Transparent fluorescent ceramic with adjustable structure, and preparation method therefor and use thereof

Abstract

The present invention belongs to the technical field of luminescent materials, and discloses a transparent fluorescent ceramic with an adjustable structure, and a preparation method therefor and the use thereof. The transparent fluorescent ceramic comprises at least one of a single MgAl2Si4O12:Eu2+ crystal phase, a single Mg2Al4Si5O18:Eu2+ crystal phase, and dual MgAl2Si4O12:Eu2+ and Mg2Al4Si5O18:Eu2+ crystal phases.

Description

Structure-adjustable transparent fluorescent ceramic and preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of luminescent materials, and particularly relates to a structure-adjustable transparent fluorescent ceramic and a preparation method and application thereof. BACKGROUND

[0002] Ceramics is a typical multiphase system material, and its microstructure is almost entirely composed of nanometer or micrometer-sized grains. The solid functional material obtained by transparentizing the ceramic has many characteristics such as high mechanical strength, good heat resistance, excellent optical performance, and the like. In recent years, transparent fluorescent ceramic materials have achieved extraordinary performance and effect in many fields such as solid-state lighting and display, laser, optical communication, X-ray imaging, and infrared imaging, so it is of great significance to deeply study and develop high-performance transparent fluorescent ceramic materials.

[0003] It is well known that although great progress has been made in ceramic technology, the preparation of transparent ceramics is still a difficult problem. There are disadvantages such as high cost and complex process in several known methods for preparing transparent ceramic materials. In addition, most ceramic blanks require high purity of raw materials, and the ceramic blanks are obtained by high-pressure forming of irregularly shaped powders, which undoubtedly produces many pores, thereby reducing the transparency and mechanical strength of the ceramic. For example, CN101628811A discloses a method for preparing Ln x Yb y Y (3-x-y) Al5O 12 , Ln w Yb z Y (2-w-z) O3 transparent ceramic by cold isostatic pressing into a green body and sintering in a vacuum sintering furnace. This method has the disadvantages of high purity requirement for precursor raw materials and high cost due to the need for a continuous vacuum environment during sintering, so it is difficult to be recognized by the market. CN106554192A discloses a method for preparing transparent ceramic by using a grouting method and a hot isostatic pressing method. Although this method has the advantage of mass production, it has the disadvantages of many manufacturing steps, long time consumption, complex process, and high cost. CN112321295A discloses a method for preparing Y3Al5O 12 transparent ceramic by using a sol-gel method or a liquid-phase coprecipitation method. The ceramic prepared by this method has the characteristics of good optical uniformity and no stress, but the preparation is relatively complex, the cost is high, and mass production is not possible. CN113548883A uses a laser beam levitation melting method to prepare transparent ceramic. This method has the characteristics of short preparation time and high density of the prepared transparent ceramic, but the high cost greatly hinders the widespread use of this method.

[0004] Therefore, it is urgent to provide a new preparation method of transparent ceramic, which does not require harsh conditions such as vacuum or high pressure, and the transparent ceramic prepared by the method has good transparency and good optical properties.

[0005] SUMMARY

[0006] The present application aims to at least solve one of the above technical problems in the prior art. To this end, the present application proposes a structure-adjustable transparent fluorescent ceramic and a preparation method and application thereof. The preparation method described in the present application uses the same precursor glass to prepare a structure-adjustable transparent blue fluorescent ceramic doped with Eu 2+ The rare earth ion structure-adjustable transparent blue fluorescent ceramic has the characteristics of low cost, simple process, and mass production, and the transparent fluorescent ceramic prepared has the characteristics of compact glass / glass-ceramic structure, that is, there is no light scattering site (pore) in the material to dissipate energy. More importantly, the same precursor glass can obtain: single MgAl2Si4O 12 :Eu 2+ crystal phase transparent fluorescent ceramic, single Mg2Al4Si5O 18 :Eu 2+ crystal phase transparent fluorescent ceramic, and MgAl2Si4O 12 :Eu 2+ , Mg2Al4Si5O 18 :Eu 2+ double crystal phase transparent fluorescent ceramic under different heat treatment temperatures. In particular, the single Mg2Al4Si5O 18 :Eu 2+ crystal phase transparent fluorescent ceramic (also known as Mg2Al4Si5O 18 :Eu 2+ fully crystallized transparent fluorescent ceramic) has good stability, good blue light emission performance (quantum efficiency of more than 88%, even up to 90%), deep defect energy level (for example, 0.73eV, 0.97eV), good light information storage capacity, and long afterglow light emission characteristics at high temperature, and the afterglow time is as long as tens of minutes.

