CN111377713A

CN111377713A - Complex phase fluorescent ceramic and preparation method thereof

Info

Publication number: CN111377713A
Application number: CN201911182074.0A
Authority: CN
Inventors: 胡松; 陈晗; 薛振海; 王正娟; 张芸莉; 李宏书; 周国红; 王士维
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2019-11-27
Filing date: 2019-11-27
Publication date: 2020-07-07
Anticipated expiration: 2039-11-27
Also published as: CN111377713B

Abstract

The invention relates to a complex phase fluorescent ceramic and a preparation method thereof, wherein the complex phase fluorescent ceramic comprises the following components: the high-heat-conductivity medium ceramic matrix comprises a high-heat-conductivity medium ceramic matrix and fluorescent ceramic main bodies which are distributed in the high-heat-conductivity medium ceramic matrix and are periodically arranged; the shortest distance L between adjacent fluorescent ceramic main bodies is 200-1000 mu m, and the volume fraction delta of the high-heat-conductivity medium ceramic main bodies in the complex-phase fluorescent ceramic is 5-60%; the fluorescent ceramic main body is rare earth doped transparent ceramic; the material of the high heat-conducting medium ceramic matrix is selected from Al₂O₃、AlN、BeO、Sc₂O₃、Si₃N₄BN, SiC and MgO.

Description

Complex phase fluorescent ceramic and preparation method thereof

Technical Field

The invention relates to a complex phase fluorescent ceramic with excellent luminous thermal stability and a preparation method thereof, in particular to a method for improving the thermal conductivity of the fluorescent ceramic, belonging to the technical field of fluorescent material application.

Background

In laser display devices based on laser-excited remote phosphor technology (LARP), a light conversion material is one of the cores and is also a research hotspot in recent years, and the light color temperature, the fluorescence quantum efficiency and the light emitting stability under high-power-density laser irradiation of the light conversion material are directly related to the quality of the devices. Inorganic luminescent materials such as resin-encapsulated fluorescent powder, rare earth doped glass, microcrystalline glass and the like compete with each other and promote the quality of laser display devices continuously. In the development process, rare earth doped transparent ceramic (fluorescent ceramic for short) is distinguished in the field of laser display by virtue of the advantages of better heat conduction, physical and chemical stability and the like compared with traditional inorganic luminescent materials such as resin encapsulated fluorescent powder, fluorescent glass and the like, and becomes one of the excellent choices of the current high-power-density LD driving luminescent material.

The biggest difference between the traditional solid-state light sources such as the LED and the LD used as the light source is that the local temperature rise effect caused by Stokes displacement, non-radiative transition and light-matter action of fluorescent materials under the excitation of the LD is more obvious, and even fluorescent ceramics with high thermal conductivity (10W/m.K) still easily show excitation saturation, fluorescence attenuation, color coordinate shift and the like under the irradiation of the LD with high power density. Moreover, as laser display gradually moves to high-brightness, compact and static modes, the rapidly increased thermal load, thermal shock and continuously compressed space bring more severe tests to the reliability, light efficiency and luminous stability of the fluorescent ceramic. Patent 1 (chinese publication No. CN107285745A) discloses an alumina-based fluorescent ceramic, which is obtained by mixing and co-firing fluorescent powder and high-thermal-conductivity alumina powder to obtain alumina-fluorescent powder composite ceramic with alumina dispersed and distributed, so that the effective thermal conductivity of the ceramic is improved, and the heat dissipation performance is enhanced. However, discontinuous Al is introduced₂O₃The grains increase the heterointerface and interface phonon scattering, and hinder the directional heat transport. Therefore, from the analysis of the interface thermal resistance, the contribution of the high thermal conductive medium in dispersion distribution to the improvement of the heat dissipation efficiency is limited.

