A Ca 1.46 Ti 1.38 Nb 1.11 O7 crystal phase transparent glass-ceramics and method of making and transparent luminescent materials

Abstract

The application relates to the technical field of transparent glass ceramic preparation, in particular to a Ca 1.46 Ti 1.38 Nb 1.11 O7 crystal phase transparent glass ceramic and a preparation method and a transparent luminescent material 1.46 Ti 1.38 Nb 1.11 O7 crystal phase transparent glass ceramic is prepared by taking calcium salt, Na salt, B source and Nb, Ti and Sb oxides as raw materials, heating the raw materials to be molten into a liquid state, performing annealing treatment after solidification forming to obtain transparent glass; the transparent glass is subjected to crystallization at 600-640 DEG C and is kept for 1-2 hours to generate Ca 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, and Ca 1.46 Ti 1.38 Nb 1.11 O7 crystal phase transparent glass ceramic is obtained. By adjusting the raw material composition and the crystallization temperature, a specific crystal phase and a crystal field environment can be formed, which can provide a doping site for rare earth ions and is beneficial to improving the luminescent intensity after doping.

Description

Technical Field

[0001] This invention relates to the field of rare earth luminescent materials technology, specifically to a Ca-containing... 1.46 Ti 1.38 Nb 1.11 O7 crystalline phase transparent glass ceramics, preparation methods, and transparent luminescent materials. Background Technology

[0002] White light-emitting diodes, or white LEDs for short, have been used as a new material to replace traditional light sources due to their advantages such as high brightness, fast response, long lifespan, low power consumption, and shock resistance. Currently, there are three main methods to achieve white LEDs, the most widely used being the use of blue LED chips to excite yellow phosphors to generate white light. However, this method has significant drawbacks. Due to the lack of sufficient red light components, the emitted white light is a "cold white light," which has poor visual effects in some applications and fails to meet usage requirements. Furthermore, compared to current near-ultraviolet excited blue and green light-emitting materials, the luminous efficiency of red light-emitting materials remains very low. These are key issues restricting further improvements in the performance of white LEDs. Therefore, researching and developing stable, efficient, and low-light-decay red light-emitting materials that can be effectively excited by near-ultraviolet and blue light has significant academic and application value.

[0003] Red luminescent materials typically use rare-earth ions as luminescent centers, achieving high-efficiency luminescence by doping them into a transparent matrix. Among these, red transparent luminescent materials based on transparent glass-ceramics are an important research topic. Transparent glass-ceramics are composite materials where crystalline and glassy phases coexist. Under precisely controlled heat treatment regimes, the nucleation and growth of microcrystals can be accurately controlled, providing an effective way to optimize material properties. Transparent glass-ceramics not only retain the high light transmittance of glass but also possess the ordered structure of a crystal structure, significantly optimizing the luminescent behavior of rare-earth ions. This makes them an ideal matrix for the efficient luminescence of rare-earth ions, with applications in lighting, displays, and anti-counterfeiting.

[0004] However, with increasing crystallinity, grain size often becomes difficult to control, easily leading to abnormal growth or even agglomeration. When the grain size is close to or larger than the visible light wavelength of 400nm to 760nm, strong Rayleigh scattering will occur at the interface between the grain and the glass phase. At this time, the incident light cannot penetrate the material and is scattered as diffuse reflection, causing the transparency of the glass ceramic to decrease sharply or even completely lose its light transmittance, which will seriously affect its optical properties. Summary of the Invention

[0005] To address the problem of abnormal grain growth leading to a significant decrease in the transparency of glass-ceramics, thereby affecting their optical properties, this invention provides a Ca-containing... 1.46 Ti 1.38Nb 1.11 O7 crystalline phase transparent glass ceramics, preparation methods, and transparent luminescent materials.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] This invention provides a Ca-containing 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass ceramic includes the following steps:

[0008] Using calcium salts, sodium salts, boron sources, and oxides of Nb, Ti, and Sb as raw materials, the raw materials are heated to a molten liquid state, solidified, and then annealed to obtain transparent glass. The transparent glass is then subjected to crystallization at 600℃~640℃ for 1h~2h to generate Ca. 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, yielding Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0009] This invention primarily involves adjusting the raw material composition to include calcium salts, Na salts, a B source, and oxides of Nb, Ti, and Sb. After molding, transparent glass is prepared through annealing. Furthermore, by controlling the crystallization temperature, Ca is obtained. 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase, obtained by crystallization, can provide doping sites for rare earth ions, which is beneficial to improving the luminescence intensity of doped rare earth ions.

[0010] In this invention, the control of the crystallization temperature has a relatively large impact on the performance of the prepared transparent glass-ceramic material. If the crystallization temperature is too high, the resulting grains will be too large, affecting the transmittance of the transparent glass-ceramic material. The transparent glass-ceramic material prepared in this application needs to meet appropriate transparency requirements. Since the goal is to produce red light, which is a type of visible light, if the grains are too large, red light will be reflected, weakening the transmittance of red light and ultimately affecting the luminescence intensity after doping.