[0007] The first aspect of the present application provides a structure-adjustable transparent fluorescent ceramic.

[0008] Specifically, a structure-adjustable transparent fluorescent ceramic includes single MgAl2Si4O 12 :Eu 2+ crystal phase, single Mg2Al4Si5O 18 :Eu 2+ crystal phase, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu2+ at least one of the two crystal phases.

[0009] Preferably, the transparent fluorescent ceramic has a blue light emitting characteristic.

[0010] Preferably, the transparent fluorescent ceramic has a quantum efficiency of more than 88%, for example 89%-92%.

[0011] Preferably, the transparent fluorescent ceramic has a defect level of 0.73-0.97eV.

[0012] Preferably, the transparent fluorescent ceramic has no pores inside. That is, the transparent fluorescent ceramic has a compact glass / glass-ceramic structure, i.e. there are no light scattering sites (pores) inside the material to dissipate energy.

[0013] The second aspect of the present application provides a method for preparing a structure-adjustable transparent fluorescent ceramic.

[0014] Specifically, a method for preparing a structure-adjustable transparent fluorescent ceramic comprises the following steps:

[0015] S1, mixing an oxide of silicon, an oxide of aluminum, an oxide of magnesium and an oxide of europium to obtain a mixture;

[0016] S2, melting the mixture in a reducing atmosphere and cooling to obtain a precursor amorphous glass;

[0017] S3, heat treating the precursor amorphous glass in a reducing atmosphere, wherein the heat treatment temperature is 800-1200℃, to obtain the transparent fluorescent ceramic.

[0018] In the present application, if the heat treatment temperature in step S3 is lower than 800℃, no crystalline phase can be precipitated, and if the heat treatment temperature is too high, the glass will soften.

[0019] Preferably, in step S1, the oxide of silicon comprises at least one of SiO2 and SiO.

[0020] Preferably, in step S1, the oxide of aluminum comprises Al2O3.

[0021] Preferably, in step S1, the oxide of magnesium comprises MgO.

[0022] Preferably, in step S1, the oxide of europium comprises Eu2O3.

[0023] Preferably, in step S1, the mixture comprises the following components in mass percentage: SiO245%-75%, Al2O318%-32%, MgO 8%-22%, Eu2O30.01%-2.2%; further preferably, SiO250%-70%, Al2O320%-30%, MgO 10%-20%, Eu2O30.01%-2%.

[0024] Further preferably, the mixture comprises the following components in mass percentage: SiO260%, Al2O325.5%, MgO 14.49%, Eu2O30.01%. Under the condition of the components, a single Mg2Al4Si5O 18 :Eu 2+ The crystal phase has the best optical performance.

[0025] Preferably, in step S2, the reducing atmosphere is provided by H2, CO or carbon powder (such as activated carbon).

[0026] Preferably, in step S2, the temperature of the melting is 1300-1600°C, further preferably 1400-1600°C.

[0027] Preferably, in step S2, the time of the melting is 1-6h, further preferably 2-5h.

[0028] Preferably, in step S2, the cooling process is direct high-temperature taking out and cooling to room temperature.

[0029] Preferably, in step S3, the temperature of the heat treatment is 1175-1200°C.

[0030] Preferably, in step S3, the reducing atmosphere is provided by H2, CO or carbon powder.

[0031] Preferably, in step S3, the time of the heat treatment is 20 minutes to 16 hours, further preferably 30 minutes to 60 minutes.

[0032] Preferably, the preparation method comprises the following steps:

[0033] S1, grinding SiO2, Al2O3, MgO and Eu2O3 to obtain a mixed powder;

[0034] S2, placing the mixed powder of step S1 in a reducing atmosphere at a temperature of 1400-1600°C for 1-6h, immediately taking out after high-temperature melting and rapidly cooling to obtain a precursor amorphous glass;

[0035] S3, heat-treating the precursor amorphous glass of step S2 in a reducing atmosphere, wherein the temperature of the heat-treatment is 800-1200℃, to obtain the transparent fluorescent ceramic material.

[0036] Preferably, in step S1, the grinding time is 20-30min, for example 20min, 25min, 30min.

