, as shown in Table 1. The moisture resistance stability of the luminescent glass of this invention is category 2 or lower, preferably category 1.

[0139] Table 1

[0140] <Acid Resistance Stability RA>

[0141] According to the surface method test method of GB / T 7962.14-2010, the acid resistance stability of glass is divided into 6 categories based on its stability to acid solutions, as shown in Table 2. The acid resistance stability of the luminescent glass of the present invention is category 4 or below, preferably category 3 or below, and more preferably category 2 or below.

[0142] Table 2

[0143] <chroma λ 80 >

[0144] chromaticity λ 80 This refers to the short-wavelength transmission spectral characteristics of glass. In this invention, the test sample thickness is 2 mm, and λ... 80 This refers to the wavelength at which the glass transmittance reaches 80%. λ 80 The lower the λ, the more transparent the glass appears and the less color distortion, which is a beneficial effect in this invention. The λ of the luminescent glass of this invention... 80 The wavelength is below 460nm, preferably below 440nm, and most preferably below 430nm.

[0145] <Basic Glass Anti-crystallization Properties>

[0146] First, the presence of crystallization in the base glass produced by conventional melting methods was observed under strong light with the naked eye and under a microscope. If the glass did not contain crystallization, it was cut into 20×20×20mm samples, placed in a muffle furnace, and held at 780℃ for 0.5 hours. The surface was then polished, and the presence of crystallization was observed under strong light with the naked eye. The crystallization resistance level is shown in Table 3. The anti-crystallization performance level of the base glass of this invention is Grade B or higher, preferably Grade A.

[0147] Table 3

[0148] <Integral fluorescence intensity>

[0149] The fluorescence spectrum and integrated fluorescence intensity of the glass of this invention were tested using a fluorescence spectrometer. The excitation wavelength was fixed at 365 nm, and the emission wavelength range was 380–780 nm. The sample consisted of two large polished glass slides (40 × 30 × 2 mm) without a mask during the UV exposure step. The excitation slit was set to 4 nm, the emission slit to 2 nm, the integration time to 1 s, and the wavelength interval for the test data was 1 nm. The integrated fluorescence intensity was the sum of the fluorescence intensities of the glass at wavelengths from 380 to 780 nm. The integrated fluorescence intensity of the luminescent glass of this invention is greater than 5 × 10⁻⁶. 6 Preferably greater than 2×10 7 More preferably, it is greater than 2.5 × 10 7 .

[0150] <Color coordinates>

[0151] The color coordinates of the glass described in this invention are determined using the CIE 1931 standard colorimetric chart based on luminous intensity. The color coordinates are two-dimensional coordinates, with the x and y coordinates determined according to the following formula:

[0152]

[0153] Where X, Y, and Z are respectively: λ λ λ in, , , This is a known and commonly used color matching function table. The luminescent glass of this invention emits a warm, soft white light when excited by 365nm light, with color coordinates ranging from (0.300, 0.400), (0.300, 0.300), (0.400, 0.400), (0.400, 0.300), preferably within the range of (0.320, 0.400), (0.310, 0.330), (0.380, 0.350), (0.390, 0.400), and more preferably between (0.325, 0.395), (0.315, 0.330), (0.375, 0.340), and (0.390, 0.395).

[0154] <Emitting spatial resolution accuracy>

[0155] The spatial resolution of the light emission of the glass described in this invention was tested using the following method. First, in steps 1-8 of the preparation process for the luminescent glass, a 40×30×2mm, six-sided polished glass sample was used. The width of the light-transmitting area of ​​the mask was 2mm, and the interval between adjacent light-transmitting areas was 3mm. The large surface of the glass was observed using an optical microscope with a CCD camera attachment, while a 405nm laser was simultaneously incident on the glass from the side to obtain a glass luminescence image at the mask interface. The spatial resolution R of the light emission was defined as the straight-line distance from the position where the luminescence intensity was 0.368 times the average luminescence intensity of the exposure area (i.e., 1 / natural logarithm e) to the position where the luminescence intensity was equal to the average luminescence intensity of the exposure area. The spatial resolution of the light emission of the luminescent glass of this invention is less than 0.5mm, preferably less than 0.1mm, and more preferably less than 0.05mm.

[0156] <Example of Illuminating Glass>

[0157] To further clarify and illustrate the technical solution of the present invention, the following non-limiting embodiments are provided. In this embodiment, optical glasses as shown in Tables 4 to 7 are obtained using the aforementioned optical glass manufacturing method. Furthermore, the characteristics of each glass are measured using the testing method described in this invention, and the measurement results are shown in Tables 4 to 7.

