WO2019179119A1 - Light-emitting ceramic and preparation method therefor - Google Patents

Light-emitting ceramic and preparation method therefor Download PDF

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WO2019179119A1
WO2019179119A1 PCT/CN2018/113869 CN2018113869W WO2019179119A1 WO 2019179119 A1 WO2019179119 A1 WO 2019179119A1 CN 2018113869 W CN2018113869 W CN 2018113869W WO 2019179119 A1 WO2019179119 A1 WO 2019179119A1
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powder
yag
luminescent
luminescent ceramic
light
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PCT/CN2018/113869
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French (fr)
Chinese (zh)
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李乾
胡飞
许颜正
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深圳光峰科技股份有限公司
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Definitions

  • the invention relates to a luminescent ceramic and a preparation method thereof, and belongs to the technical field of solid luminescent materials manufacturing.
  • infrared camera technology In order to meet the needs of all-weather monitoring, active infrared camera technology has received great attention. After more than 20 years of development, product types emerge in an endless stream, and the application field has spanned both military and civilian use, which has formed a huge market.
  • the core of infrared camera technology is infrared light source.
  • the earliest infrared light source uses halogen lamp + filter technology.
  • the biggest disadvantage of halogen lamp is large volume, insufficient heat dissipation and short life, and the red storm phenomenon is serious. Therefore, this technology has already been used. Be eliminated.
  • LEDs like the development of LEDs in the lighting market, infrared LEDs have also experienced three stages of single LEDs, LED arrays, and LED lattices (similar to COB).
  • the disadvantage of a single LED is that the power is too small and the illumination is not uniform; the LED array is prone to eccentricity, and it is not far away; the LED dot matrix improves the shortcomings of the above two methods, but it still performs under the requirements of long distance and high power. insufficient.
  • there are laser infrared light sources but the current laser infrared light sources have problems such as too concentrated energy, speckle phenomenon, too small angle, high cost, and safety at close distances.
  • a high-energy-density laser can be concentratedly irradiated onto the illuminant to excite a single-point illuminating Lambertian infrared light, which has a small optical spread and is easy to modulate. Speckle, the intensity can be much larger than LED infrared light, and it is the most ideal solution technology for high-power infrared light source in the future. Therefore, an infrared light source with high brightness, high uniformity, long life, and weak light decay is needed.
  • the technical problem to be solved by the present invention is to provide a luminescent ceramic and a preparation method thereof according to the deficiencies of the prior art, by preparing a Nd:YAG precursor powder in advance, and then adopting a vacuum sintering method, a hot pressing/SPS sintering method, and the like.
  • the flux-added Nd:YAG precursor powder and Al 2 O 3 powder are sintered into luminescent ceramics.
  • This luminescent ceramic can be combined with a 808 nm red laser semiconductor to prepare a compact, high-flux infrared light source for safety monitoring. Infrared imaging fields such as military detection.
  • the present invention provides a luminescent ceramic comprising an Al 2 O 3 matrix and a Nd:YAG luminescent center uniformly distributed in the Al 2 O 3 matrix.
  • the Al 2 O 3 has a crystal grain size of 0.5 ⁇ m to 20 ⁇ m
  • the Nd:YAG has a crystal grain size of 1 ⁇ m to 30 ⁇ m.
  • the Al 2 O 3 has a grain size of from 1 ⁇ m to 5 ⁇ m
  • the Nd:YAG has a grain size of from 5 ⁇ m to 17 ⁇ m.
  • the composition of the Nd:YAG luminescent center is Y 3 Al 5 O 12 :Nd.
  • the Nd:YAG luminescence center (220) accounts for 15%-90% of the total mass of the luminescent ceramic.
  • the luminescent ceramic further comprises BaF 2 and/or MgO, and the mass of the BaF 2 and MgO is 0.01% to 3.5% and 0.01% to 3.0%, respectively, of the Al 2 O 3 matrix.
  • the invention also provides a preparation method of a luminescent ceramic, the preparation method comprising:
  • the Y 2 O 3 , Al(OH) 3 , Nd 2 O 3 powder is weighed in a stoichiometric ratio of Y 3 Al 5 O 12 :Nd, and BaF 2 powder is added as a flux to the water.
  • the ball milled powder is calcined, the calcined product is pulverized and sintered under a reducing atmosphere, and the sintered product is pulverized to obtain a Nd:YAG precursor powder.
  • a 1 wt% to 3 wt% aqueous solution of polyethylene glycol is disposed, the Al 2 O 3 powder is mixed with an aqueous solution of polyethylene glycol, and the obtained polyethylene glycol containing Al 2 O 3 powder is obtained.
  • the MgO powder and the BaF 2 powder are added to the aqueous solution and then ball-milled, wherein the MgO powder and the BaF 2 powder respectively account for 0.01% by weight to 3% by weight of the Al 2 O 3 powder.
  • Mg(NO 3 ) 2 ⁇ 6H 2 O is weighed according to a ratio of the mass ratio of MgO to Al 2 O 3 of (0.01-3):100, and the concentration is set to 0.01 (mol/L).
  • a -1 (mol/L) nitrate ethanol solution was added to the Al 2 O 3 powder and ball milled.
  • the Nd:YAG precursor powder accounts for 15% by weight to 90% by weight of the total powder.
  • the present invention prepares the Nd:YAG precursor powder by using a vacuum sintering method, a hot pressing/SPS sintering method, and then sintering the Nd:YAG precursor powder and the Al 2 O 3 powder into a luminescent ceramic.
  • a kind of luminescent ceramic can be matched with a red laser semiconductor of 808 nm to prepare a small-sized infrared light source with high luminous flux, which is used in infrared imaging fields such as safety monitoring and military detection.
  • Figure 1 is a SEM image 1 of the luminescent ceramic of the present invention.
  • Figure 2 is a second SEM image of the luminescent ceramic of the present invention.
  • FIG. 3 is a schematic structural view of a luminescent ceramic of the present invention.
  • Fig. 4 is a view showing the emission spectrum of the luminescent ceramic of the present invention under laser excitation.
  • FIG. 1 is an SEM diagram 1 of a luminescent ceramic of the present invention
  • FIG. 2 is an SEM diagram 2 of the luminescent ceramic of the present invention
  • FIG. 3 is a schematic structural view of the luminescent ceramic of the present invention.
  • the present invention provides a luminescent ceramic comprising an Al 2 O 3 matrix 210 and Nd:YAG (Neodymium-doped Yttrium Aluminium Garnet uniformly distributed in the Al 2 O 3 matrix 210). ) illuminating center 220.
  • the black continuous phase in Figures 1 and 2 is an Al 2 O 3 matrix 210, and the off-white particles are Nd:YAG luminescent centers 220.