[0011] Preferably, the Ca-containing component, in molar percentage, 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass ceramic is made from the following raw materials:

[0012] Calcium salt 15%–16%, Nb oxide 7%–9%, ​​Ti oxide 22%–24%, B source 38%–40%, Na salt 14%–16%, and Sb oxide 0.2%–0.5%; total 100%.

[0013] More preferably, the Ca-containing component, in molar percentage, 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass ceramic is made from the following raw materials:

[0014] Calcium salt 15.7%, Nb oxide 7.9%, Ti oxide 23.1%, B source 38.4%, Na salt 14.7% and Sb oxide 0.2%; total 100%.

[0015] This invention optimizes the raw material ratio to prevent defects, increase the speed of glass melting and preparation, and meet glass quality requirements. The molar percentage of each raw material is adjusted to regulate the synthesis of glass containing Ca. 1.46 Ti 1.38 Nb 1.11 O7 phase transparent glass-ceramic material.

[0016] Preferably, the calcium salt is CaCO3; the Nb oxide is Nb2O5; the Ti oxide is TiO2; the B source is H3BO3; the Na salt is Na2CO3; and the Sb oxide is Sb2O3.

[0017] The present invention mainly determines the crystal phase composition by comparing standard cards, and the crystal field environment is conducive to increasing the probability of rare earth ion doping, thereby improving the luminescence intensity.

[0018] Preferably, the specific operation of heating the raw material to a molten liquid state is as follows:

[0019] The raw materials are heated to 900℃~1100℃ and held for 1h~2h to allow a solid-phase reaction to occur; then the temperature is further increased to 1350℃~1400℃ and held for 1h~2h to melt the raw materials into a liquid state.

[0020] In this invention, the uniformly mixed raw materials are heated to 900℃~1100℃. At this temperature, a series of physical and chemical changes occur in the components of the powder, the main solid-phase reaction in the powder is completed, and a large amount of gaseous substances are generated. This temperature is maintained for 1h~2h to ensure that the gas can escape and reduce defects. Then, the temperature is further increased to 1350℃~1400℃ to melt the raw materials into a liquid state, obtaining molten glass. This temperature is maintained for 1h~2h. When the molten glass is kept at a high temperature for a long time, due to the thermal motion and mutual diffusion of the molten glass, the streaks gradually disappear, and the chemical composition and refractive index of the molten glass gradually become consistent, ensuring that the mixture of multiple solid phases is transformed into a uniform molten glass.

[0021] Preferably, the annealing temperature is 400℃~450℃ and the annealing time is 1h~3h.

[0022] Preferably, the crystallization temperature is 600℃~640℃ and the crystallization time is 1h~2h.

[0023] In this invention, the Ca-containing 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass ceramic includes the following steps:

[0024] Weigh out each raw material according to the following molar percentages: calcium salt 15%–16%, Nb₂O₅ 7%–9%, ​​TiO₂ 22%–24%, B source 38%–40%, Na salt 14%–16%, and Sb₂O₃ 0.2%–0.5%.

[0025] All raw materials are thoroughly mixed and placed in a corundum crucible. The crucible is then placed in a silicon-molybdenum furnace and heated to 900℃–1100℃, held at this temperature for 1–2 hours, and then further heated to 1350℃–1400℃ and held at this temperature for another 1–2 hours to melt the raw materials into a liquid state, yielding molten glass. The molten glass is poured onto a preheated stainless steel mold (200℃) to solidify and is then quickly placed in a muffle furnace at 400℃–450℃ for annealing. After holding at this temperature for 1–3 hours, the mixture is cooled to room temperature with the furnace to obtain transparent glass.

[0026] Transparent glass is placed in a box-type resistance furnace, and a one-step crystallization method is used. The temperature is increased to 600℃~640℃ at a heating rate of 5℃ / min, and held for 1h~2h to produce Ca. 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, yielding Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic; used as a rare earth ion-doped luminescent matrix.

[0027] The second aspect of the present invention provides a Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic, using the Ca-containing material described in the first aspect. 1.46 Ti 1.38 Nb 1.11 O7 crystalline phase transparent glass-ceramic was prepared by a specific method.

[0028] A third aspect of the present invention provides a transparent luminescent material, wherein the transparent luminescent material is a Ca-containing material as described in the second aspect. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic is used as the luminescent matrix, and rare earth oxides are used as the doping ion source. This is achieved by doping rare earth oxides into Ca-containing... 1.46 Ti 1.38 Nb 1.11It is prepared from O7 crystalline phase transparent glass ceramics.