[0158] In some embodiments, the glass composition of the luminescent glass of the present invention is determined by the following method: The luminescent glass of the present invention is crushed, ground into powder using an agate mortar, and then ground for another 5 minutes to ensure uniform particle size. A certain amount of powder is taken, and the composition of the glass is tested using an X-ray fluorescence spectrometer (XRF). The glass contains Li... + In this case, an additional amount of powder was taken, dissolved and diluted in heated hydrofluoric acid, and Li was tested using inductively coupled plasma-atomic emission spectrometry (ICP-AES). + Element content. Results are expressed as cation molar ratio.

[0159] Table 4

[0160]

[0161] Table 5

[0162]

[0163] Table 6

[0164]

[0165] Table 7

[0166]

[0167] <Example of Glass Prefabricated Components>

[0168] By performing processes such as cutting, gluing, and grinding on the luminescent glass obtained in Examples 1 to 20 of Tables 4 to 7, glass preforms with high-precision spatial selective luminescence effects can be obtained.

[0169] <Assembly Example>

[0170] By combining the high-precision spatially selective light emission preform obtained from the above-described optical preform embodiments with optical components such as lasers, mirrors, prisms, lenses, and optical fibers, an assembly with usable functions can be obtained.

Claims

1. A method for manufacturing high-precision spatially selective luminescent transparent glass, characterized in that, The method includes the following steps: Step 1: Weigh and mix the glass raw materials according to the composition of the base glass. Place the mixed raw materials in a melting device and heat and melt them to cause the raw materials to undergo physical processes of decomposition, solid-phase reaction, melting, clarification, and homogenization to form a homogeneous glass liquid. The glass liquid flows out through the glass outflow pipe and is rapidly cooled and solidified in a glass mold to obtain a base glass blank. Alternatively, the glass liquid can be poured and / or leaked into a mold and subjected to rapid cooling, solidification, and annealing processes to obtain a base glass blank. Step 2: Process the base glass blank using cutting and / or grinding and / or polishing processes, or process the base glass blank using a hot forming method to form a base glass product with any usable shape; Step 3, place the base glass product into a container containing Ag. + After being kept at a certain temperature in an ion-containing salt bath for a certain period of time, the basic glass product is taken out and cooled to room temperature to form an ion-exchange glass product. Step 4: Mask the ion-exchange glass product and irradiate it with an ultraviolet light source for a certain period of time at a certain temperature; the temperature is -196 to 250°C; the emission wavelength of the ultraviolet light source is 350 to 500 nm and the power density is 0.01 to 10 W / cm². Step 5: Place the light-treated ion-exchange glass product into an immersion chamber free of Ag. + In an ion salt bath, after being kept at a certain temperature for a certain time, silver ions that have not formed nanoparticles in the light-treated ion-exchange glass products are removed, so that silver nanoparticles are distributed in the unmasked area of ​​the glass, resulting in high-precision spatially selective luminescent transparent glass.

2. The method of claim 1, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: Between steps 2 and 3, there is a further step: placing the basic glass product in an annealing furnace, heating it to a certain temperature, holding it at that temperature for a certain time, and then cooling it down to the final temperature at a certain cooling rate, followed by natural cooling; and / or between steps 3 and 4, there is a further step: placing the ion-exchange glass product in an Ag-free furnace. + After being kept at a certain temperature in an ion salt bath, the ionized glass product is taken out and cooled to room temperature; and / or after step 5, there is a step: the high-precision spatially selectively luminescent transparent glass is subjected to surface polishing treatment.

3. The method of claim 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The temperature for heat preservation between steps 2 and 3 is 460–630°C; the heat preservation time is 0.01–120 hours; the cooling rate is 0.2–50°C / hour; and the final temperature is 80–450°C.

4. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 2, characterized in that, The temperature for heat preservation between steps 2 and 3 is 480–600°C; the heat preservation time is 0.02–100 hours; the cooling rate is 0.5–20°C / hour; and the final temperature is 120–445°C.

5. The method of claim 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The temperature for heat preservation between steps 2 and 3 is 500–580°C; the heat preservation time is 0.03–80 hours; the cooling rate is 1–10°C / hour; and the final temperature is 160–440°C.

6. The method of claim 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The steps between steps 3 and 4 do not contain Ag. + The ion salt bath comprises, by mass percentage, 20–95% exchange material and 5–80% filling material. The exchange material is one or a mixture of lithium, sodium, and potassium salts, and the filling material is zinc salt and / or potassium salt and / or barium salt and / or sodium salt. The temperature of the salt bath is 150–550°C. The holding time is 0.01–2 hours. The cooling rate is 0.1–30°C / min.

7. The method of claim 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The steps between steps 3 and 4 do not contain Ag. + The ion salt bath, by mass percentage, comprises: 25-90% exchange material and 10-75% filling material, wherein the exchange material is sodium or potassium salt and the filling material is zinc salt and / or sodium salt and / or barium salt; the temperature of the salt bath is 175-450℃; the holding time is 0.02-1 hour; and the cooling rate is 0.5-20℃ / min.

