WO2021135883A1 - 荧光陶瓷的制备方法及荧光陶瓷 - Google Patents

荧光陶瓷的制备方法及荧光陶瓷 Download PDF

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WO2021135883A1
WO2021135883A1 PCT/CN2020/135099 CN2020135099W WO2021135883A1 WO 2021135883 A1 WO2021135883 A1 WO 2021135883A1 CN 2020135099 W CN2020135099 W CN 2020135099W WO 2021135883 A1 WO2021135883 A1 WO 2021135883A1
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sol
mixed
fluorescent
fluorescent ceramic
alumina
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French (fr)
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李乾
陈雨叁
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深圳市绎立锐光科技开发有限公司
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Definitions

  • This application relates to the technical field of fluorescent ceramics, in particular to a preparation method of fluorescent ceramics and fluorescent ceramics.
  • the present application provides a method for preparing fluorescent ceramics and fluorescent ceramics, which can improve the luminous efficiency of fluorescent ceramics.
  • the present application provides a method for preparing fluorescent ceramics, which includes the following steps: preparing nano alumina sol; mixing the nano alumina sol, vapor-phase nano alumina, and pinning materials in a preset ratio to obtain mixed oxidation
  • the aluminum slurry is prepared from the mixed alumina slurry to obtain fluorescent ceramic precursor powder; and the fluorescent ceramic precursor powder is sintered to obtain fluorescent ceramics.
  • the present application provides a fluorescent ceramic.
  • the fluorescent ceramic includes: a nano-alumina matrix, wherein there are grain boundaries between the crystal grains of the nano-alumina matrix; Phosphor; pinned particles pinned to the intersection of the grain boundaries.
  • the beneficial effect of the present application is: different from the state of the art, the present application prepares nano alumina sol by a sol-gel method, and mixes the nano alumina sol, vapor-phase nano alumina, and pinning materials to obtain mixed alumina Slurry, and the fluorescent ceramic precursor powder is obtained by mixing alumina slurry.
  • the pinning material can be uniformly pinned at the grain boundary between the crystal grains of the alumina matrix, so that a better scattering center can be formed at the grain boundary and the luminous efficiency of the fluorescent ceramic can be improved.
  • FIG. 1 is a schematic flowchart of a first embodiment of a method for preparing fluorescent ceramics according to the present application
  • FIG. 2 is a schematic diagram of the first process of step S20 in FIG. 1;
  • FIG. 3 is a schematic flow chart of a second embodiment of the method for preparing fluorescent ceramics according to the present application.
  • FIG. 4 is a schematic diagram of a second process of step S20 in FIG. 1;
  • FIG. 5 is a schematic flowchart of step S10 in FIG. 1;
  • FIG. 6 is a schematic flowchart of step S40 in FIG. 1;
  • FIG. 7 is a schematic structural diagram of an embodiment of the fluorescent ceramic of this application.
  • the fluorescent materials used in laser illumination and display technology can be roughly divided into three categories.
  • the phosphor is encapsulated by organic polymers such as silicone/organic resin; when the blue laser power increases, when the fluorescent material encapsulated by the organic matrix performs light conversion, the heat generated also increases sharply, causing Its own temperature rises sharply, which in turn causes the encapsulated silica gel/organic resin and other organic substrates to age and yellow, which in turn leads to problems such as loss of light efficiency and reduced life.
  • a fluorescent glass material which is primarily a phosphor encapsulated in SiO 2 -based glass / borosilicate group of.
  • fluorescent glass Compared with organic resin, fluorescent glass has great improvement in heat resistance, high thermal stability, low color shift, etc., but its thermal conductivity is not significantly improved compared with organic resin.
  • Fluorescent ceramics Compared with fluorescent materials encapsulated by organic substrates and inorganic glass substrates, fluorescent ceramics have significant advantages in terms of heat resistance and thermal conductivity. There are two types of fluorescent ceramics. One is prepared by doping rare earth elements in transparent ceramics such as YAG; the other is prepared by encapsulating phosphors in transparent ceramics with high thermal conductivity.
  • Fluorescent ceramics have become an important development direction in laser lighting display technology due to their excellent thermal conductivity and heat resistance. Therefore, how to improve its luminous efficiency is the focus of the industry. Fluorescent ceramics are divided into YAG: Ce 3+ pure phase fluorescent ceramics (including YAG: Ce 3+ single crystal materials) according to their internal structure, and YAG: Ce 3+ composite fluorescent ceramic materials sintered with transparent ceramic materials. Large category; among them, pure phase ceramics are difficult to have a high utilization rate of excitation light due to its own structure; when it is excited, its luminescent center is relatively small, which leads to its poor luminous efficiency. In contrast, this type of multiphase fluorescent ceramics formed by encapsulating phosphors in transparent ceramics has certain advantages. How to further improve the luminous efficiency of this type of multiphase fluorescent ceramics has also become an important research topic in the industry.
  • the present application proposes a method for preparing fluorescent ceramics and fluorescent ceramics.
  • the fluorescent ceramics have small crystal grain sizes and many grain boundaries, and use the scattering effect of the grain boundaries to improve the efficiency of fluorescent ceramics.
  • This application provides a method for preparing fluorescent ceramics. The method includes the following steps:
  • a sol is prepared by the sol-gel method.