Disclosure of Invention

In view of the above problems, an object of the present invention is to provide a periodic structure multiphase fluorescent ceramic and a preparation method thereof, wherein a high thermal conductive medium forms a continuous thermal conductive channel, so that a large amount of heterogeneous crystal boundary phonon scattering can be avoided, the directional heat transport capability of the fluorescent ceramic is significantly improved, and a fluorescent ceramic material with more excellent thermal conductivity can be obtained.

In one aspect, the present invention provides a complex phase fluorescent ceramic comprising: the high-heat-conductivity medium ceramic matrix comprises a high-heat-conductivity medium ceramic matrix and fluorescent ceramic main bodies which are distributed in the high-heat-conductivity medium ceramic matrix and are periodically arranged; the distance L between adjacent fluorescent ceramic main bodies is 200-1000 mu m, and the volume fraction delta of the high-heat-conductivity medium ceramic matrix in the complex-phase fluorescent ceramic is 5-60%;

the fluorescent ceramic main body is rare earth doped transparent ceramic; the material of the high heat-conducting medium ceramic matrix is selected from Al₂O₃、AlN、BeO、Sc₂O₃、Si₃N₄BN, SiC and MgO.

In the disclosure, the multiphase fluorescent ceramic is prepared by constructing ordered and periodically arranged fluorescent ceramic main bodies in a high heat-conducting medium ceramic matrix with continuous heat conduction. The ceramic matrix with the high heat-conducting medium is a continuous heat-conducting medium (namely a continuous heat-conducting channel is formed), heat caused by a surface heat source or heat caused by Stokes displacement and non-radiative transition in the luminescent process of the fluorescent ceramic main body is efficiently transported to a heat dissipation end, and the heat transport capacity of the ceramic is effectively enhanced, so that the low bulk phase temperature of the ceramic body is kept, and good conditions are provided for stable luminescence of the fluorescent ceramic. That is, the complex phase fluorescent ceramic of the present invention has directional heat transport property without affecting its fluorescent property. Furthermore, L is the shortest distance between the fluorescent ceramic bodies, which can also be understood as the wall thickness formed between the porous structures in the continuous heat-conducting high-thermal-conductivity medium ceramic matrix, δ is the volume fraction of the complex-phase fluorescent ceramic occupied by the high-thermal-conductivity medium ceramic matrix, and L and δ jointly determine the effective size of the fluorescent body.

Preferably, L is more than or equal to 300 mu m and less than or equal to 500 mu m; delta is between 10 and 40 percent.

Preferably, the fluorescent ceramic main body comprises YAG, RE and Al₂O₃/YAG:RE、Lu₂O₃:RE、Y₂O₃:RE、LuAG:RE、La₂Hf₂O₇:RE、YVO₄:RE、CaAlSiN₃At least one of RE; wherein RE is selected from Ce³⁺、Eu²⁺、Pr³⁺、Cr³ ⁺、Tb³⁺、Sm³⁺、Dy³⁺、Ho³⁺And Tm³⁺At least one of; the doping amount of RE is preferably 0.1 to 2 mol%. Preferably, the fluorescent materialThe section of the optical ceramic main body is circular, regular polygon or rectangle.

In another aspect, the present invention further provides a method for preparing the above complex phase fluorescent ceramic, comprising:

(1) preparing high heat-conducting medium ceramic green bodies with pore channel structures arranged in an array;

(2) preparing colloidal fluorescent ceramic main body medium slurry, and filling the colloidal fluorescent ceramic main body medium slurry into high heat conduction medium ceramic green bodies with pore channel structures arranged in an array manner by adopting a colloidal forming technology to obtain a complex phase fluorescent ceramic green body;

(3) and degreasing and sintering the obtained complex phase fluorescent ceramic blank to obtain the complex phase fluorescent ceramic.