[0037] Preferably, in step S2, the mixed powder of step S1 is placed in a reducing atmosphere at a temperature of 1450-1500℃ for 3.5-4h.

[0038] The third aspect of the present application provides an application of the transparent fluorescent ceramic with adjustable structure.

[0039] An apparatus comprising the above transparent fluorescent ceramic.

[0040] Preferably, the apparatus comprises an illumination apparatus or an optical storage apparatus.

[0041] Compared with the prior art, the present application has the following advantages:

[0042] (1) The transparent fluorescent ceramic of the present application comprises at least one of single MgAl2Si4O 12 :Eu 2+ phase, single Mg2Al4Si5O 18 :Eu 2+ phase, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ double phases. The transparent fluorescent ceramic has good stability, good blue light emission performance (quantum efficiency over 88%, even up to 90%), deep defect energy level (for example, 0.73eV, 0.97eV) and good optical information storage capacity, and has long afterglow luminescence characteristics at high temperature, and the afterglow time is up to tens of minutes.

[0043] (2) The present application uses a glass precursor heat treatment in-situ crystallization method under normal pressure to efficiently and low-cost prepare a blue light transparent fluorescent ceramic with excellent optical performance, wherein the same glass precursor is heat-treated at different temperatures to obtain: single MgAl2Si4O 12 :Eu 2+ phase transparent fluorescent ceramic, single Mg2Al4Si5O 18 :Eu 2+ phase transparent fluorescent ceramic, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18:Eu 2+ Biphase transparent fluorescent ceramic, especially single Mg2Al4Si5O 18 :Eu 2+ Transparent fluorescent ceramic with single Mg2Al4Si5O BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 is a precursor glass of Example 1, single MgAl2Si4O 12 :Eu 2+ Transparent fluorescent ceramic with single Mg2Al4Si5O 18 :Eu 2+ Transparent fluorescent ceramic with single Mg2Al4Si5O 12 :Eu 2+ Transparent fluorescent ceramic with single Mg2Al4Si5O 18 :Eu 2+ XRD pattern of biphase transparent fluorescent ceramic.

[0045] Figure 2 is MgAl2Si4O 12 :Eu 2+ Transparent fluorescent ceramic.

[0046] Figure 3 is a precursor glass and Mg2Al4Si5O 18 :Eu 2+ Transparent fluorescent ceramic.

[0047] Figure 4 is MgAl2Si4O 12 :Eu 2+ Transparent fluorescent ceramic.

[0048] Figure 5 is MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ Transparent fluorescent ceramic.

[0049] Figure 6 is Mg2Al4Si5O 18 :Eu 2+ Transparent fluorescent ceramic.

[0050] Figure 7 shows the MgAl2Si4O from Example 2 of this application. 12 Eu 2+ Excitation and emission spectra of transparent fluorescent ceramics.

[0051] Figure 8 shows the MgAl2Si4O from Example 3 of this application. 12 Eu 2+ Mg2Al4Si5O 18 Eu 2+ Excitation and emission spectra of bicrystalline transparent fluorescent ceramics.

[0052] Figure 9 shows the Mg2Al4Si5O from Example 4 of this application. 18 Eu 2+ Excitation and emission spectra of transparent fluorescent ceramics.

[0053] Figure 10 shows the Mg2Al4Si5O from Example 4 of this application. 18 Eu 2+ Quantum efficiency diagram of transparent fluorescent ceramics.

[0054] Figure 11 shows the Mg2Al4Si5O from Example 4 of this application. 18 Eu 2+ Thermoluminescence spectrum of transparent fluorescent ceramic.

[0055] Figure 12 shows the Mg2Al4Si5O from Example 4 of this application. 18 Eu 2+ Afterglow decay curves of transparent fluorescent ceramics at temperatures of 300K and 660K. Detailed Implementation

[0056] To enable those skilled in the art to more clearly understand the technical solutions described in this application, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed in this application.

[0057] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0058] Example 1

[0059] The preparation method of the precursor amorphous glass in this embodiment is as follows:

[0060] S1. Weigh each component according to the mass content of SiO2 60%, Al2O3 25.5%, MgO 14.49%, and Eu2O3 0.01%. Mix and grind SiO2, Al2O3, MgO and Eu2O3 for 30 minutes to obtain a mixed powder, and put it into a corundum crucible.