  • n (aluminum isopropoxide): n(H 2 O): n(HNO 3 ) 0.5 ⁇ 1.5:3 ⁇ 5:0.02 ⁇ 0.04
  • aluminum isopropoxide is hydrolyzed to obtain alumina.
  • the alumina and stabilizer are refluxed and stirred at 80°C for 2 hours to prepare a clear and transparent nano alumina sol with higher purity.
  • a relatively stable nano alumina sol can be prepared by controlling the hydrolysis temperature and the amount of deionized water.
  • the pinning material is an auxiliary agent or a sol containing an auxiliary agent, wherein the auxiliary agent is zirconium oxide, yttrium oxide, magnesium oxide, calcium oxide, silicon dioxide, titanium dioxide, barium oxide, calcium fluoride, and barium fluoride. At least one.
  • a mixed alumina slurry is prepared from nano alumina sol.
  • the mixed alumina slurry is used as a ball mill slurry, and a certain proportion of micron (5-20 ⁇ m) phosphor or a certain proportion of micron phosphor and micron are added to the mixed alumina slurry.
  • Grade alumina powder is ball milled and mixed, dried, ground and sieved to obtain fluorescent ceramic precursor powder.
  • S40 Sintering the fluorescent ceramic precursor powder to obtain fluorescent ceramics.
  • the fluorescent ceramic precursor powder is hot-pressed and sintered at a lower hot-pressing and sintering temperature (1400 ⁇ 1500°C) and a short holding time (0.5 ⁇ 1.5h) to prepare a small grain size (1 ⁇ 5 ⁇ m)
  • a lower hot-pressing and sintering temperature (1400 ⁇ 1500°C) and a short holding time (0.5 ⁇ 1.5h)
  • a small grain size (1 ⁇ 5 ⁇ m)
  • the uniform YAG-Al 2 O 3 complex phase fluorescent ceramics due to the small grain size and many grain boundaries, utilize the scattering effect of the grain boundaries, thereby improving the efficiency of the fluorescent ceramics.
  • this application prepares nano alumina sol by sol-gel method, and mixes nano alumina sol, gas phase nano alumina, and pinning materials to obtain mixed alumina slurry, which is oxidized by mixing.
  • the aluminum slurry obtains fluorescent ceramic precursor powder.
  • the pinning material can be evenly pinned at the grain boundary between the crystal grains of the alumina matrix, so that a better scattering center can be formed at the grain boundary and the luminous efficiency of the fluorescent ceramic can be improved.
  • step S20 includes the following steps:
  • the composite sol in this embodiment is a zirconium oxide-yttrium oxide composite sol.
  • the mixing can be carried out by high-speed shearing dispersion in the initial stage, and the mixing can be carried out by ball milling or sand milling in the later stage to prepare a uniform mixed alumina slurry.
  • the method further includes: preparing a composite sol.
  • the preparation of the composite sol includes the following steps:
  • the first solution includes 10 parts by mass of zirconium oxychloride octahydrate and 1,600 parts by mass of water; the second solution includes 3 parts by mass of yttrium chloride and 17 parts by mass of deionized water.
  • the particle size of some alumina raw material powders will increase by 3 to 5 times. It can be understood that this phenomenon is also applicable to other components in this embodiment.
  • the gas-phase alumina powder with a smaller particle size is used in the preparation process, and zirconia can be added to inhibit the excessive (abnormal) growth of alumina, so it has a positive effect on enhancing the strength and toughness of fluorescent ceramics. influences.
  • sintering aids such as zirconium oxide and yttrium oxide, they are uniformly mixed in the powder.
  • the composite phase material composed of zirconium oxide and yttrium oxide is pinned to the grain boundary of the alumina.
  • the refractive index of zirconia is 2.05, so it can form a better scattering center at the grain boundary and improve the luminous efficiency of fluorescent ceramics.
  • step S20 includes the following steps:
  • the particle size of the fumed alumina powder of the present application is 0.01-5 ⁇ m, for example, 0.01 ⁇ m, 1 ⁇ m, 3 ⁇ m or 5 ⁇ m, preferably 1 to 5 ⁇ m.
  • the mixed powder in this embodiment includes at least two of yttrium trioxide, magnesium oxide, calcium oxide, silicon dioxide, titanium dioxide, barium oxide, calcium fluoride, barium fluoride, and zirconium oxide.
  • the content accounts for 0-50% of the total mass of the sintering aid, such as 0%, 20%, 40% or 50%.
  • the mixed powder includes zirconium oxide, yttrium oxide and magnesium oxide.
  • the content of zirconium oxide accounts for 50% of the total mass of the mixed powder
  • the content of yttrium oxide accounts for 25% of the total mass of the mixed powder
  • the content of magnesium oxide accounts for the mixed powder. 25% of the total mass of the powder.
  • step S10 includes the following steps:
  • step S11 the molar ratio of aluminum isopropoxide, water and nitric acid is 0.5 to 1.5: 3 to 5: 0.02 to 0.04, preferably 1 to 1.5: 4 to 5: 0.03 to 0.04, more preferably 1: 4 to 10 : 0.03 ⁇ 0.1.
  • the addition amount of ethyl acetoacetate is 0.5-3% of the total mass of the fourth solution, such as 0.5%, 1.0%, 2.0%, or 3.0%.