Preferably, high thermal conductivity dielectric ceramic powder and photosensitive resin are mixed to serve as raw materials, and a 3D printing technology is adopted to prepare high thermal conductivity dielectric ceramic green bodies with pore structures arranged in an array; the photosensitive resin accounts for 18-40 wt% of the total mass of the raw materials, and preferably 21-26 wt%; the parameters of the 3D printing technique include: the thickness of the single layer is 0.02-0.05 mm; the illumination intensity is 2-15 mW/cm²。

Also, preferably, the photosensitive resin includes an epoxy acrylate resin, an epoxy resin, a photoinitiator, a thixotropic agent and a reactive diluent; more preferably, the photosensitive resin comprises 55-65 wt% of epoxy acrylate resin, 6-15 wt% of epoxy resin, 4-8 wt% of photoinitiator, 2-5 wt% of thixotropic agent and 10-20 wt% of reactive diluent, and the sum of the mass percentages of the components is 100 wt%.

Preferably, the colloidal fluorescent ceramic host medium slurry comprises the following components: the fluorescent ceramic comprises fluorescent ceramic dielectric powder, a dispersing agent, a curing agent and deionized water, wherein the fluorescent ceramic dielectric powder accounts for 70-82 wt% of the total mass of the colloidal fluorescent ceramic main body dielectric slurry.

Moreover, the preferable weight percentage of the fluorescent ceramic dielectric powder in the total mass of the colloidal fluorescent ceramic main body dielectric slurry is 78-82 wt%; the colloidal high-thermal-conductivity ceramic main body medium slurry further comprises the following components: 0.2 to 0.8wt% of a dispersant and 0.1 to 0.3wt% of a curing agent.

Preferably, the colloidal molding technique comprises: and injecting the colloidal fluorescent ceramic main body medium slurry into the high heat conduction medium ceramic green bodies with the pore channel structures in periodic arrangement, and curing for 10-30 hours at room temperature (22-28 ℃).

Preferably, the degreasing temperature is 800-1200 ℃, and the time is 1-5 hours; preferably, the temperature rise rate of the degreasing is 0.1-1 ℃/min.

Preferably, the sintering mode is vacuum reaction sintering; the temperature of the vacuum reaction sintering is 1650-1780 ℃, the time is 0.5-20 hours, and the vacuum degree is not lower than 10^-3Pa。

Has the advantages that:

in the disclosure, a continuous channel formed by a medium with high heat conduction property is constructed around a fluorescent ceramic main body, so that a heat transport channel can be provided for the fluorescent ceramic, and part of heat can be transported to a heat dissipation end from the high heat conduction channel, thereby reducing the heat flow density of the fluorescent main body and laying a foundation for efficient and stable luminescence of the fluorescent main body. Compared with the fluorescent ceramic without the continuous directional heat conduction channel, the balance temperature of the surface of the fluorescent ceramic excited by the LD light source with different power of 1.6-8.2W is reduced by 12-32%, and the luminous thermal stability and the excitation saturation threshold of the fluorescent ceramic are expected to be remarkably improved.

Drawings

FIG. 1 is a schematic structural view (unit size in mm) of a complex phase fluorescent ceramic prepared in example 1;

FIG. 2 is a microscopic structure view of the complex phase fluorescent ceramic prepared in example 1;

FIG. 3 is a graph showing the equilibrium temperature change of the surface of the complex phase fluorescent ceramic prepared in example 1 under different Laser (LD) excitations;