  • the grain size of Al 2 O 3 is from 0.5 ⁇ m to 20 ⁇ m, and the grain size of Nd:YAG is from 1 ⁇ m to 30 ⁇ m.
  • the grain size of the Al 2 O 3 is from 1 ⁇ m to 5 ⁇ m.
  • the crystal grain size of Nd:YAG is 5 ⁇ m to 17 ⁇ m.
  • the luminescent ceramic can be excited by red light of a wavelength of 500 nm to 820 nm. In particular, it is suitable for excitation by a red laser of 808 nm wavelength, and can emit infrared light of a wavelength of 860-1100 nm. In particular, the light intensity of the wavelength of 1064 nm in the excited light is the most Significant.
  • Fig. 4 is a view showing the emission spectrum of the luminescent ceramic of the present invention under laser excitation. As shown in Fig.
  • the Nd:YAG crystal has a maximum absorption peak at 808 nm, and can emit infrared light with a maximum emission peak at a wavelength of 1064 nm. Dissipate heat.
  • Nd:YAG ceramics whether single crystal ceramics or polycrystalline ceramics, are excited by light at 808 nm wavelength, and only some crystal grains on the surface of the ceramic are excited due to various factors such as material and crystal structure properties. Therefore, for pure phase ceramic Nd:YAG, the excitation light passes through the grain boundary and directly transmits less reflection, so that the excitation light is less likely to be reflected in the ceramic and the optical path is short, thereby exciting the light of Nd:YAG.
  • the amount is small, the light effect of the excitation light is not high, and at the same time, less laser light is generated.
  • the thermal conductivity of Nd:YAG is not high, and the large amount of heat generated by the pure phase Nd:YAG ceramic is excited. If the heat is not released in time, the temperature of the ceramic will rise, which will easily cause Nd:YAG ceramics. Thermal decay reduces light conversion efficiency.
  • the Al 2 O 3 transparent ceramic as a matrix has a very good light transmission property in the near-infrared region of 800 nm to 1600 nm, and can conduct excitation light to the interior of the luminescent ceramic without affecting light propagation.
  • the thermal conductivity can reach 20W/(k ⁇ m)-30W/(k ⁇ m), it can effectively conduct the heat generated during the wavelength conversion process. , is the ideal matrix material.
  • Luminescent ceramic YAG luminescent center 220 consisting of, Nd:: the present invention by the Al 2 O 3 substrate 210 and Nd uniformly distributed in Al 2 O 3 substrate 210, a YAG uniformly dispersed in the Al 2 O 3, increasing the phase interface,
  • the excitation light can be reflected and/or refracted to the interface; at the same time, the lattice structure of Al 2 O 3 and its material properties also cause more reflection and/or more on the grain boundary of Al 2 O 3 Refraction, such that incident light is directed multiple times to different Nd:YAG excitations. Therefore, the incident light has a longer optical path in the luminescent ceramic than the pure phase ceramic, and the absorption of the incident excitation light is more sufficient.
  • the quality of all Nd:YAG luminescent centers 220 and the total mass of the luminescent ceramics is 15%-90%.
  • the content of Nd:YAG luminescent center is too low, the luminescent center is too small and the efficiency is not high; when the content of Nd:YAG luminescent center is too high, the matrix bonding phase alumina content is too small, sintering is difficult, and it is difficult to form a dense ceramic.
  • the mass ratio of the Nd:YAG luminescent center 220 is 40% to 60%, and the number of luminescent centers is moderate, the matrix phase is also easy to be sintered, and the relative density of the luminescent ceramics is easily maximized, so the luminous efficiency is high.
  • the thermal conductivity and mechanical properties are optimized.
  • the luminescent ceramic further comprises BaF 2 and/or MgO, and the mass of the BaF 2 and MgO is 0.01% to 3.5% and 0.01% to 3.0%, respectively, of the Al 2 O 3 matrix.
  • BaF 2 accounted for 0.5% Al 2 O 3 matrix
  • MgO accounted for 0.4% Al 2 O 3 matrix.
  • BaF 2 as a flux can effectively reduce the temperature of the luminescent ceramics in the sintering process, so that Nd:YAG is not easy to enter the sintering, and the morphology of the Nd:YAG particles is prevented from being damaged, which affects the luminescence effect;
  • the addition of MgO is for Purifying the grain boundary of the matrix alumina and inhibiting the abnormal growth of the alumina grains, the sintering performance of the matrix phase is better, and the light transmission performance is stronger.
  • the invention also provides a preparation method of the above luminescent ceramic, the preparation method comprising:
  • the Y 2 O 3 , Al(OH) 3 , Nd 2 O 3 powder is accurately weighed according to the stoichiometric ratio of Y 3 Al 5 O 12 :Nd, and then BaF 2 powder having a total mass of 0.5 wt% is added as a powder.
  • the flux was ball-milled with alumina balls using water or ethanol as a carrier for 24 h.
  • the ball-milled powder was dried, ground and refined on a mortar, and calcined at 1400 ° C for 2 h, and the calcined product was pulverized using a mortar.
  • the powder pulverized in the mortar is placed in an atmosphere furnace and sintered in a reducing atmosphere (such as a nitrogen-hydrogen atmosphere) at 1500 ° C for 2 h to 12 h.
  • a reducing atmosphere such as a nitrogen-hydrogen atmosphere
  • the product is pulverized, washed, dried, and sieved to obtain a component of Y 3 Al.
  • the Nd:YAG precursor powder of 5 O 12 :Nd, the particle D 50 (50% pass particle diameter) of the Nd:YAG precursor powder ranges from 1 ⁇ m to 30 ⁇ m, preferably from 5 ⁇ m to 17 ⁇ m.
  • the preparation of the Nd:YAG precursor powder may be carried out by a coprecipitation method in addition to the above solid phase method.
  • a certain amount of high-purity Al 2 O 3 powder is weighed, and the powder has a particle diameter of 0.05 ⁇ m to 1 ⁇ m, preferably 0.06 ⁇ m to 0.2 ⁇ m, and a 1 wt% to 3 wt% aqueous solution of PEG (polyethylene glycol) is disposed.
  • PEG polyethylene glycol
  • the Al 2 O 3 nanopowder was mixed with an aqueous PEG solution.
  • the Al 2 O 3 powder is dispersed as much as possible in the solution, and the Al 2 O 3 solution is ultrasonicated for 1 h to 3 h and then used.
  • MgO, BaF 2 powder An appropriate amount of high-purity MgO, BaF 2 powder was weighed as a flux, and these two powders were added to an aqueous PEG solution containing Al 2 O 3 powder.
  • the MgO and BaF 2 powders respectively account for 0.01% by weight to 3% by weight of the mass of the Al 2 O 3 powder.
  • the mass of the MgO and BaF 2 powders are equal to 0.05% by weight to 0.4wt of the mass of the Al 2 O 3 powder. %.