8. The method of claim 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The steps between steps 3 and 4 do not contain Ag. + The ion salt bath, by mass percentage, contains 30-85% exchange material and 15-70% filling material, wherein the exchange material is potassium nitrate or sodium nitrate, and the filling material is zinc chloride, barium chloride, or barium nitrate; the temperature of the salt bath is 200-400℃; the holding time is 0.03-0.5 hours; and the cooling rate is 1-15℃ / min.

9. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 1 or 2, characterized in that, The melting temperature in step 1 is 1300–1600℃; the clarification temperature is 1350–1650℃, and the clarification time is 0.2–72 h.

10. The method of claim 1 or 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The melting temperature in step 1 is 1320–1580°C; the clarification temperature is 1380–1620°C, and the clarification time is 0.5–64 h.

11. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 1 or 2, characterized in that, The melting temperature in step 1 is 1340–1560°C; the clarification temperature is 1400–1600°C, and the clarification time is 1–48 hours.

12. The method of claim 1 or 2, wherein Step 3 contains Ag + The salt bath for ions contains, by mass percentage, 2-100% silver-containing raw material and 0-98% filler material, wherein the silver-containing raw material is silver chloride, silver nitrate, silver sulfate, or any mixture thereof; the filler material is potassium, barium, sodium, or magnesium nitrates or chlorides; the temperature of the salt bath is 280-400℃; the holding time is 1-720h; and the cooling rate is 0.1-20℃ / min.

13. The method of claim 1 or 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: Step 3 contains Ag + The ion salt bath, by mass percentage, contains 10-60% silver-containing raw material and 40-90% filler material, wherein the silver-containing raw material is a mixture of silver chloride and silver nitrate; the filler material is a mixture of potassium, sodium or barium, sodium nitrates; the temperature of the salt bath is 300-390℃; the holding time is 12-360h; and the cooling rate is 0.5-15℃ / min.

14. The method of claim 1 or 2, wherein Step 3 contains Ag + The salt bath for ions contains, by mass percentage, 20-50% silver-containing raw material and 50-80% filler material, wherein the silver-containing raw material is silver nitrate and the filler material is barium nitrate or sodium nitrate; the temperature of the salt bath is 320-380℃; the holding time is 24-240h; and the cooling rate is 1-10℃ / min.

15. The method of claim 1 or 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The temperature in step 4 is -40 to 250°C; the emission wavelength of the ultraviolet light source is 350 to 480 nm; the power density of the ultraviolet light source is 0.1 to 2 watts per square centimeter; and the time is 0.01 to 24 hours.

16. The method of claim 1 or 2, wherein The temperature in step 4 is 0–200°C; the emission wavelength of the ultraviolet light source is 350–460 nm; the power density of the ultraviolet light source is 0.2–1.5 W / cm²; and the time is 0.02–10 h.

17. The method of claim 1 or 2, wherein Step 4: The ultraviolet light source emits light with a wavelength of 365nm laser, 405nm laser, 450nm laser, or mercury lamp; the time is 0.1 to 2 hours.

18. The method of claim 1 or 2, wherein Step 5 describes the process of not containing Ag. + The ion salt bath, by mass percentage, comprises: 5-90% exchange raw material and 10-95% filling raw material; the exchange raw material is sodium salt, potassium salt, or a mixture of both; the filling raw material is zinc sulfate and / or barium chloride and / or zinc chloride and / or zinc nitrate and / or zinc metaphosphate; the temperature is 400-600℃; and the time is 0.1-72h.

19. The method of claim 1 or 2, wherein Step 5 describes the process of not containing Ag. + The ion salt bath comprises, by mass percentage, 15-85% exchange material and 15-85% filling material; the exchange material is potassium nitrate, sodium nitrate, or a mixture of both, and the filling material is barium chloride and / or zinc chloride; the temperature is 420-580℃; and the time is 0.5-48h.

20. The method of claim 1 or 2, wherein Step 5 describes the process of not containing Ag. + The ion salt bath, by mass percentage, comprises: 30-80% exchange material and 20-70% filling material; the exchange material is potassium nitrate or sodium nitrate, and the filling material is zinc chloride; the temperature is 440-560℃; and the time is 2-36 hours.

21. The method of claim 1 or 2, wherein The luminescent transparent glass has a moisture resistance of Class 2 or below; and / or an acid resistance of Class 4 or below; and / or λ 80 Below 460 nm; and / or fluorescence integral intensity greater than 5 × 10⁻⁶ 6 ; and / or the color coordinate range is within the range enclosed by (0.300, 0.400), (0.300, 0.300), (0.400, 0.400), (0.400, 0.300); and / or the luminous spatial resolution is less than 0.5 mm.