[0029] This invention controls the composition and content of raw materials, as well as the crystallization temperature, to grow a specific crystal phase on transparent glass, forming a crystal field environment and improving the luminescence intensity of doped rare earth ions.

[0030] Preferably, the transparent luminescent material is prepared by the following method:

[0031] Using rare earth oxides, calcium salts, sodium salts, boron sources, and oxides of Nb, Ti, and Sb as raw materials, the raw materials are heated to a molten liquid state, solidified, and then annealed to obtain transparent glass. The transparent glass is then subjected to crystallization at 600℃~640℃ for 1h~2h to generate Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase forms a crystal field environment, resulting in a Ca-containing crystal. 1.46 Ti 1.38 Nb 1.11 O7 phase transparent luminescent material.

[0032] Preferably, the transparent luminescent material is prepared from the following raw materials by mole percentage:

[0033] The composition is as follows: calcium salt 15%–16%, Nb oxide 7%–9%, ​​Ti oxide 22%–24%, B source 38%–40%, Na salt 14%–16%, Sb oxide 0.2%–0.5%, and rare earth oxide 0.2%–0.5%; totaling 100%. Among these, the calcium salt is CaCO3; the Nb oxide is Nb2O5; the Ti oxide is TiO2; the B source is H3BO3; the Na salt is Na2CO3; the Sb oxide is Sb2O3; and the rare earth oxide is Eu2O3.

[0034] More preferably, the transparent luminescent material is made from the following raw materials by mole percentage:

[0035] Calcium salt 15.7%, Nb2O 57.9%, TiO2 23.1%, B source 38.2%, Na salt 14.7%, Sb2O 30.2% and rare earth oxides 0.2%; total 100%.

[0036] This invention involves doping rare earth oxides with Ca... 1.46 Ti 1.38 Nb 1.11 A transparent luminescent material is prepared from O7 crystalline phase transparent glass-ceramic. The preparation method of the transparent luminescent material includes the following steps:

[0037] Weigh out each raw material according to the following molar percentages: calcium salt 15%–16%, Nb₂O₅ 7%–9%, ​​TiO₂ 22%–24%, B source 38%–40%, Na salt 14%–16%, Sb₂O₃ 0.2%–0.5%, and rare earth oxides 0.2%–0.5%.

[0038] All raw materials are thoroughly mixed and placed in a corundum crucible. The crucible is then placed in a silicon-molybdenum furnace and heated to 900℃–1100℃, held at this temperature for 1–2 hours, and then further heated to 1350℃–1400℃ and held at this temperature for another 1–2 hours to melt the raw materials into a liquid state, yielding molten glass. The molten glass is poured onto a preheated stainless steel mold (200℃) to solidify and is then quickly placed in a muffle furnace at 400℃–450℃ for annealing. After holding at this temperature for 1–3 hours, the mixture is cooled to room temperature with the furnace to obtain transparent glass.

[0039] Transparent glass is placed in a box-type resistance furnace, and a one-step crystallization method is used. The temperature is increased to 600℃~640℃ at a heating rate of 5℃ / min, and held for 1h~2h to produce Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase forms a crystal field environment, yielding Eu. 3+ Doping with Ca 1.46 Ti 1.38 Nb 1.11 A transparent luminescent material of O7 crystalline transparent glass-ceramic was obtained. The resulting transparent luminescent material was cut, and then double-sided grinding and polishing were performed using a grinding and polishing machine to finally obtain a transparent luminescent material with a thickness of 1 mm.

[0040] The beneficial effects of this invention are:

[0041] 1. This invention mainly involves adjusting the raw material composition to include calcium salts, Na salts, B sources, and oxides of Nb, Ti, and Sb. After molding, transparent glass is prepared by annealing, and the crystallization temperature is controlled to precipitate Ca. 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, and Ca obtained by crystallization 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase can provide doping sites for rare earth ions, which is beneficial to improving the luminescence intensity of doped rare earth ions.

[0042] 2. The transparent glass-ceramic material of the present invention can serve as a luminescent matrix, through the formation of Ca... 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase and crystal field environment enhance the luminescence intensity after doping and have a significant effect on luminescence performance.

[0043] 3. The preparation of the transparent glass-ceramic material of the present invention requires a relatively short heat treatment time, which can effectively shorten the production cycle of the sample. Attached Figure Description

[0044] Figure 1 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 X-ray diffraction pattern of O7 crystalline transparent glass-ceramic sample

[0045] Figure 2 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 Ca in O7 crystalline transparent glass-ceramic sample 1.46 Ti 1.38 Nb 1.11 Crystal structure diagram of the O7 phase.

[0046] Figure 3 Eu prepared in Example 7 3+ Doped transparent luminescent material and Ca from Example 1 1.46 Ti 1.38 Nb 1.11 Emission spectrum of O7 crystalline transparent glass-ceramic.