  • the above Al 2 O 3 solution added with MgO, BaF 2 powder is charged into a polytetrafluoroethylene ball mill tank, and ball milled with an ultra-low wear rate zirconia ball, and the ball milling time is 1 h-72 h, preferably 24 h-36 h. .
  • the Nd:YAG precursor powder prepared in S1 is placed in the above-mentioned polytetrafluoroethylene ball mill tank, mixed with the ball-milled Al 2 O 3 solution containing MgO and BaF 2 , and then ball milled at a low speed.
  • the time is from 10 min to 120 min, preferably 40 min.
  • the Nd:YAG precursor powder accounts for 15% by weight to 90% by weight of the total powder.
  • the resulting slurry was dried and granulated using a spray drying apparatus to obtain a dry powder.
  • the dry powder is calcined in a muffle furnace at a temperature of from 500 ° C to 650 ° C to remove organic components in the powder for a period of from 1 h to 10 h.
  • the calcined powder was granulated through a mesh of 80 mesh, 150 mesh, and 200 mesh to obtain a raw material powder having high fluidity.
  • the present invention does not limit the above process parameters (temperature, pressure, time, etc.), and those skilled in the art can adjust the above process parameters according to actual needs, and can also be used in addition to SPS and hot press sintering.
  • the vacuum sintering furnace is sintered.
  • the luminescence ceramics prepared in the present embodiment were tested for light efficiency.
  • the luminous efficacy in the present invention specifically refers to infrared light of 1000 nm to 1100 nm excited by a 808 nm laser, and the luminous efficacy thereof is 62 lm/W.
  • the first embodiment has the same steps S1 and S2, except that in S2, a certain amount of powder having a particle diameter of 0.05 ⁇ m-1 ⁇ m (preferably 0.06 ⁇ m-0.2 ⁇ m) is weighed. After the pure Al 2 O 3 powder, a certain amount of Mg(NO 3 ) 2 ⁇ 6H 2 O is weighed according to the ratio of the mass ratio of MgO to Al 2 O 3 of (0.01-3):100, and the concentration is set to 0.01. A (mol/L)-1 (mol/L) nitrate ethanol solution was added to the Al 2 O 3 powder and stirred.
  • S2 a certain amount of powder having a particle diameter of 0.05 ⁇ m-1 ⁇ m (preferably 0.06 ⁇ m-0.2 ⁇ m) is weighed. After the pure Al 2 O 3 powder, a certain amount of Mg(NO 3 ) 2 ⁇ 6H 2 O is weighed according to the ratio of the mass ratio of MgO to Al 2 O 3 of (0.01-3):100, and the concentration is set
  • the above-mentioned nitrate ethanol solution to which the Al 2 O 3 powder is added is charged into a polytetrafluoroethylene ball mill tank, and ball-milled with an ultra-low wear rate zirconia ball, and the ball milling time is 1 h to 72 h, preferably 24 h to 36 h.
  • the nitrate ethanol solution prepared by using Mg(NO 3 ) 2 ⁇ 6H 2 O is used instead of the PEG (polyethylene glycol) aqueous solution and the MgO and BaF 2 powders, and the preparation method is simple, and When the dry powder is calcined in S3, Mg(NO 3 ) 2 ⁇ 6H 2 O can be decomposed into MgO, which also has the action of a flux.
  • the light-emitting ceramics prepared in this example were tested for light efficiency, and the luminous efficacy was 66 lm/W.
  • the present invention preliminarily prepares a Nd:YAG precursor powder, and then uses a vacuum sintering method, a hot pressing/SPS sintering method and the like to sinter the flux-added Nd:YAG precursor powder and Al 2 O 3 powder into a powder.
  • Luminous ceramics which can be combined with 808nm red laser semiconductors to produce small-sized, high-intensity infrared light sources for infrared imaging in security surveillance and military detection.

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Abstract

Disclosed is a light-emitting ceramic, comprising an Al2O3 matrix (210) and an Nd:YAG light-emitting center (220) uniformly distributed in an Al2O3 matrix. A method for preparing the light-emitting ceramic comprises: preparing an Nd: YAG precursor powder in advance, and then sintering the Nd: YAG precursor powder, to which a fluxing agent has been added, and Al2O3 powder into the light-emitting ceramic by means of a process such as a vacuum sintering method or a hot pressing /SPS sintering method. The light-emitting ceramic may be combined with an 808 nm red laser semiconductor to prepare an infrared light source with a small volume and a high luminous flux for use in infrared imaging fields such as safety monitoring and military detection.

Description

发光陶瓷及其制备方法Luminous ceramic and preparation method thereof 技术领域Technical field
本发明涉及一种发光陶瓷及其制备方法，属于固体发光材料制造技术领域。The invention relates to a luminescent ceramic and a preparation method thereof, and belongs to the technical field of solid luminescent materials manufacturing.
背景技术Background technique
为了满足全天候监控的需要，主动红外摄像技术获得了极大关注，经过20多年的发展，产品种类层出不穷，应用领域横跨军民两用，已经形成了一个巨大的市场。红外摄像技术的核心是红外光源，最早的红外光源使用卤素灯+滤光片的技术，卤素灯的最大缺点是体积大、散热不充分且寿命极短，红暴现象严重，因此这种技术已经被淘汰。取代卤素灯的是LED，如同照明市场LED的发展，红外用LED也经历了单颗LED、LED阵列、LED点阵(类似COB)三个阶段。单颗LED的缺点是功率太小且光照不均匀；LED阵列易产生偏心现象，且照不远；LED点阵改善了前述两种方式的缺点，但是在远距离、高功率的要求下表现还是不足。除LED外还有激光红外光源，但当前的激光红外光源还有能量太集中、散斑现象、角度太小、成本高、近距离时的安全性等问题没有得到很好解决。In order to meet the needs of all-weather monitoring, active infrared camera technology has received great attention. After more than 20 years of development, product types emerge in an endless stream, and the application field has spanned both military and civilian use, which has formed a huge market. The core of infrared camera technology is infrared light source. The earliest infrared light source uses halogen lamp + filter technology. The biggest disadvantage of halogen lamp is large volume, insufficient heat dissipation and short life, and the red storm phenomenon is serious. Therefore, this technology has already been used. Be eliminated. Instead of halogen lamps, LEDs, like the development of LEDs in the lighting market, infrared LEDs have also experienced three stages of single LEDs, LED arrays, and LED lattices (similar to COB). The disadvantage of a single LED is that the power is too small and the illumination is not uniform; the LED array is prone to eccentricity, and it is not far away; the LED dot matrix improves the shortcomings of the above two methods, but it still performs under the requirements of long distance and high power. insufficient. In addition to LEDs, there are laser infrared light sources, but the current laser infrared light sources have problems such as too concentrated energy, speckle phenomenon, too small angle, high cost, and safety at close distances.