FIG. 4 is a graph showing the equilibrium temperature change of the surface of the fluorescent ceramic without the continuous oriented thermal conductive matrix prepared in comparative example 1 under different Laser (LD) excitations.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the present disclosure, a complex phase fluorescent ceramic with built-in continuous directional heat conducting channel has directional heat transport property. The complex phase fluorescent ceramic comprises a high heat-conducting medium ceramic matrix and fluorescent ceramic main bodies which are distributed in the high heat-conducting medium ceramic matrix and are arranged periodically. In fact, the high thermal conductivity ceramic matrix itself of the present invention can be regarded as being distributed around the fluorescent ceramic body in an array arrangement (also called a periodic arrangement), so as to form a continuous thermal conduction channel (or called a continuous directional channel) to reduce the temperature of the fluorescent ceramic body, and further enhance the luminescence stability and the excitation saturation threshold. The shortest distance between adjacent fluorescent ceramic bodies can be 200 mu m or less and L or 1000 mu m or less. The volume fraction of the high heat-conducting medium ceramic matrix can be more than or equal to 5% and less than or equal to 60%. Wherein L is also substantially the thickness of the space between the ceramic substrates of the high thermal conductive medium. Preferably 300 μm.ltoreq.L.ltoreq.500. mu.m. Preferably, delta is between 10% and 40%.

In an alternative embodiment, the fluorescent ceramic body may be a rare earth doped transparent ceramic. Wherein, the fluorescent ceramic main body without the heat conduction channel emits high-intensity fluorescence under the excitation of ultraviolet or blue light. When continuous high-heat-conduction ceramic media are constructed around the fluorescent ceramic main body to form the heat conduction channel, partial heat of the fluorescent ceramic main body can be transferred to the heat conduction channel and further transported to a heat dissipation end from the heat conduction channel, and therefore the heat flow density of the fluorescent ceramic main body is effectively reduced. As shown in fig. 1, when an excitation light source is incident from the ceramic surface, the fluorescent ceramic body emits fluorescence with heat generation. Part of the heat is rapidly transferred to the continuous heat conducting channel and is transported to the other surface from the heat conducting channel formed by the high heat conducting medium ceramic matrix until the heat is dissipated.

In an alternative embodiment, the high thermal conductivity ceramic dielectric matrix may preferably be Al₂O₃、AlN、BeO、Sc₂O₃、Si₃N₄Polycrystalline ceramics such as BN, SiC and MgO, more preferably Al₂O₃And MgO ceramics. The rare earth doped transparent ceramic can be YAG, RE, Al₂O₃/YAG:RE、Lu₂O₃:RE、Y₂O₃:RE、LuAG:RE、La₂Hf₂O₇:RE、YVO₄:RE、CaAlSiN₃RE ceramic. Wherein RE is Ce³⁺、Eu²⁺、Pr³⁺、Cr³⁺、Tb³⁺、Sm³⁺、Dy³⁺、Ho³⁺、Tm³⁺And the doping content may be 0.1 to 2 mol%.

In the embodiment of the invention, the complex phase fluorescent ceramic blank can be prepared by adopting a technology of combining 3D printing and colloidal state forming, and then the complex phase fluorescent ceramic is prepared by degreasing and sintering. The preparation method of the complex phase fluorescent ceramic provided by the invention is exemplarily described as follows.

Preparation of 3D printing ceramic slurry (slurry for high heat-conducting medium). Weighing raw material powder (ceramic powder for short) of the required high heat-conducting medium ceramic, wherein the ceramic powder comprises: al (Al)₂O₃、AlN、BeO、Sc₂O₃、Si₃N₄BN, SiC, MgO powder and the like, preferably Al₂O₃And MgO. And weighing a proper amount of photosensitive resin, and fully mixing the ceramic powder and the photosensitive resin to prepare ceramic slurry. Wherein, the ceramic powder can account for 60-82 wt% of the total mass of the ceramic powder and the photosensitive resin, and preferably 74-79 wt%. In an alternative embodiment, wherein the photosensitive resin comprises an epoxy acrylate resin, an epoxy resin, a photoinitiator, a thixotropic agent, and a reactive diluent. For example, the photosensitive resin comprises 55-65 wt% of epoxy acrylate resin, 6-15 wt% of epoxy resin, 4-8 wt% of photoinitiator, 2-5 wt% of thixotropic agent and 10-20 wt% of reactive diluent, and the sum of the mass percentages of the components is 100 wt%. Wherein, the photoinitiator can be at least one of 2, 2-diethoxy acetophenone, benzophenone, 4-phenyl benzophenone, chlorinated benzophenone and the like. The thixotropic agent may be at least one of hydrogenated castor oil, fumed silica, polyamide wax, and the like. The reactive diluent can be at least one of tetrahydrofuran acrylate, ditrimethylol propane acrylate, pentaerythritol tetraacrylate and the like.