  • aluminum isopropoxide can be added to hot deionized water for magnetic stirring; then nitric acid is added in batches, and stirred until the solution is clear and transparent to obtain the third solution.
  • the stabilizer is added to the third solution and stirred evenly to obtain the fourth solution, which is then gelled and dried to obtain nano alumina sol.
  • the above step S30 specifically includes: adding phosphor and sintering aid to the mixed alumina slurry, mixing and ball milling the mixture for 30 to 60 minutes to obtain a fluorescent ceramic precursor powder.
  • the ball milling time is 30 minutes to 60 minutes, for example, 30 minutes, 40 minutes, 50 minutes, or 60 minutes.
  • the number of revolutions of the ball mill is 30-100r/min.
  • the main purpose of the low speed is to control the impact force on the phosphor during ball milling and avoid damage to the surface morphology of the phosphor.
  • the phosphor can be a phosphor, and the phosphor commonly used in the field of fluorescent ceramics can be used.
  • the mixed slurry is dried at a constant temperature in a vacuum to obtain a dry powder.
  • the dry powder is calcined in a muffle furnace at 500°C to 650°C (for example, 500°C, 550°C, 600°C, or 650°C) to remove organic components in the powder. Then, the calcined powder is passed through 80 mesh, 150 mesh, and 200 mesh sieves to obtain high fluidity fluorescent ceramic precursor powder.
  • the amount of phosphor added is 20% to 80% of the total mass of the phosphor ceramic precursor slurry, such as 20%, 40%, 60% or 80%; preferably, the amount of phosphor added is 30% to 70% of the total mass of the fluorescent ceramic precursor slurry, such as 30%, 40%, 60%, or 70%.
  • the phosphor is a YAG phosphor doped with lanthanide elements, and the doping amount is 1% to 5%, for example, 1.0%, 2.0%, or 5.0%.
  • the addition amount of the aforementioned sintering aid is 0.1% to 1.5% of the total mass of the fluorescent ceramic precursor slurry, for example, 0.1%, 0.5%, 1.0%, or 1.5%.
  • the sintering aid is at least one of magnesium oxide, calcium oxide, and yttrium oxide.
  • yttrium oxide and/or magnesium oxide is used as the sintering aid in this embodiment; more preferably, yttrium oxide is used as the sintering aid in this embodiment.
  • yttrium oxide powder particles When using yttrium oxide powder particles as an auxiliary agent, it can be used as a sintering aid for fluorescent ceramics to promote liquid phase sintering, or as a stabilizer for zirconia, so that the phase transition behavior of zirconia is not so severe and relatively gentle Volume change.
  • Magnesium oxide and yttrium oxide together can be used as sintering aids for fluorescent ceramics, which can significantly improve liquid phase sintering and lower the sintering temperature.
  • Yttrium oxide and magnesium oxide are all trace amounts of additives. If their content is less than 0.1% relative to the mass of the alumina matrix, the effect of the additives will be reduced; if their content is higher than 1.5%, it will affect the alumina matrix. transparency.
  • the three powder particles of zirconia, yttrium oxide, and magnesium oxide need to be fully mixed with the alumina powder particles in order to function most effectively.
  • step S40 includes the following steps:
  • S41 Sintering the fluorescent ceramic precursor powder at a sintering temperature of 1300 to 1550°C, a sintering time of 0.5 to 2 hours, a sintering pressure of 20 to 180 MPa, and the sintering is performed in an oxygen-free atmosphere.
  • the annealing temperature is 1200°C to 1400°C
  • the annealing time is 5 hours to 20 hours
  • the annealing treatment is performed in an air atmosphere.
  • the fluorescent ceramic precursor powder undergoes a high pressure pretreatment of more than 5 MPa before sintering, so as to keep the fluorescent ceramic precursor powder compact.
  • the sintering method may adopt a direct sintering method, a hot press sintering method, or a spark plasma sintering (SPS) method.
  • the fluorescent ceramic precursor powder obtained in step S50 can be loaded into a mold, and tableted under a pressure of 20 MPa to 40 MPa (for example, 20 MPa, 30 MPa, or 40 MPa), and the resulting sample can be subjected to 200 MPa cold isostatic pressing. Then put the sample into a sintering furnace and sinter it under a protective atmosphere such as nitrogen, argon, and hydrogen.
  • the sintering temperature is 1300°C to 1550°C, for example, 1300°C, 1400°C or 1550°C;
  • the sintering time is 0.5 hour to 2 hours, for example, 0.5 hour, 1 hour, 1.5 hours or 2 hours;
  • the sintering pressure is 20 to 180MPa, For example, 20MPa, 80MPa, 130MPa or 180MPa.
  • the fluorescent ceramic precursor powder after hot pressing and sintering can be annealed to obtain fluorescent ceramics.
  • the annealing temperature is 1200°C to 1400°C, for example, 1200°C, 1300°C or 1400°C; the annealing time is 5 hours to 20 hours, for example, 5 hours, 10 hours, 15 hours or 20 hours, and the annealing treatment is in an air atmosphere. Proceed under.
  • the fluorescent ceramic precursor powder may also undergo high pressure pretreatment of more than 5 MPa before sintering, so as to keep the fluorescent ceramic precursor powder compact.