使用激光激发红外光的光致发光技术，可以使高能量密度的激光集中照射于发光体之上，激发出单点发光的朗伯红外光，这种光的光学扩展量小，易调制，无散斑，强度可远大于LED红外光，安全性高，是未来大功率红外光源的最理想解决方案技术。因此，亟需一种高亮度、高均匀性、长寿命、弱光衰的红外光源。Using a photoluminescence technology that uses laser excitation of infrared light, a high-energy-density laser can be concentratedly irradiated onto the illuminant to excite a single-point illuminating Lambertian infrared light, which has a small optical spread and is easy to modulate. Speckle, the intensity can be much larger than LED infrared light, and it is the most ideal solution technology for high-power infrared light source in the future. Therefore, an infrared light source with high brightness, high uniformity, long life, and weak light decay is needed.
发明内容Summary of the invention
本发明所要解决的技术问题在于针对现有技术的不足，提供一种发光陶瓷及其制备方法，通过预先制备Nd:YAG前驱粉体，之后采用 真空烧结法、热压/SPS烧结法等工艺将加有助熔剂的Nd:YAG前驱粉体、Al 2O 3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。 The technical problem to be solved by the present invention is to provide a luminescent ceramic and a preparation method thereof according to the deficiencies of the prior art, by preparing a Nd:YAG precursor powder in advance, and then adopting a vacuum sintering method, a hot pressing/SPS sintering method, and the like. The flux-added Nd:YAG precursor powder and Al 2 O 3 powder are sintered into luminescent ceramics. This luminescent ceramic can be combined with a 808 nm red laser semiconductor to prepare a compact, high-flux infrared light source for safety monitoring. Infrared imaging fields such as military detection.
本发明所要解决的技术问题是通过如下技术方案实现的：The technical problem to be solved by the present invention is achieved by the following technical solutions:
本发明提供一种发光陶瓷，所述发光陶瓷包括Al 2O 3基质以及均匀分布在Al 2O 3基质中的Nd:YAG发光中心。 The present invention provides a luminescent ceramic comprising an Al 2 O 3 matrix and a Nd:YAG luminescent center uniformly distributed in the Al 2 O 3 matrix.
优选地，所述Al 2O 3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm。 Preferably, the Al 2 O 3 has a crystal grain size of 0.5 μm to 20 μm, and the Nd:YAG has a crystal grain size of 1 μm to 30 μm.
优选地，所述Al 2O 3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。 Preferably, the Al 2 O 3 has a grain size of from 1 μm to 5 μm, and the Nd:YAG has a grain size of from 5 μm to 17 μm.
优选地，所述Nd:YAG发光中心的组分为Y 3Al 5O 12:Nd。 Preferably, the composition of the Nd:YAG luminescent center is Y 3 Al 5 O 12 :Nd.
优选地，所述Nd:YAG发光中心(220)占发光陶瓷总质量的15％-90％。Preferably, the Nd:YAG luminescence center (220) accounts for 15%-90% of the total mass of the luminescent ceramic.
优选地，所述发光陶瓷还包括BaF 2和/或MgO，所述BaF 2、MgO的质量分别占所述Al 2O 3基质的0.01％～3.5％、0.01％～3.0％。 Preferably, the luminescent ceramic further comprises BaF 2 and/or MgO, and the mass of the BaF 2 and MgO is 0.01% to 3.5% and 0.01% to 3.0%, respectively, of the Al 2 O 3 matrix.
本发明还提供一种发光陶瓷的制备方法，所述制备方法包括：The invention also provides a preparation method of a luminescent ceramic, the preparation method comprising:
S1：制备Nd:YAG前驱粉体；S1: preparing a Nd:YAG precursor powder;
S2：制备含Al 2O 3粉末的水溶液； S2: preparing an aqueous solution containing Al 2 O 3 powder;
S3：将Nd:YAG前驱粉体与含Al 2O 3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。 S3: mixing the Nd:YAG precursor powder with an aqueous solution containing Al 2 O 3 powder, and then drying and granulating to obtain a dry powder, which is calcined, granulated, and then sintered to obtain a luminescent ceramic.
优选地，在S1中，按Y 3Al 5O 12:Nd的化学计量比称量Y 2O 3、Al(OH) 3、Nd 2O 3粉末，并加入BaF 2粉末作为助熔剂，以水或乙醇作为载体进行球磨，球磨后的粉料进行煅烧，煅烧产物粉碎后在还原气氛下烧结，烧结产物粉碎后得到Nd：YAG前驱粉体。 Preferably, in S1, the Y 2 O 3 , Al(OH) 3 , Nd 2 O 3 powder is weighed in a stoichiometric ratio of Y 3 Al 5 O 12 :Nd, and BaF 2 powder is added as a flux to the water. Or ethanol as a carrier for ball milling, the ball milled powder is calcined, the calcined product is pulverized and sintered under a reducing atmosphere, and the sintered product is pulverized to obtain a Nd:YAG precursor powder.
优选地，在S2中，配置1wt％-3wt％的聚乙二醇水溶液，将Al 2O 3粉末与聚乙二醇水溶液混合，并在制得的含Al 2O 3粉末的聚乙二醇水溶液中加入MgO粉末和BaF 2粉末后球磨，其中，MgO粉末、BaF 2粉末分别占Al 2O 3粉末的0.01wt％-3wt％。 Preferably, in S2, a 1 wt% to 3 wt% aqueous solution of polyethylene glycol is disposed, the Al 2 O 3 powder is mixed with an aqueous solution of polyethylene glycol, and the obtained polyethylene glycol containing Al 2 O 3 powder is obtained. The MgO powder and the BaF 2 powder are added to the aqueous solution and then ball-milled, wherein the MgO powder and the BaF 2 powder respectively account for 0.01% by weight to 3% by weight of the Al 2 O 3 powder.
优选地，在S2中，按照MgO与Al 2O 3的质量比为(0.01-3):100的 比例，称取Mg(NO 3) 2·6H 2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al 2O 3粉末后球磨。 Preferably, in S2, Mg(NO 3 ) 2 ·6H 2 O is weighed according to a ratio of the mass ratio of MgO to Al 2 O 3 of (0.01-3):100, and the concentration is set to 0.01 (mol/L). A -1 (mol/L) nitrate ethanol solution was added to the Al 2 O 3 powder and ball milled.
优选地，在S3中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。Preferably, in S3, the Nd:YAG precursor powder accounts for 15% by weight to 90% by weight of the total powder.
综上所述，本发明通过预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将Nd:YAG前驱粉体、Al 2O 3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。 In summary, the present invention prepares the Nd:YAG precursor powder by using a vacuum sintering method, a hot pressing/SPS sintering method, and then sintering the Nd:YAG precursor powder and the Al 2 O 3 powder into a luminescent ceramic. A kind of luminescent ceramic can be matched with a red laser semiconductor of 808 nm to prepare a small-sized infrared light source with high luminous flux, which is used in infrared imaging fields such as safety monitoring and military detection.