[0047] Figure 4 Eu prepared in Example 7 3+ Color coordinates of doped transparent luminescent materials.

[0048] Figure 5 For Example 1, Ca-containing 1.46 Ti 1.38 Nb 1.11 Scanning electron microscope image of an O7 crystalline phase transparent glass-ceramic sample.

[0049] Figure 6 For example 5, the Ca-containing 1.46 Ti 1.38 Nb 1.11 Scanning electron microscope image of an O7 crystalline phase transparent glass-ceramic sample. Detailed Implementation

[0050] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0051] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0052] Transparent glass-ceramics are composite materials in which crystalline and glassy phases coexist. Under precisely controlled heat treatment regimes, the nucleation and growth of microcrystals can be precisely controlled. Rare-earth pyrochlore-type materials possess excellent optical properties, high thermal and chemical stability, low cost, low phonon energy, and high melting point, making them widely applicable in the field of luminescent materials.

[0053] In rare earth pyrochlore-type materials, the pyrochlore structure is a crystal structure composed of oxides with the chemical formula A2B2O7. The A site is usually a rare earth ion with a large radius, and the B site is a high-valence cation with a small radius.

[0054] This invention aims to prepare a Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass ceramics and transparent luminescent materials prepared by doping rare earth oxides with O7 as the luminescent matrix.

[0055] In this invention, Ca is contained 1.46 Ti 1.38 Nb 1.11 The glass matrix composition of the O7 crystalline transparent glass-ceramic is Na2CO3-CaCO3-Nb2O5-TiO2-H3BO3-Sb2O3. The Ca-containing... 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramics can be used as rare earth ion-doped luminescent substrates, exhibiting excellent luminescent properties.

[0056] In Ca 1.46 Ti 1.38 Nb 1.11 In the O7 crystal phase, Ca 2+ The ion occupies the A site, Nb 5+ Ion-substituted Ti 4+ The ion occupies the B site, and the A site contains a divalent alkaline earth cation Ca. 2+ With B position Nb 5+ The formation of ions balances the charge, maintains lattice neutrality, and suppresses the formation of impurity phases, ensuring the formation of a single pyrochlore crystal phase. Furthermore, the A and B sites in the crystal phase are occupied by different metal cations, which gives the pyrochlore structure material a wide range of adjustment possibilities in its applications, providing doping sites for rare earth ions and improving their luminescence intensity. Therefore, the Ca-containing material prepared in this invention... 1.46 Ti 1.38 Nb 1.11O7 crystal phase, transparent glass ceramic with glass matrix composition of Na2CO3-CaCO3-Nb2O5-TiO2-H3BO3-Sb2O3 can serve as a luminescent matrix, which is of great significance for the preparation of transparent luminescent materials by rare earth ion doping.

[0057] The technical solution of the present invention will be further described below through specific embodiments.

[0058] In the following embodiments, unless otherwise specified, the methods described are conventional methods; and unless otherwise specified, the reagents and materials described are commercially available.

[0059] Example 1

[0060] A type containing Ca 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass ceramic includes the following steps:

[0061] The components are weighed in the following proportions according to the molar percentage: CaCO3 15.7%, Nb2O 57.9%, TiO2 23.1%, H3BO3 38.4%, Na2CO3 14.7%, and Sb2O3 0.2%; total 100%.

[0062] Using CaCO3, Nb2O5, TiO2, H3BO3, Na2CO3, and Sb2O3 as raw materials, 50 grams of the raw materials were weighed out and thoroughly mixed. The mixture was placed in a corundum crucible and then placed in a silicon-molybdenum furnace. The temperature was raised to 1100℃ and held for 1 hour. The temperature was then further raised to 1400℃ and held for another hour to melt the raw materials into a liquid state, yielding molten glass. The molten glass was poured into a preheated stainless steel mold (200℃) to solidify and shape. It was then quickly placed in a muffle furnace at 450℃ for annealing and held for 2 hours to produce Ca2+. 1.46 Ti 1.38 Nb 1.11 O7 crystalline phase was cooled to room temperature in the furnace to obtain a transparent glass sample. The transparent glass sample was then placed in a box furnace and subjected to a one-step crystallization method, with the temperature increased to 610°C at a heating rate of 5°C / min, held at that temperature for 2 hours, and then cooled to room temperature in the furnace to obtain a Ca-containing sample. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0063] The obtained Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramics are cut using a cutting machine, then ground and polished to finally obtain Ca-containing... 1.46 Ti 1.38 Nb 1.11O7 crystalline phase transparent glass-ceramic sample. Example 1, containing Ca. 1.46 Ti 1.38 Nb 1.11 The thickness of the O7 crystalline phase transparent glass-ceramic sample is 1 mm.