[0061] S2, the crucible with the mixed powder of step S1 is placed in a large crucible with activated carbon and a cover, and is melted in a box furnace at 1500℃ for 4h, and is immediately taken out after melting and is cooled at room temperature to obtain a precursor amorphous glass.

[0062] The XRD pattern of the precursor amorphous glass prepared in this example is shown as "Glass" in Fig. 1 (in Fig. 1, "Intensity" represents intensity, and "degree" represents degree), and Fig. 1 shows that the XRD pattern of the precursor amorphous glass of Example 1 has no diffraction peak, indicating that no crystal is precipitated in the glass, and the prepared glass is amorphous, and Fig. 3 shows that the precursor amorphous glass with a thickness of 1.5mm has high transmittance, and the covered text can be clearly seen through the precursor amorphous glass.

[0063] Example 2

[0064] The MgAl2Si4O 12 :Eu 2+ The preparation method of the transparent fluorescent ceramic is as follows:

[0065] S1, each component is weighed according to the mass content of SiO2 60%, Al2O3 25.5%, MgO 14.49%, and Eu2O3 0.01%, and SiO2, Al2O3, MgO and Eu2O3 are mixed and ground for 30min to obtain a mixed powder, and are loaded into a corundum crucible;

[0066] S2, the crucible with the mixed powder of step S1 is placed in a large crucible with activated carbon and a cover, and is melted in a box furnace at 1500℃ for 4h, and is immediately taken out after melting and is cooled at room temperature to obtain a precursor amorphous glass;

[0067] S3, the precursor amorphous glass of step S2 is heat treated in a reducing atmosphere (H2), and the heat treatment temperature is 930℃, and the time is 16h, to obtain a MgAl2Si4O 12 :Eu 2+ transparent fluorescent ceramic.

[0068] The XRD pattern of the transparent fluorescent ceramic prepared in this example is shown as "930℃ 16h" in Fig. 1 ("930℃ 16h" corresponds to Example 2), and Fig. 1 shows that the XRD diffraction peak of the transparent fluorescent ceramic of Example 2 is consistent with the standard card PDF#27-0716 (MgAl2Si4O 12 :Eu 2+) one-to-one correspondence, and completely without amorphous diffraction hump corresponding to the precursor amorphous glass ("Glass"), and further combined with the scanning electron microscope (SEM) figure (Figure 4, "ceramic" in Figure 4 represents ceramic), it can be seen that the transparent fluorescent ceramic grain prepared in this embodiment is about dozens of microns and the grain boundary is very small, indicating that the MgAl2Si4O 12 :Eu 2+ transparent fluorescent ceramic is successfully prepared. 12 :Eu 2+ The transparent fluorescent ceramic of Example 2 with a thickness of 1.5 mm shows good transparency, and Figure 2 directly shows that the transparent fluorescent ceramic can clearly see the covered text.

[0069] From Figure 7 (Figure 7, "Wavelength" represents wavelength, "Intensity" represents intensity), the excitation (curve 1 in Figure 7) and emission spectrum (curve 2 in Figure 7) of the MgAl2Si4O 12 :Eu 2+ transparent fluorescent ceramic of Example 2 can be effectively excited in the wavelength range of 230nm-430nm, and the emission spectrum range covers 375nm-750nm, and the emission peak is at 440nm in the blue light region.

[0070] Example 3

[0071] The MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ transparent fluorescent ceramic of this embodiment is prepared as follows:

[0072] S1, according to the mass content of SiO2 60%, Al2O3 25.5%, MgO 14.49%, and Eu2O3 0.01%, each component is weighed, SiO2, Al2O3, MgO and Eu2O3 are mixed and ground for 30min to obtain a mixed powder, and then loaded into a corundum crucible;

[0073] S2, the crucible loaded with the mixed powder in step S1 is placed in a large crucible covered with activated carbon, and is kept at 1500℃ in a box furnace for 4h to melt, and is immediately taken out after melting and cooled at room temperature to obtain a precursor amorphous glass;

[0074] S3, the precursor amorphous glass in step S2 is heat treated in a reducing atmosphere (CO), the heat treatment temperature is 1100℃, and the time is 30min, to obtain MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O18 Eu 2+ Bicrystalline transparent fluorescent ceramic.