下面结合附图和具体实施例，对本发明的技术方案进行详细地说明。The technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
附图说明DRAWINGS
图1为本发明发光陶瓷的SEM图一；Figure 1 is a SEM image 1 of the luminescent ceramic of the present invention;
图2为本发明发光陶瓷的SEM图二；Figure 2 is a second SEM image of the luminescent ceramic of the present invention;
图3为本发明发光陶瓷的结构示意图；3 is a schematic structural view of a luminescent ceramic of the present invention;
图4为本发明发光陶瓷在激光激发下的发射光谱图。Fig. 4 is a view showing the emission spectrum of the luminescent ceramic of the present invention under laser excitation.
具体实施方式detailed description
图1为本发明发光陶瓷的SEM图一；图2为本发明发光陶瓷的SEM图二；图3为本发明发光陶瓷的结构示意图。如图1至图3所示，本发明提供一种发光陶瓷，所述发光陶瓷包括Al 2O 3基质210以及均匀分布在Al 2O 3基质210中的Nd:YAG(Neodymium-doped Yttrium Aluminium Garnet)发光中心220。图1和图2中的黑色连续相为Al 2O 3基质210，灰白色的颗粒为Nd:YAG发光中心220。 1 is an SEM diagram 1 of a luminescent ceramic of the present invention; FIG. 2 is an SEM diagram 2 of the luminescent ceramic of the present invention; and FIG. 3 is a schematic structural view of the luminescent ceramic of the present invention. As shown in FIGS. 1 to 3, the present invention provides a luminescent ceramic comprising an Al 2 O 3 matrix 210 and Nd:YAG (Neodymium-doped Yttrium Aluminium Garnet uniformly distributed in the Al 2 O 3 matrix 210). ) illuminating center 220. The black continuous phase in Figures 1 and 2 is an Al 2 O 3 matrix 210, and the off-white particles are Nd:YAG luminescent centers 220.
其中，Al 2O 3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm，优选地，所述Al 2O 3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。 Wherein, the grain size of Al 2 O 3 is from 0.5 μm to 20 μm, and the grain size of Nd:YAG is from 1 μm to 30 μm. Preferably, the grain size of the Al 2 O 3 is from 1 μm to 5 μm. The crystal grain size of Nd:YAG is 5 μm to 17 μm.
所述发光陶瓷可以被500nm-820nm波长的红光激发，特别的，适用于808nm波长的红激光激发，可以发出860-1100nm波长的红外光， 特别地，被激发光中1064nm波长的光强度最为显著。图4为本发明发光陶瓷在激光激发下的发射光谱图。如图4所示，得益于 4F 3/2→ 4I 9/2的能级跃迁，Nd:YAG晶体在808nm时有最大吸收峰，可发出最大发射峰为1064nm波长的红外光，同时散发热量。 The luminescent ceramic can be excited by red light of a wavelength of 500 nm to 820 nm. In particular, it is suitable for excitation by a red laser of 808 nm wavelength, and can emit infrared light of a wavelength of 860-1100 nm. In particular, the light intensity of the wavelength of 1064 nm in the excited light is the most Significant. Fig. 4 is a view showing the emission spectrum of the luminescent ceramic of the present invention under laser excitation. As shown in Fig. 4, thanks to the energy level transition of 4 F 3/2 → 4 I 9/2 , the Nd:YAG crystal has a maximum absorption peak at 808 nm, and can emit infrared light with a maximum emission peak at a wavelength of 1064 nm. Dissipate heat.
目前现有的Nd:YAG陶瓷无论是单晶陶瓷还是多晶陶瓷，其在808nm波长的光激发时，仅陶瓷表面部分晶粒进行了激发，因为其材料和晶体结构属性等多个因素的影响，使得对于纯相陶瓷的Nd：YAG，激发光经过晶界会直接透过而较少发生反射，使得激发光在陶瓷中被反射的机会较少从而光程短，进而激发Nd:YAG的光量少，激发光的光效不高，同时产生的受激光也少。同时，Nd:YAG的热导率不高，纯相的Nd:YAG陶瓷被激发而发光所产生的大量热量，若热量未及时传导散发出去，会导致陶瓷温度上升，容易引起Nd:YAG陶瓷的热衰而降低光转换效率。At present, existing Nd:YAG ceramics, whether single crystal ceramics or polycrystalline ceramics, are excited by light at 808 nm wavelength, and only some crystal grains on the surface of the ceramic are excited due to various factors such as material and crystal structure properties. Therefore, for pure phase ceramic Nd:YAG, the excitation light passes through the grain boundary and directly transmits less reflection, so that the excitation light is less likely to be reflected in the ceramic and the optical path is short, thereby exciting the light of Nd:YAG. When the amount is small, the light effect of the excitation light is not high, and at the same time, less laser light is generated. At the same time, the thermal conductivity of Nd:YAG is not high, and the large amount of heat generated by the pure phase Nd:YAG ceramic is excited. If the heat is not released in time, the temperature of the ceramic will rise, which will easily cause Nd:YAG ceramics. Thermal decay reduces light conversion efficiency.
而本发明中，作为基质的Al 2O 3透明陶瓷在800nm-1600nm的近红外区都有非常良好的透光性能，在不会影响光传播的情况下，可将激发光传导至发光陶瓷内部以激发更多的作为发光中心的Nd:YAG陶瓷颗粒，且其热导率可以达到20W/(k·m)-30W/(k·m)，能有效将波长转换过程中产生的热量传导出去，是理想的基质材料。本发明中由Al 2O 3基质210以及均匀分布在Al 2O 3基质210中的Nd:YAG发光中心220组成的发光陶瓷，Nd:YAG均匀分散在Al 2O 3中，增加了相界面，激发光可以在向界面之间发生反射和/或折射；同时，Al 2O 3的晶格结构及其材料特性也使得在Al 2O 3的晶界上也会发生较多的反射和/或折射，从而使得入射光被多次导向不同的Nd:YAG进行激发。因此相比纯相陶瓷，入射光在这种发光陶瓷中的光程更长，对入射激发光的吸收也更充分。 In the present invention, the Al 2 O 3 transparent ceramic as a matrix has a very good light transmission property in the near-infrared region of 800 nm to 1600 nm, and can conduct excitation light to the interior of the luminescent ceramic without affecting light propagation. In order to excite more Nd:YAG ceramic particles as the center of luminescence, and its thermal conductivity can reach 20W/(k·m)-30W/(k·m), it can effectively conduct the heat generated during the wavelength conversion process. , is the ideal matrix material. Luminescent ceramic YAG luminescent center 220 consisting of, Nd:: the present invention by the Al 2 O 3 substrate 210 and Nd uniformly distributed in Al 2 O 3 substrate 210, a YAG uniformly dispersed in the Al 2 O 3, increasing the phase interface, The excitation light can be reflected and/or refracted to the interface; at the same time, the lattice structure of Al 2 O 3 and its material properties also cause more reflection and/or more on the grain boundary of Al 2 O 3 Refraction, such that incident light is directed multiple times to different Nd:YAG excitations. Therefore, the incident light has a longer optical path in the luminescent ceramic than the pure phase ceramic, and the absorption of the incident excitation light is more sufficient.