  • the fluorescent ceramic 100 includes a nano-alumina matrix 110, pinned particles 101 and phosphor 102. Among them, there are grain boundaries 104 between the crystal grains 103 of the nano alumina matrix 110, the phosphor 102 is dispersed in the nano alumina matrix 110, and the pinned particles 101 are dispersed at the intersection of the grain boundaries 104.
  • the nano-alumina substrate 110 may be a cubic crystal system transparent ceramic with a garnet structure
  • the phosphor 102 may be a phosphor with a garnet structure
  • the transparent ceramic material with a garnet structure may include silicate, aluminate or Aluminosilicate garnet structure material.
  • the phosphor 102 and the nano-alumina substrate 110 both have a garnet structure, which can optimize the luminescence and mechanical properties of the fluorescent ceramic 100. First of all, the two structures are the same, so that the interface between the phosphor 102 and the nano-alumina substrate 110 is clean, and the generation of pores is avoided, thereby preventing light from being reflected during the process of entering the phosphor 102 from the nano-alumina substrate 110.
  • the existence of the pores here makes the refractive index difference between the nano alumina matrix 110 and the pores larger.
  • the structure of the nano alumina matrix 110 and the phosphor 102 will be the same
  • the refractive index is similar, so that when the light enters the phosphor 102, it is not easy to be reflected back to the nano-alumina matrix 110.
  • the phosphor 102 and the nano-alumina substrate 110 both belong to the garnet structure, and the hardness of the two is the same or similar.
  • the phosphor 102 may be lanthanide-doped YAG phosphor particles with a particle size of 5 ⁇ m-30 ⁇ m, for example, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, or 30 ⁇ m.
  • the doping amount is 1% to 5%, for example, 1%, 2%, 3%, or 5%.
  • the lanthanide-doped YAG phosphor particles account for 40%-50% of the total mass of the fluorescent ceramic 100, for example, 40%, 42%, 45% or 50%.
  • the fluorescent powder 102 must have a sufficient amount to ensure the luminous intensity of the fluorescent ceramic 100.
  • the lanthanide-doped YAG phosphor particles account for 40% to 50% of the total mass of the phosphor ceramic 100, the phosphor 102 with large grain size improves the luminous efficiency, and there is no impurity phase, and the grain boundary 104 is pure , The uniform light performance is good, which can meet the needs of high-power light sources such as lasers; at the same time, due to the addition of scattering particles, when the incident excitation light irradiates the scattering particles, the excitation light is scattered; after the excitation light is scattered, the excitation light The optical path in the ceramic becomes longer, thereby improving the light conversion efficiency.
  • this application prepares nano alumina sol by sol-gel method, and mixes nano alumina sol, gas phase nano alumina, and pinning materials to obtain mixed alumina slurry, which is oxidized by mixing.
  • the aluminum slurry obtains fluorescent ceramic precursor powder.
  • the pinning material can be uniformly pinned at the grain boundary between the crystal grains of the alumina matrix, so that a better scattering center can be formed at the grain boundary and the luminous efficiency of the fluorescent ceramic can be improved.
  • the grain size of the crystal grains 103 of the nano alumina matrix 110 is 0.01-5 m, for example, 0.01 m, 1 m, 3 m or 5 m, preferably 1-5 m.
  • the content of the pinned particles 101 is 0.001% to 3% of the total mass of the fluorescent ceramic 100, for example, 0.001%, 1.0%, 2.0%, or 3.0%.
  • the content of the phosphor 12 is 40%-60% of the total mass of the fluorescent ceramic 100, for example, 40%, 45%, 50% or 60%.
  • the pinned particles 101 include at least one of zirconium oxide, yttrium oxide, magnesium oxide, calcium oxide, silicon dioxide, titanium dioxide, barium oxide, calcium fluoride, and barium fluoride.
  • the content of zirconium oxide accounts for the total pinned particles 101. 0-50% of the quality.
  • the pinned particles 101 include zirconium oxide, yttrium oxide, and magnesium oxide.
  • the content of zirconia accounts for 50% of the total mass of the pinned particles 101
  • the content of yttrium oxide accounts for 25% of the total mass of the pinned particles 101
  • the content of magnesium oxide accounts for 25% of the total mass of the pinned particles 101.
  • the above-mentioned phosphor 102 is YAG phosphor particles doped with lanthanide elements, the doping amount is 1% to 5%, and the particle size of the phosphor 102 is 5 ⁇ m to 30 ⁇ m.
  • the YAG nano alumina matrix 110 is doped with Ce at a percentage of 1% to 5%.
  • Lu can be doped, so that the YAG nano alumina matrix 110 can also be doped with Lu.
  • Luminescence as a supplement to the luminescence of the fluorescent ceramic 100.
  • the YAG nano alumina matrix 110 is used as the bonding medium to bond YAG phosphor particles with large grain size, which can be further achieved within a certain range by adjusting the doping content of Ce or Lu in the bonding medium.
  • the color coordinates of the fluorescent ceramic 100 are adjustable; the YAG nano alumina matrix 110 and the YAG phosphor particles with large grain size have different doping content and different fluorescence spectrum ranges. The two complement each other and improve the color rendering of the laser. Sex. Moreover, scattering particles with high refractive index are uniformly distributed in the fluorescent ceramic 100. When the incident excitation light irradiates the scattering particles, the excitation light is scattered; after the excitation light is scattered, the optical path of the excitation light in the ceramic becomes longer. Thereby improving the light conversion efficiency.