[0075] The XRD pattern of the bicrystalline transparent fluorescent ceramic prepared in this embodiment is shown in Figure 1 (1100℃ for 30 min) (1100℃ for 30 min in Figure 1 corresponds to Example 3). Figure 1 shows that MgAl2Si4O is simultaneously precipitated in the bicrystalline transparent fluorescent ceramic of Example 3. 12 Eu 2+ (PDF#27-0716) and Mg2Al4Si5O 18 Eu 2+ (PDF#84-1219) Bicrystalline phase, in which there are no amorphous diffraction peaks corresponding to the precursor amorphous glass (“Glass”), and Mg2Al4Si5O 18 Eu 2+ The diffraction peak intensity of the crystalline phase is greater than that of MgAl2Si4O 12 Eu 2+ Crystal phase, indicating the presence of Mg2Al4Si5O in the bicrystalline transparent fluorescent ceramic of Example 3. 18 Eu 2+ The crystalline phase is dominant. Further scanning electron microscopy testing was performed on the bicrystalline transparent fluorescent ceramic prepared in Example 3. As shown in Figure 5 (where "ceramic" indicates ceramic), it also represents MgAl2Si4O. 12 Eu 2+ Rhombic grains of the crystal phase are randomly embedded in Mg2Al4Si5O 18 Eu 2+ In fluorescent ceramics where the crystalline phase is dominant.

[0076] Figure 8 shows the MgAl2Si4O3 composition (where "Wavelength" represents wavelength and "Intensity" represents intensity). 12 Eu 2+ and Mg2Al4Si5O 18 Eu 2+ The excitation (curve 1 in Figure 8) and emission (curve 2 in Figure 8) spectra of the bicrystalline transparent fluorescent ceramic show that the transparent fluorescent ceramic of Example 3 can be effectively excited in the 230nm-430nm wavelength range, and the emission spectrum covers the 375nm-750nm range, with the emission peak at 458nm in the blue light region.

[0077] Example 4

[0078] This example uses Mg2Al4Si5O 18 Eu 2+ The preparation method of transparent fluorescent ceramics is as follows:

[0079] S1, according to the mass content of SiO260%, Al2O325.5%, MgO 14.49%, Eu2O30.01%, each component is weighed, SiO2, Al2O3, MgO and Eu2O3 are mixed and ground for 30 min to obtain a mixed powder, and then loaded into a corundum crucible;

[0080] S2, the crucible loaded with the mixed powder in step S1 is loaded into a large crucible covered with activated carbon, and is kept at 1500℃ in a box furnace for 4h to be melted, and then immediately taken out and cooled at room temperature to obtain a precursor amorphous glass;

[0081] S3, the precursor amorphous glass in step S2 is heat treated in a reducing atmosphere (CO) at a temperature of 1175℃ for 30 min to obtain a Mg2Al4Si5O 18 :Eu 2+ fully crystallized transparent ceramic.

[0082] The XRD pattern of the fully crystallized transparent fluorescent ceramic prepared in this example is shown in Figure 1. Figure 1 shows that the XRD diffraction peaks of the fully crystallized transparent ceramic of Example 4 correspond to the standard card PDF #84-1219 (Mg2Al4Si5O 18 :Eu 2+ ), and there is no amorphous diffraction hump corresponding to the precursor amorphous glass ("Glass"), and further combined with the scanning electron microscope (SEM) image in Figure 6 (where "ceramic" represents ceramic), it can be seen that the grain size of the fully crystallized transparent fluorescent ceramic prepared in this example is about tens of microns and the grain boundary is very small, indicating that the Mg2Al4Si5O 18 :Eu 2+ fully crystallized transparent ceramic is successfully prepared.

[0083] Figure 3(B) directly shows that the fully crystallized transparent fluorescent ceramic of Example 4 with a thickness of 1mm exhibits good transparency, and the covered text can be clearly seen through the Mg2Al4Si5O 18 :Eu 2+ fully crystallized transparent fluorescent ceramic.

[0084] Figure 9 (where "Wavelength" represents wavelength and "Intensity" represents intensity) is the emission spectrum of the Mg2Al4Si5O 2+ :Eu 18 doped with 0.1(wt%) of Eu 2+The excitation (curve 1 in FIG. 9) and emission (curve 2 in FIG. 9) spectra of the fully crystallized transparent fluorescent ceramic show that the fully crystallized transparent fluorescent ceramic can be effectively excited at 220 nm-440 nm, the emission band covers 375 nm-700 nm, and the emission peak is at blue light 450 nm.