[0064] The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 X-ray diffraction analysis was performed on the O7 crystalline phase transparent glass-ceramic sample to determine the Ca content. 1.46 Ti 1.38 Nb 1.11 The crystal phase of the O7 crystalline transparent glass-ceramic sample is shown in the following results. Figure 1 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 The crystal structure diagram of the O7 crystalline phase transparent glass-ceramic sample was obtained using Diamond software, as shown below. Figure 2 .

[0065] Figure 1 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 X-ray diffraction pattern of O7 crystalline phase transparent glass-ceramic sample. Ca 1.46 Ti 1.38 Nb 1.11 The standard card for the O7 crystal phase is JCPDS#97-024-5806.

[0066] like Figure 1 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 A comparison of the X-ray diffraction pattern of the O7 crystalline transparent glass-ceramic sample with the standard card revealed that the Ca-containing sample obtained in Example 1... 1.46 Ti 1.38 Nb 1.11 In the O7 crystalline transparent glass-ceramic sample, the crystalline phase precipitated in the glass matrix is ​​Ca. 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, indicating that the Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 Successful preparation of O7 crystalline phase transparent glass-ceramic samples.

[0067] Figure 2 The Ca-containing sample obtained in Example 1 1.46 Ti 1.38 Nb 1.11 Ca in O7 crystalline transparent glass-ceramic sample 1.46Ti 1.38 Nb 1.11 Crystal structure diagram of the O7 phase. The gray spheres represent Ca. 2+ The cyan spheres represent Ti. 4+ The blue spheres represent Nb / Ti, and the red spheres represent O. 2- Nb and Ti can appear in the same location in the crystal.

[0068] Depend on Figure 2 It can be seen that Ca 1.46 Ti 1.38 Nb 1.11 O7 crystal space group is Fd3m (no. 227), with a unit cell parameter of a = 10.2301 Å. Each unit cell contains 8 molecules, i.e., Z = 8, and the unit cell volume is 1070.6 Å. 3 .

[0069] Example 2

[0070] A type containing Ca 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass-ceramics differs from that in Example 1 in that it involves the preparation of Ca-containing... 1.46 Ti 1.38 Nb 1.11 The raw material ratios for O7 crystalline transparent glass ceramics vary. See Table 1 for details.

[0071] Table 1 Raw Material Composition

[0072]

[0073] Note: A1 refers to the raw material composition of Example 1.

[0074] The Ca-containing materials prepared in Examples 1 and 2 of this invention 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic sample contains Ca 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase can be used as a luminescent matrix for rare-earth ion doping to prepare transparent luminescent materials, and has the advantages of simple preparation conditions, low phonon energy, and structural stability. Therefore, the pyrochlore-containing Ca-type materials obtained in the embodiments of this invention... 1.46 Ti 1.38 Nb 1.11 Transparent glass-ceramic samples with the O7 crystal phase have potential applications in transparent luminescent materials.

[0075] Example 3

[0076] A type containing Ca1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass-ceramic differs from that in Example 1 in that the crystallization temperature is 600℃ and the crystallization time is 2 hours. Specifically:

[0077] A transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, heating to 600°C at a rate of 5°C / min and holding for 2 hours. The sample was then cooled to room temperature with the furnace to obtain a Ca-containing sample. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0078] Example 4

[0079] A type containing Ca 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass-ceramic differs from that in Example 1 in that the crystallization temperature is 640℃ and the crystallization time is 1 hour. Specifically:

[0080] A transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, heating to 640°C at a rate of 5°C / min, holding at that temperature for 1 hour, and then cooling to room temperature with the furnace to obtain a Ca-containing sample. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0081] Example 5

[0082] A type containing Ca 1.46 Ti 1.38 Nb 1.11 The preparation method of O7 crystalline transparent glass-ceramic differs from that in Example 1 in that the crystallization temperature is 640℃ and the crystallization time is 2 hours. Specifically:

[0083] A transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, with the temperature increased to 640°C at a rate of 5°C / min and held for 2 hours. The sample was then cooled to room temperature with the furnace to obtain a Ca-containing sample. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0084] When containing Ca 1.46 Ti 1.38 Nb 1.11 When the transmittance of O7 crystalline phase transparent glass-ceramic samples is low, the light emitted from the luminescent center will be largely absorbed or scattered by the material. To ensure high transmittance of the samples, the grain size is strictly controlled by adjusting the heat treatment temperature and time.

[0085] For the Ca-containing samples of Examples 1, 3, 4, and 5 1.46 Ti 1.38 Nb 1.11 Scanning electron microscopy analysis was performed on the O7 crystalline phase transparent glass-ceramic sample.

[0086] Figure 5 For Example 1, Ca-containing 1.46 Ti 1.38 Nb 1.11 Scanning electron microscope image of an O7 crystalline phase transparent glass-ceramic sample. Figure 6 For example 5, the Ca-containing 1.46 Ti 1.38 Nb 1.11 Scanning electron microscope image of an O7 crystalline phase transparent glass-ceramic sample.