Preparing the high heat-conducting medium ceramic green body with the pore structure arranged in an array. The layer-by-layer process can be carried out by adopting a model designed by a 3D printing technology according to the periodic structure parameters of the pore canalAnd printing to obtain the high heat-conducting medium ceramic green bodies with the pore channel structures arranged in an array. In an alternative embodiment, the 3D printing parameters include: the thickness of the single layer can be 0.03-0.05 mm; the illumination intensity can be 2-15 mW/cm². Wherein L is the wall thickness between the porous channels in the ceramic body with high heat conductivity. The pore structure is round, regular polygon or rectangle. The regular polygon can be a regular triangle, a square, a regular hexagon, etc. The side length (or diameter) of the pore channel structure can be adjusted adaptively according to L and delta.

And preparing colloidal fluorescent ceramic main body medium slurry (colloidal fluorescent ceramic slurry for short). Specifically, fluorescent ceramic dielectric powder, a dispersant, a curing agent and a solvent are mixed. The fluorescent ceramic dielectric powder can be rare earth doped transparent ceramic (e.g., YAG: Ce, Al)₂O₃/YAG:Ce、Lu₂O₃:Tm、Y₂O₃:Dy、LuAG:Pr、La₂Hf₂O₇:Ce、YVO₄:Ce、CaAlSiN₃Eu ceramics, etc.). In an optional embodiment, the fluorescent ceramic dielectric powder accounts for 70-82 wt%, preferably 78-82 wt% of the total mass of the slurry. The dispersing agent accounts for 0.2-0.8% of the total mass of the powder. The curing agent accounts for 0.1-0.3% of the total mass of the powder. The mass fraction of the solvent is determined by the contents of the fluorescent ceramic dielectric powder, the curing agent and the dispersing agent. Wherein the dispersant can be isobutylene-maleic anhydride copolymer-600, etc. The curing agent may be isobutylene-maleic anhydride copolymer-104 or the like. The solvent may be deionized water or the like.

And filling the colloidal fluorescent ceramic main body medium slurry into the periodic pore channel structure of the high-heat-conductivity medium ceramic main body green body by adopting a colloidal forming technology to obtain the complex-phase fluorescent ceramic green body. Specifically, the filling and forming process includes: and injecting the colloidal fluorescent ceramic main body medium slurry into the pore channel structure of the high heat-conducting medium ceramic green body with the pore channel structure in array arrangement and performing spontaneous solidification. For example, the spontaneous solidification process is generally completed by curing at room temperature (22-28 ℃) for 10-30 hours.

And (3) carrying out degreasing heat treatment on the complex-phase fluorescent ceramic blank to remove organic matters, thus obtaining a ceramic biscuit with strength. In an optional embodiment, the temperature of the degreasing heat treatment may be 800-1200 ℃, the time may be 1-5 hours, and the temperature rise rate may be 0.1-1 ℃/min.

And sintering the ceramic biscuit at high temperature to obtain the compact complex phase fluorescent ceramic. Wherein the high temperature sintering may be vacuum sintering. In an optional embodiment, the temperature of the vacuum sintering can be 1650-1780 ℃, the heat preservation time can be 0.5-20 hours, and the vacuum degree is not lower than 10^-3Pa. Preferably, the obtained complex phase fluorescent ceramic is annealed for 2-10 hours in an annealing furnace at 1300-1500 ℃, and the purpose is to eliminate the internal stress of the complex phase ceramic and eliminate the oxygen vacancy defect.