其中，所有Nd:YAG发光中心220的质量和占发光陶瓷总质量的15％-90％。当Nd:YAG发光中心含量过低时，发光中心太少，效率不高；当Nd:YAG发光中心含量过高时，基质粘接相氧化铝含量太少，烧结困难，难以形成致密的陶瓷。优选地，在本发明中，Nd:YAG发光中心220的质量占比为40％～60％，此时发光中心数量适中，基质相也 易于烧结，发光陶瓷的相对密度易于达到最高，因此发光效率、导热性能、力学性能均达到最优。Among them, the quality of all Nd:YAG luminescent centers 220 and the total mass of the luminescent ceramics is 15%-90%. When the content of Nd:YAG luminescent center is too low, the luminescent center is too small and the efficiency is not high; when the content of Nd:YAG luminescent center is too high, the matrix bonding phase alumina content is too small, sintering is difficult, and it is difficult to form a dense ceramic. Preferably, in the present invention, the mass ratio of the Nd:YAG luminescent center 220 is 40% to 60%, and the number of luminescent centers is moderate, the matrix phase is also easy to be sintered, and the relative density of the luminescent ceramics is easily maximized, so the luminous efficiency is high. The thermal conductivity and mechanical properties are optimized.
优选地，发光陶瓷还包括BaF 2和/或MgO，所述BaF 2、MgO的质量分别占所述Al 2O 3基质的0.01％～3.5％、0.01％～3.0％。例如BaF 2占Al 2O 3基质的0.5％，MgO占Al 2O 3基质的0.4％。 Preferably, the luminescent ceramic further comprises BaF 2 and/or MgO, and the mass of the BaF 2 and MgO is 0.01% to 3.5% and 0.01% to 3.0%, respectively, of the Al 2 O 3 matrix. E.g. BaF 2 accounted for 0.5% Al 2 O 3 matrix, MgO accounted for 0.4% Al 2 O 3 matrix.
BaF 2作为助熔剂，能有效降低发光陶瓷在烧结成型工艺中的温度，从而使Nd:YAG不易进入烧结，避免Nd:YAG颗粒的形貌受到破坏，影响发光效果；MgO的加入，则是为了净化基质氧化铝的晶界，并抑制氧化铝晶粒的异常长大，能使基质相的烧结性能更好，透光性能更强。 BaF 2 as a flux can effectively reduce the temperature of the luminescent ceramics in the sintering process, so that Nd:YAG is not easy to enter the sintering, and the morphology of the Nd:YAG particles is prevented from being damaged, which affects the luminescence effect; the addition of MgO is for Purifying the grain boundary of the matrix alumina and inhibiting the abnormal growth of the alumina grains, the sintering performance of the matrix phase is better, and the light transmission performance is stronger.
本发明还提供一种上述发光陶瓷的制备方法，所述制备方法包括：The invention also provides a preparation method of the above luminescent ceramic, the preparation method comprising:
S1：制备Nd:YAG前驱粉体；S1: preparing a Nd:YAG precursor powder;
S2：制备含Al 2O 3粉末的水溶液； S2: preparing an aqueous solution containing Al 2 O 3 powder;
S3：将Nd:YAG前驱粉体与含Al 2O 3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。 S3: mixing the Nd:YAG precursor powder with an aqueous solution containing Al 2 O 3 powder, and then drying and granulating to obtain a dry powder, which is calcined, granulated, and then sintered to obtain a luminescent ceramic.
下面结合具体实施例对制备方法进行详细说明。The preparation method will be described in detail below in conjunction with specific examples.
实施例一 Embodiment 1
在S1中，按Y 3Al 5O 12:Nd的化学计量比准确称量Y 2O 3、Al(OH) 3、Nd 2O 3粉末，之后加入粉末总质量0.5wt％的BaF 2粉末作为助熔剂，以水或乙醇作为载体，用氧化铝球进行球磨混合24h。 In S1, the Y 2 O 3 , Al(OH) 3 , Nd 2 O 3 powder is accurately weighed according to the stoichiometric ratio of Y 3 Al 5 O 12 :Nd, and then BaF 2 powder having a total mass of 0.5 wt% is added as a powder. The flux was ball-milled with alumina balls using water or ethanol as a carrier for 24 h.
将球磨好的粉料干燥后在研钵上进行研磨细化，在1400℃下煅烧2h，煅烧产物使用研钵粉碎。The ball-milled powder was dried, ground and refined on a mortar, and calcined at 1400 ° C for 2 h, and the calcined product was pulverized using a mortar.
将研钵粉碎的粉体放入气氛炉中，在还原气氛(如氮氢气气氛)下，1500℃烧结2h-12h，产物经粉碎、洗涤、烘干、筛分后获得组分为Y 3Al 5O 12:Nd的Nd:YAG前驱粉体，Nd:YAG前驱粉体的颗粒D 50(50％通过粒径)的范围为1μm-30μm，优选为5μm-17μm。 The powder pulverized in the mortar is placed in an atmosphere furnace and sintered in a reducing atmosphere (such as a nitrogen-hydrogen atmosphere) at 1500 ° C for 2 h to 12 h. The product is pulverized, washed, dried, and sieved to obtain a component of Y 3 Al. The Nd:YAG precursor powder of 5 O 12 :Nd, the particle D 50 (50% pass particle diameter) of the Nd:YAG precursor powder ranges from 1 μm to 30 μm, preferably from 5 μm to 17 μm.
需要说明的是，制备Nd:YAG前驱粉体除了可以采用上述固相法外还可以采用共沉淀法。It should be noted that the preparation of the Nd:YAG precursor powder may be carried out by a coprecipitation method in addition to the above solid phase method.