  • the lanthanide-doped YAG phosphor particles are Ce or Lu-doped YAG phosphor particles.
  • Step 1 Preparation of alumina sol
  • Step 2 Preparation of zirconium oxide-yttrium oxide composite sol
  • Step 3 Preparation of thickened alumina slurry
  • the added mass ratio ranges from 1/1 to 1/5, and the more optimized range is Between 1/2 and 1/3.5; the mixing is carried out by high-speed shear dispersion in the initial stage; the mixing is carried out by ball milling or sand milling in the later stage to prepare a uniform mixed alumina slurry;
  • Step 3 Mix the alumina slurry and phosphor ball mill mixture
  • a certain proportion of YAG:Ce 3+ phosphor is added to the alumina slurry in step 2, wherein the amount of phosphor added is between 20% and 80%, more preferably 30% to 70%.
  • the sintering aid can be one or more of magnesium oxide, calcium oxide, yttrium oxide, etc., and the addition amount of the sintering aid is 0.1% to 1.5%. Ball mill mixing is performed again for 30 minutes to 60 minutes. A mixed slurry of mixed alumina slurry and phosphor powder can be prepared.
  • the above-mentioned slurry is dried, ground, sieved and other conventional granulation processes to prepare the powder to be sintered.
  • Step 5 Hot pressing sintering and annealing treatment
  • the mixed powder to be sintered into a graphite mold pre-press the powder under low pressure, and then place the graphite mold in an SPS hot pressing furnace, in a vacuum/argon atmosphere, at 1300°C ⁇ 1550 Heat preservation and sintering at °C for 0.5 hour to 2 hours, the pressure during sintering is 20MPa-180MPa.
  • the hot-press sintered fluorescent ceramics are annealed at 1200°C to 1400°C in an air atmosphere for 5 hours to 20 hours to prepare YAG-Al 2 O 3 multiphase fluorescent ceramics.
  • Step 1 Preparation of alumina sol
  • Step 2 Thickening of alumina sol and preparation of its slurry
  • Step 3 Mix the alumina slurry and phosphor ball mill mixture
  • a certain proportion of YAG:Ce 3+ phosphor is added to the alumina slurry in step 2, wherein the amount of phosphor added is between 20% and 80%, more preferably 30% to 70%.
  • the sintering aid can be one or more of magnesium oxide, calcium oxide, yttrium oxide, etc., and the addition amount of the sintering aid is 0.1% to 1.5%. Ball mill mixing is performed again for 30 minutes to 60 minutes. A mixed slurry of mixed alumina slurry and phosphor powder can be prepared.
  • the above-mentioned slurry is dried, ground, sieved and other conventional granulation processes to prepare the powder to be sintered.
  • Step 5 Hot pressing sintering and annealing treatment
  • the mixed powder to be sintered into a graphite mold pre-press the powder under low pressure, and then place the graphite mold in an SPS hot pressing furnace, in a vacuum/argon atmosphere, at 1300°C ⁇ 1550 Heat preservation and sintering at °C for 0.5 hour to 2 hours, the pressure during sintering is 20MPa to 180MPa.
  • the hot-press sintered fluorescent ceramics are annealed at 1200°C to 1400°C in an air atmosphere for 5 hours to 20 hours to prepare YAG-Al 2 O 3 multiphase fluorescent ceramics.
  • the present application also provides a light-emitting device, including an excitation light source and the above-mentioned fluorescent ceramic, wherein the excitation light source is a laser light source, and the fluorescent ceramic is irradiated by the excitation light source to generate high-brightness light.
  • the light-emitting device can be applied to a projection and display system, such as a liquid crystal display (LCD, Liquid Crystal Display) or a digital light processor (DLP, Digital Light Processor) projector. It can also be applied to lighting systems, such as automotive lighting. It can also be applied to the field of 3D display technology.
  • the above-mentioned fluorescent ceramics can also be made into a movable device, such as a color wheel, so that the excitation light emitted by the excitation light source is incident on the rotating color wheel, thereby generating laser light.
  • the projection device may be an educational projector, a laser TV, a micro-projector or a cinema machine, etc.
  • the projection device includes the light-emitting device of the above-mentioned embodiment. For the specific structure of the light-emitting device, refer to the above-mentioned embodiment .
  • this application prepares nano alumina sol by sol-gel method, and mixes nano alumina sol, gas phase nano alumina and pinning materials to obtain mixed alumina slurry, which is oxidized by mixing.
  • the aluminum slurry obtains fluorescent ceramic precursor powder.
  • the pinning material can be evenly pinned at the grain boundary between the crystal grains of the alumina matrix, so that a better scattering center can be formed at the grain boundary and the luminous efficiency of the fluorescent ceramic can be improved.