[0085] FIG. 10 (in FIG. 10, "Wavelength" represents wavelength, and "Intensity" represents intensity) is a thermoluminescence spectrum of the Mg2Al4Si5O 18 :Eu 2+ transparent fluorescent ceramic of Example 4, and the results show that the transparent fluorescent ceramic prepared in Example 4 has a quantum efficiency as high as 90%. 18 :Eu 2+ transparent fluorescent ceramic.

[0086] FIG. 11 (in FIG. 11, "Temperature" represents temperature, and "TL intensity" represents the corresponding luminescence intensity at a specific temperature) is a thermoluminescence spectrum of the Mg2Al4Si5O 18 :Eu 2+ transparent fluorescent ceramic of Example 4, and the results show that the transparent fluorescent ceramic has a wide thermoluminescence peak and the thermoluminescence peak extends to high temperature 700 K, and further calculation shows that the trap depth of the transparent fluorescent ceramic is 0.73 eV and 0.97 eV, respectively, indicating that the transparent fluorescent ceramic has very deep defect energy levels and good defect energy storage performance.

[0087] FIG. 12 (in FIG. 12, "Time" represents time, "Log intensity" represents the logarithm of intensity, and "λ ex " represents an excitation light wavelength of 365 nm, and "Backgrand" represents background) is a luminescence decay curve of the Mg2Al4Si5O 18 :Eu 2+ transparent fluorescent ceramic of Example 4 at temperatures of 300 K and 660 K, respectively, and the results show that the initial afterglow intensity of the transparent fluorescent ceramic at 660 K is one order of magnitude higher than that at 300 K, which is related to the accelerated release of trapped carriers, and the afterglow performance shows a clear enhancement trend after 5 min as the temperature rises, indicating that the transparent fluorescent ceramic is expected to be used in related high-temperature afterglow scenarios.

[0088] The present application uses in-situ crystallization of glass precursors under normal pressure by heat treatment to efficiently and low-cost prepare transparent blue fluorescent ceramics with excellent optical performance, wherein heat treatment of the same glass precursor at different temperatures can respectively obtain: single MgAl2Si4O 12 :Eu2+ crystalline transparent fluorescent ceramic, single Mg2Al4Si5O 18 :Eu 2+ crystalline transparent fluorescent ceramic, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ biphase transparent fluorescent ceramic, wherein Mg2Al4Si5O 18 :Eu 2+ full crystalline transparent fluorescent ceramic, has good blue light emitting performance (quantum efficiency reaches 90%), has deeper defect energy levels (0.73 eV and 0.97 eV respectively) and has good light information storage capacity.

[0089] In summary, the same precursor glass is used to prepare a Eu 2+ rare earth ion doped transparent blue light fluorescent ceramic material with adjustable structure under normal pressure by in-situ crystallization method, the method has low cost, simple process and can be mass produced, and the prepared ceramic has a compact glass / glass ceramic structure, i.e. there is no light scattering part (pore) in the material to dissipate energy, and has good transparency. Importantly, the same precursor glass can obtain single MgAl2Si4O 12 :Eu 2+ crystalline transparent fluorescent ceramic, single Mg2Al4Si5O 18 :Eu 2+ crystalline transparent fluorescent ceramic, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ biphase transparent fluorescent ceramic. When the heat treatment temperature is within the scope of the application, the single MgAl2Si4O 12 :Eu 2+ crystalline transparent fluorescent ceramic, single Mg2Al4Si5O 18 :Eu 2+ crystalline transparent fluorescent ceramic, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ biphase transparent fluorescent ceramic can all emit broadband spectra of 375-700 nm under ultraviolet excitation, and more importantly, Mg2Al4Si5O 18 :Eu 2+The fully crystallized transparent fluorescent ceramic has good thermal stability, high efficiency blue light emission (quantum efficiency of 90%) and good optical information storage capacity (deep defect energy level degrees of 0.73 eV and 0.97 eV), and is expected to be used in the fields of high-power lighting and optical information storage.