[0087] Figure 5 The Ca-containing 1.46 Ti 1.38 Nb 1.11 The heat treatment conditions for the O7 crystalline phase transparent glass-ceramic sample were: 610℃ for 2 hours. Figure 5 The scanning electron microscope images show that the grains are uniformly distributed and the grain size is around 150 nm. Figure 6 The Ca-containing 1.46 Ti 1.38 Nb 1.11 The heat treatment conditions for the O7 crystalline phase transparent glass-ceramic sample were: 640℃ for 2 hours. Figure 6 The scanning electron microscope images show that the grain size is around 400 nm, and some grains show agglomeration.

[0088] Table 2 Grain growth under different heat treatment conditions

[0089]

[0090] Compare Figure 5 and Figure 6 Scanning electron microscope images revealed that when the heat treatment temperature was 640℃, the grain size was significantly larger, approaching or exceeding 400nm, which enhanced the scattering of light and thus affected the luminescence intensity.

[0091] Ca-containing samples obtained under different heat treatment conditions 1.46 Ti 1.38 Nb 1.11 The grain growth of the O7 crystalline phase transparent glass-ceramic sample is shown in Table 2. When Ca is present... 1.46 Ti 1.38 Nb 1.11When the crystallization temperature of the O7 crystalline phase transparent glass-ceramic sample is between 600℃ and 640℃, and the crystallization time is between 1h and 2h, the grain size is much smaller than 400nm, and the Ca obtained from the crystallization... 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase has a uniform grain distribution and meets the appropriate transparency requirements, which can provide doping sites for rare earth ions and is beneficial to improving the luminescence intensity of doped rare earth ions.

[0092] Example 7

[0093] A transparent luminescent material, comprising the Ca-containing material described in Example 1. 1.46 Ti 1.38 Nb 1.11 Using O7 crystalline transparent glass-ceramic as the luminescent matrix and Eu2O3 as the doping ion source, Eu2O3 is doped into Ca-containing... 1.46 Ti 1.38 Nb 1.11 It is prepared from O7 crystalline phase transparent glass ceramics.

[0094] The preparation method of transparent luminescent materials includes the following steps:

[0095] The components are weighed in the following proportions according to the molar percentage: CaCO3 15.7%, Nb2O 57.9%, TiO2 23.1%, H3BO3 38.2%, Na2CO3 14.7%, Sb2O3 0.2% and Eu2O3 0.2%; total 100%.

[0096] Using CaCO3, Nb2O5, TiO2, H3BO3, Na2CO3, Sb2O3, and Eu2O3 as raw materials, 50 grams of the raw materials were weighed out and thoroughly mixed. The mixture was placed in a corundum crucible and then placed in a silicon-molybdenum furnace. The temperature was raised to 1100℃ and held for 1 hour. The temperature was then further raised to 1400℃ and held for another hour to melt the raw materials into a liquid state, yielding molten glass. The molten glass was poured into a preheated stainless steel mold (200℃) to solidify and shape. It was then quickly placed in a muffle furnace at 450℃ for annealing and held for 2 hours. Afterward, the furnace was cooled to room temperature to obtain Eu2O3. 3+ Doped transparent glass samples; Eu 3+ The doped transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, heating to 610°C at a rate of 5°C / min and holding for 2 hours to produce Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystalline phase forms a crystal field environment, which is then cooled to room temperature in the furnace to obtain Eu. 3+ Doped transparent luminescent materials.

[0097] The obtained Eu 3+The doped transparent luminescent material was cut using a cutting machine, then ground and polished to obtain a transparent luminescent material sample. The thickness of the transparent luminescent material sample obtained in Example 7 was 1 mm.

[0098] Example 8

[0099] A transparent luminescent material, comprising the Ca-containing material described in Example 3. 1.46 Ti 1.38 Nb 1.11 Using O7 crystalline transparent glass-ceramic as the luminescent matrix and Eu2O3 as the doping ion source, Eu2O3 is doped into Ca-containing... 1.46 Ti 1.38 Nb 1.11 It is prepared from O7 crystalline phase transparent glass ceramics.

[0100] The preparation method of transparent luminescent materials includes the following steps:

[0101] The components are weighed in the following proportions according to the molar percentage: CaCO3 15.7%, Nb2O 57.9%, TiO2 23.1%, H3BO3 38.2%, Na2CO3 14.7%, Sb2O3 0.2% and Eu2O3 0.2%; total 100%.