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Abstract

涉及荧光陶瓷技术领域，具体公开了一种荧光陶瓷的制备方法及荧光陶瓷，该方法包括以下步骤：制备纳米氧化铝溶胶；以预设比例混合所述纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料由所述混合氧化铝浆料制备得到荧光陶瓷前驱体粉末；将所述荧光陶瓷前驱体粉末烧结，得到荧光陶瓷。通过上述方式，能够提高荧光陶瓷的发光效率。

Description

荧光陶瓷的制备方法及荧光陶瓷 技术领域
本申请涉及荧光陶瓷技术领域，特别是涉及荧光陶瓷的制备方法及荧光陶瓷。
背景技术
蓝色激光激发荧光材料获得可见光的技术，作为一种全新的光源技术，在激光显示领域中的应用获得了显著的进展，并受到了市场的认可，相关技术不断获得重视。当前研究的热点和难点主要是针对激光激发荧光粉的特性来开发新型的荧光材料(波长转换材料、发光材料)，这些材料必须拥有优秀的性能，比如光学转换效率高，亮度高，单位发光面积能够承受更大功率激光照射，具有高导热性能，寿命长等。
对于荧光陶瓷而言，如何提高其发光效率至关重要。荧光陶瓷中纯相陶瓷由于其自身结构原因，难以对激发光有较高的利用率；在荧光陶瓷受激发时，其荧光粉相对较少而导致其发光效率较差。因此，亟需发明一种新型荧光陶瓷，来提升目前透明荧光陶瓷的发光效率。
发明内容
本申请提供一种荧光陶瓷的制备方法及荧光陶瓷，能够提高荧光陶瓷的发光效率。
一方面，本申请提供了一种荧光陶瓷的制备方法，包括以下步骤：制备纳米氧化铝溶胶；以预设比例混合所述纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料由所述混合氧化铝浆料制备得到荧光陶瓷前驱体粉末；将所述荧光陶瓷前驱体粉末烧结，得到荧光陶瓷。
另一方面，本申请提供了一种荧光陶瓷，荧光陶瓷包括：纳米氧化 铝基质，其中，所述纳米氧化铝基质的晶粒之间存在有晶界；分散于所述纳米氧化铝基质中的荧光粉；钉扎于所述晶界相交处的钉扎粒子。
本申请的有益效果是：区别于现有技术的情况，本申请通过溶胶凝胶法制备出纳米氧化铝溶胶，并混合纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料，并由混合氧化铝浆料得到荧光陶瓷前驱体粉末。在后续烧结过程中，钉扎材料可以均匀地钉扎在氧化铝基质的晶粒之间的晶界处，因此能够在晶界处形成较好的散射中心，提升荧光陶瓷的发光效率。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。其中：
图1为本申请荧光陶瓷的制备方法第一实施例的流程示意图；
图2为图1中步骤S20的第一流程示意图；
图3为本申请荧光陶瓷的制备方法第二实施例的流程示意图；
图4为图1中步骤S20的第二流程示意图；
图5为图1中步骤S10的流程示意图；
图6为图1中步骤S40的流程示意图；
图7为本申请荧光陶瓷一实施例的结构示意图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性的劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
目前，激光显示技术作为一种高端显示技术已经得到了飞速的发展。随着该技术的发展，高亮度，小体积的激光光源产品成为主流技术 方向。因此，对激光激发的荧光材料的性能要求也越来越高。传统的硅胶封装的荧光材料、低熔点玻璃封装的荧光材料已经不能满足产品需求。而荧光陶瓷材料无论是在耐热、导热上均有显著的优势，成为大功率、高功率密度激发下的光源产品中的首选波长转换材料。
对于用于激光照明和显示技术中的荧光材料大致可分为三类。(1)通过有机硅胶/有机树脂等有机聚合物对荧光粉进行封装；当随着蓝色激光功率的增加，有机基质所封装的荧光材料在进行光转换时，所产生热量也急剧增加，致使其自身温度大幅上升，进而导致封装的硅胶/有机树脂等有机基质老化泛黄，进而引发光效损失、寿命减少等问题。(2)荧光玻璃材料，其主要是将荧光粉封装在SiO 2基/硼硅酸盐基的玻璃中。荧光玻璃较有机树脂而言，在耐热性、高热稳定性、低色偏移等上有很大改善，但是其在导热性能上较有机树脂并无显著性的提高。(3)荧光陶瓷，荧光陶瓷较有机基质和无机玻璃基质所封装的荧光材料，在无论是在耐热还是热导率上均有显著的优势。荧光陶瓷分为两种，一种是通过在YAG等透明陶瓷中掺杂稀土元素制备而成；另外一种是通过将荧光粉封装在高导热系数的透明陶瓷中。