22. The method of claim 1 or 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The luminescent transparent glass has a moisture resistance of Class 1; and / or an acid resistance of Class 3 or below; and / or λ 80 The fluorescence intensity is below 440 nm; and / or the integrated fluorescence intensity is greater than 2 × 10⁻⁶. 7 ; and / or the color coordinates are within the range bounded by (0.320, 0.400), (0.310, 0.330), (0.380, 0.350), (0.390, 0.400); and / or the luminous spatial resolution is less than 0.1 mm.

23. The method of claim 1 or 2, wherein the high-precision spatially selective luminescent transparent glass is manufactured by the steps of: The luminescent transparent glass has an acid resistance stability of Class 2 or below; and / or λ 80 Below 430 nm; and / or with an integrated fluorescence intensity greater than 2.5 × 10⁻⁶. 7 ; and / or the color coordinate range is between (0.325, 0.395), (0.315, 0.330), (0.375, 0.340), (0.390, 0.395); and / or the luminous spatial resolution is below 0.05 mm.

24. The method of claim 1 or 2, wherein The composition of the base glass is expressed as a mole percentage, and the cations include: Mg 2+ : 0~7.5%; Al 3+ : 10~35%; B 3+ 3-20%; Si 4+ : 10~55%; P 5+ : 0~6%; Na + 5-40%; Zn 2+ : 0~5%; Ca 2+ : 0~5%; Sr 2+ : 0~10%; Ba 2+ :0~8%; La 3+ : 0~4%; Y 3+ : 0~5%; Zr 4+ : 0~3%; Yb 3+ : 0~10%; Nb 5+ +Ta 5+ +Gd 3+ : 0~5%; K + : 0~20%; Li + : 0~10%.

25. The method of claim 24, wherein the high-precision spatially selective luminescent transparent glass is manufactured by a method comprising: Its components are expressed as mole percentages, of which: Zn 2+ : 0–3%; and / or Mg 2+ : 0–5%; and / or Ca 2+ : 0–2%; and / or Sr 2 + : 0–5%; and / or Ba 2+ : 0–3%; and / or Al 3+ : 12–32%; and / or B 3+ : 2-18%; and / or La 3+ : 0~1%; and / or Y 3+ : 0–2%; and / or Zr 4+ : 0–2%; and / or Si 4+ : 15–52.5%; and / or P 5+ : 0.2–5%; and / or Yb 3+ : 0–5%; and / or Nb 5+ +Ta 5+ +Gd 3+ : 0–1%; and / or Na + : 10–35%; and / or K + : 0–15%; and / or Li + : 0-2%.

26. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 24, characterized in that, Its components are expressed as mole percentages, of which: Zn 2+ : 0–2.5%; and / or Mg 2+ : 0.5–2.5%; and / or: does not contain Ca 2+ ; and / or Sr 2+ : 0–2.5%; and / or Ba 2+ : 0–1%; and / or Al 3+ 15-30%; and / or B 3+ : 4–16%; and / or La 3+ : 0~0.5%; and / or Y 3+ : 0–1.5%; and / or Zr 4+ : 0~1%; and / or Si 4+ 20-50%; and / or P 5+ : 0.4–4%; and / or Yb 3+ : 0–2%; and / or: does not contain Nb 5+ +Ta 5+ +Gd 3+ ; and / or Na + : 15-30%; and / or K + : 0–12%; and / or Li + : 0~1%.

27. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 24, characterized in that, Its components are expressed as mole percentages, of which: (1.5×Li + +0.8×Na + +K + ) is 12-32%; and / or (Zn 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ ) is 0-10%; and / or (Na) + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ The range is 0.125 to 2.

333.

28. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 24, characterized in that, Its components are expressed as mole percentages, of which: (1.5×Li + +0.8×Na + +K + The percentages are 13-31%; and / or (Zn) 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ ) is 1-6%; and / or (Na) + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ It ranges from 0.5 to 2.

29. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 24, characterized in that, Its components are expressed as mole percentages, of which: (1.5×Li + +0.8×Na + +K + ) is 14-30%; and / or (Zn 2+ +Mg 2+ +Ca 2+ +Ba 2+ +Sr 2+ ) is 2-5%; and / or (Na) + +K + +Li + +Zn 2+ +1.5×Mg 2+ +Ca 2+ +2×Ba 2+ +Sr 2+ -Al 3+ ) / B 3+ The range is 0.875 to 1.

667.

30. The method for manufacturing high-precision spatially selective luminescent transparent glass according to claim 24, characterized in that, The components are expressed in mole percent, the anion contains O 2- : 100%.

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