[0102] Using CaCO3, Nb2O5, TiO2, H3BO3, Na2CO3, Sb2O3, and Eu2O3 as raw materials, 50 grams of the raw materials were weighed out and thoroughly mixed. The mixture was placed in a corundum crucible and then placed in a silicon-molybdenum furnace. The temperature was raised to 900℃ and held for 2 hours. The temperature was then further raised to 1350℃ and held for 2 hours to melt the raw materials into a liquid state, yielding molten glass. The molten glass was poured into a preheated stainless steel mold at 200℃ to solidify and shape. It was then quickly placed in a muffle furnace at 400℃ for annealing and held for 3 hours. Afterward, the furnace was cooled to room temperature to obtain Eu2O3. 3+ Doped transparent glass samples; Eu 3+ The doped transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, heating to 600°C at a rate of 5°C / min and holding for 2 hours to produce Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystalline phase forms a crystal field environment, which is then cooled to room temperature in the furnace to obtain Eu. 3+ Doped transparent luminescent materials.

[0103] The obtained Eu 3+ The doped transparent luminescent material was cut using a cutting machine, then ground and polished to obtain a transparent luminescent material sample. The thickness of the transparent luminescent material sample obtained in Example 8 was 1 mm.

[0104] Example 9

[0105] A transparent luminescent material, comprising the Ca-containing material described in Example 4. 1.46 Ti 1.38 Nb 1.11 Using O7 crystalline transparent glass-ceramic as the luminescent matrix and Eu2O3 as the doping ion source, Eu2O3 is doped into Ca-containing... 1.46 Ti 1.38 Nb 1.11 It is prepared from O7 crystalline phase transparent glass ceramics.

[0106] The preparation method of transparent luminescent materials includes the following steps:

[0107] The components are weighed in the following proportions according to the molar percentage: CaCO3 15.7%, Nb2O 57.9%, TiO2 23.1%, H3BO3 38.2%, Na2CO3 14.7%, Sb2O3 0.2% and Eu2O3 0.2%; total 100%.

[0108] Using CaCO3, Nb2O5, TiO2, H3BO3, Na2CO3, Sb2O3, and Eu2O3 as raw materials, 50 grams of the raw materials were weighed out and thoroughly mixed. The mixture was placed in a corundum crucible and then placed in a silicon-molybdenum furnace. The temperature was raised to 1000℃ and held for 1.5 hours. The temperature was then further raised to 1400℃ and held for another 1.5 hours to melt the raw materials into a liquid state, yielding molten glass. The molten glass was poured into a preheated stainless steel mold (200℃) to solidify and shape. It was then quickly placed in a muffle furnace at 450℃ for annealing and held for 2 hours. Afterward, the furnace was cooled to room temperature to obtain Eu2O3. 3+ Doped transparent glass samples; Eu 3+ The doped transparent glass sample was placed in a box furnace and subjected to a one-step crystallization method, heating to 640°C at a rate of 5°C / min and holding for 1 hour to produce Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystalline phase forms a crystal field environment, which is then cooled to room temperature in the furnace to obtain Eu. 3+ Doped transparent luminescent materials.

[0109] The obtained Eu 3+ The doped transparent luminescent material was cut using a cutting machine, then ground and polished to obtain a transparent luminescent material sample. The thickness of the transparent luminescent material sample obtained in Example 9 was 1 mm.

[0110] The following measurements were taken using a fluorescence spectrometer to measure the Eu2O3-doped Ca in the above-mentioned embodiments. 1.46 Ti 1.38 Nb 1.11 Eu prepared from O7 crystalline transparent glass-ceramics 3+The emission spectrum of the doped transparent luminescent material, with an excitation wavelength of 395 nm.

[0111] Figure 3 Eu prepared in Example 7 3+ Doped transparent luminescent material and Ca from Example 1 1.46 Ti 1.38 Nb 1.11 Emission spectrum of O7 crystalline transparent glass-ceramic.

[0112] Depend on Figure 3 It can be seen that the Eu prepared in Example 7 3+ The emission spectrum of the doped transparent luminescent material has three emission peaks at 579 nm, 591 nm, and 615 nm, corresponding to Eu, respectively. 3+ ion 5 D0→ 7 F0、 5 D0→ 7 F1 5 D0→ 7 Electron radiative transition to the F2 energy level. Comparatively, Eu prepared in Example 7... 3+ Doped transparent luminescent material and Ca from Example 1 1.46 Ti 1.38 Nb 1.11 The emission spectrum of O7 crystalline transparent glass ceramics shows that the Eu prepared in Example 7... 3+ The luminescence intensity of the doped transparent luminescent material is significantly higher than that of the Ca in Example 1. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic.

[0113] By comparing Eu prepared under different heat treatment regimes 3+ The emission spectrum of the doped transparent luminescent material showed that when the crystallization temperature was >640℃, the grain size was close to 400nm, which enhanced the scattering of light and resulted in a lower luminescence intensity.