荧光陶瓷因其优异导热和耐热的性能而成为激光照明显示技术中一个重要发展方向。因此如何提高其发光效率是业界关注的重点。荧光陶瓷按照其材料内部结构分为YAG：Ce 3+纯相荧光陶瓷(包含YAG：Ce 3+单晶材料)、YAG：Ce 3+与透明陶瓷材料共同烧结而成的复相荧光陶瓷材料两大类；其中纯相陶瓷由于自身结构原因，难以对激发光有较高的利用率；在其受激发时，其发光中心相对较少而导致其发光效率较差。相对比而言，将荧光粉封装在透明陶瓷中所形成的这类复相荧光陶瓷更具有一定的优越性。怎样进一步提升这类复相荧光陶瓷的发光效率，也成为业界研究的一个重要课题。
基于此，本申请提出一种荧光陶瓷的制备方法及荧光陶瓷，该荧光陶瓷的晶粒尺寸小，晶界多，利用了晶界的散射作用，从而提高荧光陶瓷的效率。
请参阅图1，本申请提供了一种荧光陶瓷的制备方法，该制备方法 包括以下步骤：
S10：制备纳米氧化铝溶胶。
本步骤通过溶胶凝胶法制备出溶胶。
具体地，将异丙醇铝按照n(异丙醇铝):n(H 2O):n(HNO 3)＝0.5～1.5:3～5:0.02～0.04的摩尔比例，逐滴加入到水与硝酸的混合溶液中，异丙醇铝水解后得到氧化铝。再将氧化铝与稳定剂在80℃条件下，回流搅拌2h，即可制备出纯度较高、澄清透明的纳米氧化铝溶胶。
进一步地，本实施例可以通过控制水解温度和去离子水的用量，可使得制备较为稳定的纳米氧化铝溶胶。
S20：以预设比例混合纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料。
其中，钉扎材料为助剂或含有助剂的溶胶，其中，助剂为氧化锆、氧化钇、氧化镁、氧化钙、二氧化硅、二氧化钛、氧化钡、氟化钙、氟化钡中的至少一种。
S30：由混合氧化铝浆料制备得到荧光陶瓷前驱体粉末。
由纳米氧化铝溶胶制得混合氧化铝浆料，将混合氧化铝浆料作为球磨浆料，向其中添加一定比例微米级(5～20μm)的荧光粉或添加一定比例微米级的荧光粉和微米级的氧化铝粉，进行球磨混料，干燥、研磨过筛后得到荧光陶瓷前驱体粉末。
S40：将荧光陶瓷前驱体粉末烧结，得到荧光陶瓷。
将荧光陶瓷前驱体粉末在较低的热压烧结温度(1400～1500℃)和较短保温时间(0.5～1.5h)下热压烧结，从而制备出一种晶粒尺寸小(1～5μm)且均匀的YAG-Al 2O 3复相荧光陶瓷，由于晶粒尺寸小，晶界多，利用了晶界的散射作用，从而提高荧光陶瓷的效率。
区别于现有技术的情况，本申请通过溶胶凝胶法制备出纳米氧化铝溶胶，并混合纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料，并由混合氧化铝浆料得到荧光陶瓷前驱体粉末。在后续烧结过程中，钉扎材料可以均匀地钉扎在氧化铝基质的晶粒之间的晶界处，因此能够在晶界处形成较好的散射中心，提升荧光陶瓷的发光效 率。
请参阅图2，在一实施例中，上述步骤S20包括以下步骤：
S211：提供钉扎材料，钉扎材料为复合溶胶。
其中，在本实施中的复合溶胶为氧化锆-氧化钇复合溶胶。
S212：混合纳米氧化铝溶胶和复合溶胶，得到第一混合溶胶。
S213：向1质量份的第一混合溶胶中加入1～5质量份的气相纳米氧化铝，分散处理后，得到混合氧化铝浆料。
优选地，向1质量份的第一混合溶胶中加入2～3.5质量份的气相纳米氧化铝。初期可以通过高速剪切分散进行混料，后期可以采用球磨或砂磨方式进行混料，进而制备出均匀的混合氧化铝浆料。
进一步地，该方法还包括：制备复合溶胶。请参阅图3，制备复合溶胶包括以下步骤：
S221：配置第一溶液和第二溶液。
其中，第一溶液包括10质量份八水合氯氧化锆和1600质量份水；第二溶液包括3质量份氯化钇和17质量份去离子水。
S222：向第一溶液中加入50质量份尿素，混匀，制得氧化锆溶胶。
S223：向氧化锆溶胶中加入第二溶液和17质量份聚乙二醇400，混匀，制得复合溶胶。
通常，由于团聚和烧结过程中晶粒的异常长大现象，部分氧化铝原料粉末粒径会增大3～5倍。可以理解，这一现象同样适用于本实施例中的其他成分。但是，本实施例中，采用粒径较小的气相氧化铝粉体在制备过程中，可以添加氧化锆抑制氧化铝过度(异常)长大的作用，因此对增强荧光陶瓷强度和韧性有积极的影响。同时，由于添加了氧化锆、氧化钇等烧结助剂，其均匀混合在粉料之中，在烧结过程中，氧化锆、氧化钇组成的复合相材料钉扎在氧化铝的晶界处，其中氧化锆的折射率为2.05，因此，能够在晶界处形成较好的散射中心，提升荧光陶瓷的发光效率。
请参阅图4，在一实施例中，上述步骤S20包括以下步骤：
S231：向1质量份纳米氧化铝溶胶中加入0.01～0.25质量份混合粉 体，分散处理后，得到第二混合溶胶。
S232：向第二混合溶胶中加入1～5质量份气相纳米氧化铝，分散处理后，得到混合氧化铝浆料。
例如，纳米氧化铝溶胶1质量份、气相氧化铝粉体1、3或5质量份、混合粉体0.01、0.05、0.20或0.25质量份。其中，本申请的气相氧化铝粉体的粒径为0.01～5μm，例如0.01μm、1μm、3μm或5μm，优选为1～5μm。