在S2中，称取一定数量的高纯Al 2O 3粉末，粉末粒径为0.05μm-1μm，优选为0.06μm-0.2μm，配置1wt％-3wt％的PEG(聚乙二醇)水 溶液，将Al 2O 3纳米粉末与PEG水溶液混合。优选地，为了破坏Al 2O 3粉末颗粒之间的二次团聚，让Al 2O 3粉末在溶液中尽可能地分散，将Al 2O 3溶液超声1h-3h后备用。 In S2, a certain amount of high-purity Al 2 O 3 powder is weighed, and the powder has a particle diameter of 0.05 μm to 1 μm, preferably 0.06 μm to 0.2 μm, and a 1 wt% to 3 wt% aqueous solution of PEG (polyethylene glycol) is disposed. The Al 2 O 3 nanopowder was mixed with an aqueous PEG solution. Preferably, in order to destroy the secondary agglomeration between the Al 2 O 3 powder particles, the Al 2 O 3 powder is dispersed as much as possible in the solution, and the Al 2 O 3 solution is ultrasonicated for 1 h to 3 h and then used.
称取适量的高纯MgO、BaF 2粉末作为助熔剂，将这两种粉末添加入含Al 2O 3粉末的PEG水溶液中。所述MgO、BaF 2粉末分别占Al 2O 3粉末质量的0.01wt％-3wt％，优选地，MgO、BaF 2粉末的质量一样，均占Al 2O 3粉末质量的0.05wt％-0.4wt％。之后将上述加入MgO、BaF 2粉末的Al 2O 3溶液装入聚四氟乙烯球磨罐中，用超低磨失率的氧化锆球进行球磨，球磨时间为1h-72h，优选为24h-36h。 An appropriate amount of high-purity MgO, BaF 2 powder was weighed as a flux, and these two powders were added to an aqueous PEG solution containing Al 2 O 3 powder. The MgO and BaF 2 powders respectively account for 0.01% by weight to 3% by weight of the mass of the Al 2 O 3 powder. Preferably, the mass of the MgO and BaF 2 powders are equal to 0.05% by weight to 0.4wt of the mass of the Al 2 O 3 powder. %. Then, the above Al 2 O 3 solution added with MgO, BaF 2 powder is charged into a polytetrafluoroethylene ball mill tank, and ball milled with an ultra-low wear rate zirconia ball, and the ball milling time is 1 h-72 h, preferably 24 h-36 h. .
在S3中，将S1中制备的Nd：YAG前驱粉体，装入上述聚四氟乙烯球磨罐，与球磨后的含有MgO、BaF 2的Al 2O 3溶液混合后，低速进行再次球磨，球磨时间为10min-120min，优选为40min。其中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。 In S3, the Nd:YAG precursor powder prepared in S1 is placed in the above-mentioned polytetrafluoroethylene ball mill tank, mixed with the ball-milled Al 2 O 3 solution containing MgO and BaF 2 , and then ball milled at a low speed. The time is from 10 min to 120 min, preferably 40 min. Among them, the Nd:YAG precursor powder accounts for 15% by weight to 90% by weight of the total powder.
球磨结束后，所得浆料使用喷雾干燥设备干燥造粒，获得干粉。After the completion of the ball milling, the resulting slurry was dried and granulated using a spray drying apparatus to obtain a dry powder.
所述干粉在马弗炉中进行500℃-650℃的煅烧，除去粉末中的有机成分，时间为1h-10h。煅烧后的粉末过80目、150目、200目筛造粒，得到高流动性的原料粉。The dry powder is calcined in a muffle furnace at a temperature of from 500 ° C to 650 ° C to remove organic components in the powder for a period of from 1 h to 10 h. The calcined powder was granulated through a mesh of 80 mesh, 150 mesh, and 200 mesh to obtain a raw material powder having high fluidity.
称取适量原料粉末装入石墨模具中，在5MPa-15MPa压强下进行预压制，然后将石墨模具放入SPS放电等离子烧结炉内，在真空或氩气保护气氛下烧结，烧结温度1250℃-1650℃，保温0.5h-6h，烧结压力为30MPa-200MPa，优选为40MPa-100MPa。烧结完成后，卸除压力并随炉冷却。最后获得发光陶瓷。Weigh the appropriate amount of raw material powder into the graphite mold, pre-compact under the pressure of 5MPa-15MPa, then put the graphite mold into the SPS discharge plasma sintering furnace, and sinter under vacuum or argon atmosphere, sintering temperature 1250 ° C -1650 °C, heat preservation 0.5h-6h, sintering pressure is 30MPa-200MPa, preferably 40MPa-100MPa. After the sintering is completed, the pressure is removed and cooled with the furnace. Finally, a luminescent ceramic is obtained.
需要补充的是，本发明并不限制上述工艺参数(温度、压力、时间等)，本领域技术人员可以根据实际需要对上述工艺参数进行调整，另外，除SPS和热压烧结外，还可以使用真空烧结炉进行烧结。It should be noted that the present invention does not limit the above process parameters (temperature, pressure, time, etc.), and those skilled in the art can adjust the above process parameters according to actual needs, and can also be used in addition to SPS and hot press sintering. The vacuum sintering furnace is sintered.
对本实施例中所制备的发光陶瓷进行光效测试，本发明中的光效特指每瓦808nm激光所激发的1000nm-1100nm红外光，其光效达62lm/W。The luminescence ceramics prepared in the present embodiment were tested for light efficiency. The luminous efficacy in the present invention specifically refers to infrared light of 1000 nm to 1100 nm excited by a 808 nm laser, and the luminous efficacy thereof is 62 lm/W.
实施例二Embodiment 2
本实施例与实施例一相比，其S1和S2工序相同，不同处在于，在S2中，在称取一定数量的粉末粒径为0.05μm-1μm(优选为0.06μm-0.2μm)的高纯Al 2O 3粉末后，按照MgO与Al 2O 3的质量比为(0.01-3):100的比例，称取一定数量的Mg(NO 3) 2·6H 2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al 2O 3粉末后搅拌。 Compared with the first embodiment, the first embodiment has the same steps S1 and S2, except that in S2, a certain amount of powder having a particle diameter of 0.05 μm-1 μm (preferably 0.06 μm-0.2 μm) is weighed. After the pure Al 2 O 3 powder, a certain amount of Mg(NO 3 ) 2 ·6H 2 O is weighed according to the ratio of the mass ratio of MgO to Al 2 O 3 of (0.01-3):100, and the concentration is set to 0.01. A (mol/L)-1 (mol/L) nitrate ethanol solution was added to the Al 2 O 3 powder and stirred.
之后将上述加入Al 2O 3粉末的硝酸盐乙醇溶液装入聚四氟乙烯球磨罐中，用超低磨失率的氧化锆球进行球磨，球磨时间为1h-72h，优选为24h-36h。 Thereafter, the above-mentioned nitrate ethanol solution to which the Al 2 O 3 powder is added is charged into a polytetrafluoroethylene ball mill tank, and ball-milled with an ultra-low wear rate zirconia ball, and the ball milling time is 1 h to 72 h, preferably 24 h to 36 h.