In the present disclosure, the multiphase fluorescent ceramics with different duty ratios of the heat conduction channels can be obtained by adjusting L and δ. And under the excitation of ultraviolet light or blue light, the surface equilibrium temperature of the obtained fluorescent ceramic with the heat conduction channel enhanced heat transport is obviously reduced compared with that of the fluorescent ceramic with a non-directional heat transport structure, namely the directional heat transport capability is obviously improved.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1

The preparation process of the fluorescent ceramic with the complex phase inside in the embodiment 1 comprises the following steps:

(1) accurately weigh 80g of Al₂O₃And adding 19.3g of photosensitive resin into the ceramic powder, mixing, and fully mixing by adopting a planetary mill to obtain ceramic slurry. The composition of the photosensitive resin contained 12.3g of an epoxy acrylate resin, 1.2g of an epoxy resin, 1.2g of 2, 2-diethoxyacetophenone, 0.8g of hydrogenated castor oil and 3.8g of tetrahydrofuran acrylate;

(2) as shown in FIG. 1, the internal periodic structure parameters of the periodic structure multiphase fluorescent ceramic are designed as follows: delta is 40%; setting the pore structure into a regular hexagon, setting the wall thickness among porous pores in the matrix to be 300 mu m, setting the effective side length of the pore structure to be 700 mu m, and inputting the effective side length into a 3D printer program;

(3) and pouring the obtained ceramic slurry into a trough of a 3D printer, and printing the alumina ceramic green bodies arranged in an array form in the pore channel framework according to design parameters. Wherein the 3D printing parameters include: the single layer thickness is 0.02 mm; the illumination intensity is 6mW/cm²；

(4) Accurately weigh 100g of 20wt% Al₂O₃YAG, 0.4 mol% Ce fluorescent main body powder, adding 27g deionized water, 0.2g dispersant and 0.3g curing agent, mixing and fully mixing by adopting a planetary ball mill to obtain colloidal fluorescent ceramic main body medium slurry;

(5) injecting the colloidal fluorescent ceramic slurry into the alumina ceramic frame pore channel, and performing spontaneous solidification to obtain ceramic with alumina as shell and Al as matrix₂O₃/YAG:Ce³⁺A complex phase fluorescent ceramic body which is a core;

(6) degreasing the obtained complex phase fluorescent ceramic blank in a muffle furnace, wherein the specific process comprises the following steps: heating to 1100 ℃ at the heating rate of 0.2 ℃/min, and then preserving heat for 2 hours to obtain a composite ceramic biscuit;

(7) sintering the composite ceramic biscuit by adopting a vacuum reaction technology, wherein the specific process comprises the following steps: vacuum degree of not less than 10^-3Pa, heating to 1720 deg.C and keeping the temperature for 6 hours. And then carrying out annealing treatment in an annealing furnace at 1400 ℃ after furnace cooling, wherein the heat preservation time is 6 hours, so as to obtain the complex phase fluorescent ceramic with the aluminum oxide polycrystalline ceramic channels arranged in a periodic manner, and the microstructure of the complex phase fluorescent ceramic is shown in figure 2.

As shown in fig. 3, depending on the high thermal conductivity of alumina, the equilibrium temperature of the complex phase fluorescent ceramic with the alumina polycrystalline ceramic channels arranged in an array is 34.2 ℃ under the excitation of a laser source with a power of 1.60W, 40.4 ℃ under the excitation of a laser source with a power of 3.38W, 45.7 ℃ under the excitation of a laser source with a power of 4.93W, 53.9 ℃ under the excitation of a laser source with a power of 6.47W, and 62.6 ℃ under the excitation of a laser source with a power of 8.13W, compared with the fluorescent ceramic without the ceramic matrix with the high thermal conductivity medium in comparative example 1, the equilibrium temperature of the complex phase fluorescent ceramic is respectively reduced by 12.8%, 26.9%, 29.8%, 31.5%, and 25.2%, and the thermal transport capacity is significantly improved.