[0114] When the crystallization temperature is between 600℃ and 640℃ and the crystallization time is between 1h and 2h, the grain size is much smaller than 400nm, and the Ca obtained from crystallization... 1.46 Ti 1.38 Nb 1.11 O7 crystalline phase, with uniform grain distribution. Similar to Eu, which has a crystallization temperature >640℃. 3+ Compared with doped transparent luminescent materials, the luminescence intensity is significantly and effectively improved.

[0115] In Example 7, Eu2O3 was used to dope Ca. 1.46 Ti 1.38 Nb 1.11Eu prepared from O7 crystalline transparent glass-ceramics 3+ The color coordinates were calculated from the emission spectrum data of the doped transparent luminescent material, and the results are as follows: Figure 4 As shown.

[0116] Figure 4 Eu prepared in Example 7 3+ Color coordinates of doped transparent luminescent materials.

[0117] Depend on Figure 4 The results show that the Eu prepared in Example 7 3+ The color coordinates of the doped transparent luminescent material are (0.5285, 0.3371), which are located in the red light region.

[0118] In summary, the analysis shows that, compared with Ca before doping... 1.46 Ti 1.38 Nb 1.11 Compared to O7 crystalline transparent glass-ceramics, the Eu of the embodiments of the present invention 3+ The luminescence intensity of doped transparent luminescent materials is significantly enhanced. In this embodiment of the invention, Ca is used. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic serves as the luminescent matrix, which is compatible with the crystal growth environment and provides doping sites for rare earth ions, thus improving the luminescence intensity of rare earth ions.

[0119] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A substance containing Ca 1.46 Ti 1.38 Nb 1.11 The method for preparing O7 crystalline phase transparent glass-ceramics is characterized by, Includes the following steps: Using calcium salts, sodium salts, boron sources, and oxides of Nb, Ti, and Sb as raw materials, the raw materials are heated to melt into a liquid state, solidified, and then annealed to obtain transparent glass. Transparent glass was subjected to crystallization at 600℃~640℃ for 1h~2h to produce Ca. 1.46 Ti 1.38 Nb 1.11 O7 crystal phase, yielding Ca-containing 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramics; The procedure for heating the raw materials to a molten, liquid state is as follows: The raw materials are heated to 900℃~1100℃ and held for 1h~2h to allow a solid-phase reaction to occur; then the temperature is further increased to 1350℃~1400℃ and held for 1h~2h to melt the raw materials into a liquid state. The Ca-containing content, expressed as a molar percentage, is... 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass ceramic is made from the following raw materials: Calcium salt 15%–16%, Nb oxide 7%–9%, ​​Ti oxide 22%–24%, B source 38%–40%, Na salt 14%–16%, and Sb oxide 0.2%–0.5%; total 100%; The calcium salt is CaCO3; the oxide of Nb is Nb2O5; the oxide of Ti is TiO2; the source of B is H3BO3; the sodium salt is Na2CO3; and the oxide of Sb is Sb2O3.

2. The Ca-containing [material] according to claim 1 1.46 Ti 1.38 Nb 1.11 The method for preparing O7 crystalline phase transparent glass-ceramics is characterized by, The Ca-containing content, expressed as a molar percentage, is... 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass ceramic is made from the following raw materials: Calcium salt 15.7%, Nb oxide 7.9%, Ti oxide 23.1%, B source 38.4%, Na salt 14.7% and Sb oxide 0.2%; total 100%.

3. The Ca-containing [material] according to claim 1 1.46 Ti 1.38 Nb 1.11 The method for preparing O7 crystalline phase transparent glass-ceramics is characterized by, The annealing temperature is 400℃~450℃, and the annealing time is 1h~3h.

4. A substance containing Ca 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic, characterized in that... The Ca-containing compound as described in any one of claims 1 to 3 1.46 Ti 1.38 Nb 1.11 O7 crystalline phase transparent glass-ceramic was prepared by a specific method.

5. A transparent luminescent material, characterized in that, The transparent luminescent material is the Ca-containing material as described in claim 4. 1.46 Ti 1.38 Nb 1.11 O7 crystalline transparent glass-ceramic is used as the luminescent matrix, and rare earth oxides are used as the doping ion source. This is achieved by doping rare earth oxides into Ca-containing... 1.46 Ti 1.38 Nb 1.11 It is prepared from O7 crystalline phase transparent glass ceramics.

6. The transparent luminescent material according to claim 5, characterized in that, The transparent luminescent material is prepared by the following method: Using rare earth oxides, calcium salts, Na salts, B sources, and oxides of Nb, Ti, and Sb as raw materials, the raw materials are heated to melt into a liquid state, solidified and shaped, and then annealed to obtain transparent glass. Transparent glass was subjected to crystallization at 600℃~640℃ for 1h~2h to produce Ca. 1.46 Ti 1.38 Nb 1.11 The O7 crystal phase forms a crystal field environment, resulting in a Ca-containing crystal. 1.46 Ti 1.38 Nb 1.11 O7 phase transparent luminescent material.

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