本实施例与实施例一相比，用Mg(NO 3) 2·6H 2O制备的硝酸盐乙醇溶液来代替PEG(聚乙二醇)水溶液以及MgO、BaF 2粉末，制备方法较为简单，且在S3中干粉在煅烧时，Mg(NO 3) 2·6H 2O能够分解为MgO，其同样具有助熔剂的作用。 Compared with the first embodiment, the nitrate ethanol solution prepared by using Mg(NO 3 ) 2 ·6H 2 O is used instead of the PEG (polyethylene glycol) aqueous solution and the MgO and BaF 2 powders, and the preparation method is simple, and When the dry powder is calcined in S3, Mg(NO 3 ) 2 ·6H 2 O can be decomposed into MgO, which also has the action of a flux.
对本实施例中所制备的发光陶瓷进行光效测试，其光效达66lm/W。The light-emitting ceramics prepared in this example were tested for light efficiency, and the luminous efficacy was 66 lm/W.
综上所述，本发明预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将加有助熔剂的Nd:YAG前驱粉体、Al 2O 3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。 In summary, the present invention preliminarily prepares a Nd:YAG precursor powder, and then uses a vacuum sintering method, a hot pressing/SPS sintering method and the like to sinter the flux-added Nd:YAG precursor powder and Al 2 O 3 powder into a powder. Luminous ceramics, which can be combined with 808nm red laser semiconductors to produce small-sized, high-intensity infrared light sources for infrared imaging in security surveillance and military detection.

Claims (10)

  1. 一种发光陶瓷，其特征在于，所述发光陶瓷包括Al 2O 3基质(210)以及均匀分布在Al 2O 3基质中的Nd:YAG发光中心(220)。 A luminescent ceramic characterized in that the luminescent ceramic comprises an Al 2 O 3 matrix (210) and an Nd:YAG luminescent center (220) uniformly distributed in the Al 2 O 3 matrix.
  2. 如权利要求1所述的发光陶瓷，其特征在于，所述Al 2O 3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm；优选地，所述Al 2O 3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。 The luminescent ceramic according to claim 1, wherein said Al 2 O 3 has a crystal grain size of from 0.5 μm to 20 μm, and Nd:YAG has a crystal grain size of from 1 μm to 30 μm; preferably, said Al The crystal grain size of 2 O 3 is from 1 μm to 5 μm, and the crystal grain size of the Nd:YAG is from 5 μm to 17 μm.
  3. 如权利要求1所述的发光陶瓷，其特征在于，所述Nd:YAG发光中心(220)的组分为Y 3Al 5O 12:Nd。 The luminescent ceramic according to claim 1, wherein the composition of the Nd:YAG luminescent center (220) is Y 3 Al 5 O 12 :Nd.
  4. 如权利要求1所述的发光陶瓷，其特征在于，所述Nd:YAG发光中心(220)占发光陶瓷总质量的15％-90％。The luminescent ceramic of claim 1 wherein said Nd:YAG luminescent center (220) comprises from 15% to 90% of the total mass of the luminescent ceramic.
  5. 如权利要求1所述的发光陶瓷，其特征在于，所述发光陶瓷还包括BaF 2和/或MgO，所述BaF 2、MgO的质量分别占所述Al 2O 3基质的0.01％～3.5％、0.01％～3.0％。 The luminescent ceramic according to claim 1, wherein the luminescent ceramic further comprises BaF 2 and/or MgO, and the mass of the BaF 2 and MgO is 0.01% to 3.5% of the Al 2 O 3 matrix, respectively. , 0.01% to 3.0%.
  6. 一种发光陶瓷的制备方法，其特征在于，所述制备方法包括：A method for preparing a luminescent ceramic, characterized in that the preparation method comprises:
    S1：制备Nd:YAG前驱粉体；S1: preparing a Nd:YAG precursor powder;
    S2：制备含Al 2O 3粉末的水溶液； S2: preparing an aqueous solution containing Al 2 O 3 powder;
    S3：将Nd:YAG前驱粉体与含Al 2O 3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。 S3: mixing the Nd:YAG precursor powder with an aqueous solution containing Al 2 O 3 powder, and then drying and granulating to obtain a dry powder, which is calcined, granulated, and then sintered to obtain a luminescent ceramic.
  7. 如权利要求6所述的制备方法，其特征在于，在S1中，按Y 3Al 5O 12:Nd的化学计量比称量Y 2O 3、Al(OH) 3、Nd 2O 3粉末，并加入BaF 2粉末作为助熔剂，以水或乙醇作为载体进行球磨，球磨后的粉料进行煅烧，煅烧产物粉碎后在还原气氛下烧结，烧结产物粉碎后得到Nd：YAG前驱粉体。 The preparation method according to claim 6, wherein in S1, Y 2 O 3 , Al(OH) 3 , Nd 2 O 3 powder is weighed according to a stoichiometric ratio of Y 3 Al 5 O 12 :Nd. BaF 2 powder is added as a flux, and water or ethanol is used as a carrier for ball milling. The ball milled powder is calcined, the calcined product is pulverized and sintered under a reducing atmosphere, and the sintered product is pulverized to obtain a Nd:YAG precursor powder.
  8. 如权利要求6所述的制备方法，其特征在于，在S2中，配置1wt％-3wt％的聚乙二醇水溶液，将Al 2O 3粉末与聚乙二醇水溶液混合，并在制得的含Al 2O 3粉末的聚乙二醇水溶液中加入MgO粉末和BaF 2粉末后球磨，其中，MgO粉末、BaF 2粉末分别占Al 2O 3粉末的0.01wt％-3wt％。 The preparation method according to claim 6, wherein in S2, a 1 wt% to 3 wt% aqueous solution of polyethylene glycol is disposed, and the Al 2 O 3 powder is mixed with the aqueous polyethylene glycol solution, and is obtained. The MgO powder and the BaF 2 powder are added to the aqueous solution of the polyethylene glycol containing Al 2 O 3 powder, followed by ball milling, wherein the MgO powder and the BaF 2 powder respectively account for 0.01% by weight to 3% by weight of the Al 2 O 3 powder.
  9. 如权利要求6所述的制备方法，其特征在于，在S2中，按照MgO与Al 2O 3的质量比为(0.01-3):100的比例，称取Mg(NO 3) 2·6H 2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al 2O 3粉末后球磨。 The preparation method according to claim 6, wherein in S2, Mg(NO 3 ) 2 ·6H 2 is weighed according to a ratio of mass ratio of MgO to Al 2 O 3 of (0.01-3):100. O, a nitrate ethanol solution having a concentration of 0.01 (mol/L) -1 (mol/L) is placed, and the Al 2 O 3 powder is added and ball milled.
  10. 如权利要求6至9任一项所述的制备方法，其特征在于，在S3中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。The preparation method according to any one of claims 6 to 9, wherein in S3, the Nd:YAG precursor powder accounts for 15% by weight to 90% by weight of the total powder.
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