Comparative example 1

The preparation process of the fluorescent ceramic without the ceramic matrix of the high thermal conductivity medium in the comparative example 1 includes:

(1) accurately weigh 100g of 20wt% Al₂O₃YAG, 0.4 mol% Ce fluorescent main body powder, adding 27g deionized water, 0.2g dispersant and 0.3g curing agent, mixing and fully mixing by adopting a planetary ball mill to obtain colloidal fluorescent ceramic main body medium slurry;

(2) injecting the colloidal fluorescent ceramic slurry into a plastic mold, and performing spontaneous solidification to obtain Al₂O₃YAG 0.4 mol% Ce fluorescent ceramic green body;

(3) degreasing the fluorescent ceramic blank in a muffle furnace, wherein the specific process comprises the following steps: heating to 1100 ℃ at the heating rate of 0.2 ℃/min, and then preserving heat for 2 hours to obtain a biscuit;

(4) sintering the ceramic biscuit by adopting a vacuum reaction technology, wherein the specific process comprises the following steps: vacuum degree of not less than 10^-3Pa, heating to 1720 deg.C and keeping the temperature for 6 hours. And then, cooling along with the furnace, and then annealing treatment is carried out in an annealing furnace at 1400 ℃, the heat preservation time is 6 hours, so that the fluorescent ceramic is obtained, and the processing is carried out so that the thickness of the fluorescent ceramic is consistent with that of the complex phase ceramic in the embodiment 1.

As shown in fig. 4, in the fluorescent ceramic of the ceramic substrate without high thermal conductivity medium in comparative example 1, the equilibrium temperature of the lower surface of the fluorescent ceramic is 38.6 ℃ when excited by a laser source with a power of 1.60W, 55.3 ℃ when excited by a laser source with a power of 3.38W, 65.1 ℃ when excited by a laser source with a power of 4.93W, 78.7 ℃ when excited by a laser source with a power of 6.47W, and 83.7 ℃ when excited by a laser source with a power of 8.13W.

Example 2

The complex phase fluorescent ceramic in the embodiment 2 is basically the same as the embodiment 1, except that: ce is selected as a fluorescent ceramic main body (the doping amount is 0.15mol percent), MgO is selected as a high heat-conducting medium ceramic matrix, L is 450 mu m, and delta is 28 percent.

By means of the high heat conduction characteristic of MgO, the balance temperature of the surface of the periodic structure multiphase fluorescent ceramic excited by a laser source with the power of 8.13W is 66.5 ℃, compared with the fluorescent ceramic without the high heat conduction medium ceramic matrix in the comparative example 2, the surface balance temperature is reduced by 25.6%, and the heat transfer capacity is remarkably improved.

Comparative example 2

The preparation process of the fluorescent ceramic in the comparative example 2 is basically consistent with that of the comparative example 1, and the difference is that: LuAG, 0.15 mol% Ce was selected as the phosphor.

In the comparative example 2, the surface equilibrium temperature of the fluorescent ceramic without the ceramic matrix of the high thermal conductive medium is 89.4 ℃ when the laser source of 8.13W excites the surface.

Comparative example 3

The preparation process of the fluorescent ceramic in the comparative example 3 is basically consistent with that of the comparative example 2, and the difference is that: a composite powder consisting of 78g of LuAG-Ce and 22g of MgO powder is selected as the powder for the fluorescent body.

In the multiphase fluorescent ceramic obtained in the comparative example 3, MgO is dispersed and distributed, a continuous heat conduction channel is difficult to form, and the balance temperature of the lower surface of the multiphase fluorescent ceramic excited by a laser source with the power of 8.13W is 79.2 ℃.