[0090] Comparative Example 1

[0091] The Mg2Al4Si5O 18 :Mn 2+ The preparation method of the transparent fluorescent ceramic is as follows:

[0092] S1, each component was weighed according to the mass content of SiO2 60%, Al2O3 25.5%, MgO 14.49% and MnCO3 0.01%, SiO2, Al2O3, MgO and MnCO3 were mixed and ground for 30 min to obtain a mixed powder, and the mixed powder was loaded into a corundum crucible;

[0093] S2, the crucible loaded with the mixed powder in step S1 was loaded into a large crucible covered with activated carbon, and was melted at 1500 DEG C for 4 h in a box furnace, and was immediately taken out after melting and cooled at room temperature to obtain a precursor amorphous glass;

[0094] S3, the precursor amorphous glass in step S2 was heat treated in a reducing atmosphere (H2), the heat treatment temperature was 1175 DEG C, and the time was 30 min, to obtain Mg2Al4Si5O 18 :Mn 2+ The fully crystallized transparent ceramic.

[0095] The Mg2Al4Si5O 18 :Mn 2+ The fully crystallized transparent ceramic does not have light emission phenomenon.

[0096] Comparative Example 2

[0097] The Mg2Al4Si5O 18 :Tb 3+ The preparation method of the transparent fluorescent ceramic is as follows:

[0098] S1, each component was weighed according to the mass content of SiO2 60%, Al2O3 25.5%, MgO 14.49% and Tb2O3 0.01%, SiO2, Al2O3, MgO and Tb2O3 were mixed and ground for 30 min to obtain a mixed powder, and the mixed powder was loaded into a corundum crucible;

[0099] S2, the crucible with mixed powder in step S1 is put into a large crucible with activated carbon and cover, and is kept in a box furnace at 1500℃ for 4h to be melted, and is taken out immediately after melting and is cooled at room temperature to obtain a precursor amorphous glass;

[0100] S3, the precursor amorphous glass in step S2 is heat treated in a reducing atmosphere (H2), the heat treatment temperature is 1175℃, and the time is 30min to obtain Mg2Al4Si5O 18 :Tb 3+ Fully crystallized transparent ceramic.

[0101] Mg2Al4Si5O 18 :Tb 2+ The fully crystallized transparent ceramic does not emit light.

[0102] Finally, it should be noted that the above examples are used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A transparent fluorescent ceramic, characterized in that, including single MgAl2Si4O 12 :Eu 2+ crystal phase, single Mg2Al4Si5O 18 :Eu 2+ crystal phase, and MgAl2Si4O 12 :Eu 2+ and Mg2Al4Si5O 18 :Eu 2+ at least one of the two crystal phases.

2. The transparent fluorescent ceramic of claim 1, wherein, The transparent fluorescent ceramic has a blue light emitting characteristic.

3. The transparent fluorescent ceramic of claim 1, wherein, The quantum efficiency of the transparent fluorescent ceramic is more than 88%.

4. The transparent fluorescent ceramic of claim 1, wherein, The defect energy level of the transparent fluorescent ceramic is 0.73-0.97 eV.

5. The transparent fluorescent ceramic of claim 1, wherein, The transparent fluorescent ceramic has no internal porosity.

6. The method of producing a transparent fluorescent ceramic according to any one of claims 1 to 5, characterized in that, The method comprises the following steps: S1, mixing an oxide of silicon, an oxide of aluminum, an oxide of magnesium and an oxide of europium to obtain a mixture; S2, melting the mixture in a reducing atmosphere to obtain a precursor amorphous glass; S3, heat treating the precursor amorphous glass in a reducing atmosphere at a temperature of 800-1200 DEG C to obtain the transparent fluorescent ceramic.

7. The preparation method according to claim 6, characterized in that, In step S1, the oxide of silicon comprises at least one of SiO2 and SiO; and / or, the oxide of aluminum comprises Al2O3; and / or, the oxide of magnesium comprises MgO; and / or, the oxide of europium comprises Eu2O3.

8. The preparation method according to claim 6, characterized in that, In step S1, the mixture comprises the following components with the following mass percentages: SiO2 45%-75%, Al2O3 18%-32%, MgO 8%-22%, and Eu2O3 0.01%-2.2%; and / or, in step S2, the reducing atmosphere is provided by H2, CO or carbon powder; and / or, in step S2, the melting temperature is 1300-1600 DEG C.

9. The preparation method according to claim 6, characterized in that, In step S3, the heat treatment temperature is 1175-1200 DEG C; and / or, in step S3, the reducing atmosphere is provided by H2, CO or carbon powder; and / or, in step S3, the heat treatment time is 20 minutes to 16 hours.

10. An apparatus, comprising: The method comprises the transparent fluorescent ceramic of any one of claims 1-5. The method comprises the transparent fluorescent ceramic of any one of claims 1-5.

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