Claims

1. A complex phase fluorescent ceramic, comprising: the high-heat-conductivity medium ceramic matrix comprises a high-heat-conductivity medium ceramic matrix and fluorescent ceramic main bodies which are distributed in the high-heat-conductivity medium ceramic matrix and are periodically arranged; the shortest distance L between adjacent fluorescent ceramic main bodies is 200-1000 mu m, and the volume fraction delta of the high-heat-conductivity medium ceramic main bodies in the complex-phase fluorescent ceramic is 5-60%;

2. The complex phase fluorescent ceramic according to claim 1, wherein L is less than or equal to 300 μm and less than or equal to 500 μm; delta is between 10 and 40 percent.

3. The complex phase fluorescent ceramic as claimed in claim 1 or 2, wherein the fluorescent ceramic body comprises YAG, RE, and Al₂O₃/YAG:RE、Lu₂O₃:RE、Y₂O₃:RE、LuAG:RE、La₂Hf₂O₇:RE、YVO₄:RE、CaAlSiN₃At least one of RE; wherein RE is selected from Ce³⁺、Eu²⁺、Pr³⁺、Cr³⁺、Tb³⁺、Sm³⁺、Dy³⁺、Ho³⁺And Tm³⁺At least one of; the doping amount of RE is preferably 0.1 to 2 mol%.

4. The complex phase fluorescent ceramic according to any one of claims 1 to 3, wherein the cross-sectional shape of the fluorescent ceramic body is a circle, a regular polygon, or a rectangle.

5. A method of preparing a complex phase fluorescent ceramic as claimed in any one of claims 1 to 4, comprising:

6. The preparation method according to claim 5, wherein the high thermal conductivity medium ceramic powder and the photosensitive resin are mixed to serve as raw materials, and the high thermal conductivity medium ceramic with the pore structure arranged in an array is prepared by adopting a 3D printing technologyA ceramic green body; the photosensitive resin accounts for 18-40 wt% of the total mass of the raw materials, and preferably 21-26 wt%; the parameters of the 3D printing technique include: the thickness of the single layer is 0.02-0.05 mm; the illumination intensity is 2-15 mW/cm²。

7. The preparation method according to claim 6, wherein the photosensitive resin comprises an epoxy acrylate resin, an epoxy resin, a photoinitiator, a thixotropic agent and a reactive diluent; more preferably, the photosensitive resin comprises 55-65 wt% of epoxy acrylate resin, 6-15 wt% of epoxy resin, 4-8 wt% of photoinitiator, 2-5 wt% of thixotropic agent and 10-20 wt% of reactive diluent, and the sum of the mass percentages of the components is 100 wt%.

8. The method of any one of claims 5-7, wherein the colloidal fluorescent ceramic host media slurry comprises: the fluorescent ceramic dielectric powder comprises fluorescent ceramic dielectric powder, a dispersing agent, a curing agent and deionized water, wherein the fluorescent ceramic dielectric powder accounts for 70-82 wt% of the total mass of the colloidal fluorescent ceramic main body dielectric slurry, and is preferably 78-82 wt%; preferably, the components of the colloidal fluorescent ceramic host medium slurry further include: 0.2 to 0.8wt% of a dispersant and 0.1 to 0.3wt% of a curing agent.

9. The method of any one of claims 5 to 8, wherein the colloidal shaping technique comprises: and injecting the colloidal fluorescent ceramic main body medium slurry into the high heat conduction medium ceramic green bodies with the pore structure arranged in an array manner, and curing for 10-30 hours at room temperature.

10. The method according to any one of claims 5 to 9, wherein the degreasing is performed at a temperature of 800 to 1200 ℃ for 1 to 5 hours; preferably, the temperature rise rate of the degreasing is 0.1-1 ℃/min.

11. The production method according to any one of claims 5 to 10, wherein the sintering is performed by vacuum reaction sintering; the above-mentionedThe temperature of the vacuum reaction sintering is 1650-1780 ℃, the time is 0.5-20 hours, and the vacuum degree is not lower than 10^-3Pa。