其中，在本实施例中的混合粉体包括三氧化二钇、氧化镁、氧化钙、二氧化硅、二氧化钛、氧化钡、氟化钙、氟化钡、氧化锆中的至少两种，氧化锆的含量占烧结助剂总质量的0～50％，例如0％、20％、40％或50％。
优选地，混合粉体包括氧化锆、氧化钇以及氧化镁，氧化锆的含量占混合粉体总质量的50％，氧化钇的含量占混合粉体总质量的25％，氧化镁的含量占混合粉体总质量的25％。
请参阅图5，在一实施例中，上述步骤S10包括以下步骤：
S11：将异丙醇铝加入水与硝酸的混合溶液当中，其中异丙醇铝、水与硝酸的摩尔比为1:4～10:0.03～0.1，得到第三溶液。
步骤S11中，异丙醇铝、水与硝酸的摩尔比为0.5～1.5:3～5:0.02～0.04，优选为1～1.5:4～5:0.03～0.04，更优选为1:4～10:0.03～0.1。
S12：向第三溶液中加入乙酰乙酸乙酯，得到第四溶液。
其中，乙酰乙酸乙酯的添加量为第四溶液的总质量的0.5～3％，例如0.5％、1.0％、2.0％或3.0％。
S13：对第四溶液进行回流处理，得到纳米氧化铝溶胶。
具体地，可以将异丙醇铝加入热的去离子水中进行磁力搅拌；再分批加入硝酸，搅拌至溶液澄清透明，得到第三溶液。向第三溶液中加入稳定剂搅拌均匀，得到第四溶液，然后凝胶化和干燥，得到纳米氧化铝溶胶。
在一实施例中，上述步骤S30具体为：向混合氧化铝浆料中加入荧光粉和烧结助剂，混匀并球磨混料30分钟～60分钟，得到荧光陶瓷前驱体粉末。
将混合后的混合氧化铝浆料、荧光粉和烧结助剂在低速下进行球磨，得到混合浆料。球磨时间为30分钟～60分钟，例如，30分钟、40分钟、50分钟或60分钟。球磨的转数为30-100r/分钟。需要说明的是，采用低速的主要目的在于控制球磨时对荧光粉的冲击力度，避免对荧光粉表面形态的破坏荧光粉可以为荧光粉，可使用荧光陶瓷领域常用的荧光粉。
球磨结束后，采用真空恒温将混合浆料干燥获得干粉。干粉在马弗炉中在500℃～650℃(例如，500℃、550℃、600℃或650℃)下进行煅烧，以除去粉末中的有机成分。然后，将煅烧后的粉末过80目、150目、200目筛，得到高流动性的荧光陶瓷前驱体粉末。
本实施例中，上述荧光粉的添加量为荧光陶瓷前驱体浆料的总质量的20％～80％，例如20％、40％、60％或80％；优选地，荧光粉的添加量为荧光陶瓷前驱体浆料的总质量的30％～70％，例如30％、40％、60％或70％。荧光粉为镧系元素掺杂的YAG荧光粉，掺杂量为1％～5％，例如1.0％、2.0％或5.0％。
上述烧结助剂的添加量为荧光陶瓷前驱体浆料的总质量的0.1％～1.5％，例如0.1％、0.5％、1.0％或1.5％。
烧结助剂为氧化镁、氧化钙、氧化钇中的至少一种。优选地，氧化钇和/或氧化镁作为本实施例的烧结助剂；更优选氧化钇作为本实施例的烧结助剂。
当使用氧化钇粉末颗粒作为助剂时，既可以作为荧光陶瓷的烧结助剂，促进液相烧结，也可以作为氧化锆的稳定剂，使氧化锆的相变行为不那么剧烈，为相对缓和的体积变化。氧化镁和氧化钇一起可以作为荧光陶瓷的烧结助剂，可以显著提高液相烧结，降低烧结温度。氧化钇、氧化镁都是微量含量的助剂，如果它们的含量相对于氧化铝基质质量低于0.1％，则助剂作用减少；如果它们的含量高于1.5％，则会影响氧化铝基质的透明度。氧化锆、氧化钇、氧化镁这三种粉末颗粒都需要与氧化铝粉末颗粒充分地混合，才能最有效地发挥作用。
请参阅图6，在一实施例中，上述步骤S40包括以下步骤：
S41：将荧光陶瓷前驱体粉末烧结处理，烧结温度为1300～1550℃，烧结时间为0.5小时～2小时，烧结压力为20～180MPa，烧结在无氧气氛下进行。
S42：将热压烧结后的荧光陶瓷前驱体粉末进行退火处理，得到荧光陶瓷，退火温度为1200℃～1400℃，退火时间为5小时～20小时，退火处理在空气气氛下进行。
进一步地，该荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压预处理，以使荧光陶瓷前驱体粉末保持致密。
具体地，烧结方法可采用直接烧结法、热压烧结法或放电等离子烧结SPS(spark plasma sintering)法。具体可以将步骤S50中获得的荧光陶瓷前驱体粉末装入模具中，在20MPa～40MPa(例如，20MPa、30MPa或40MPa)的压力下进行压片，将所得样片再经过200MPa冷等静压处理，然后将样片放入烧结炉内，在氮气、氩气、氢气等保护气氛下烧结。烧结温度为1300℃～1550℃，例如，1300℃、1400℃或1550℃；烧结时间为0.5小时～2小时，例如，0.5小时、1小时、1.5小时或2小时；烧结压力为20～180MPa，例如，20MPa、80MPa、130MPa或180MPa。
进一步地，可将热压烧结后的荧光陶瓷前驱体粉末进行退火处理，得到荧光陶瓷。
其中，退火温度为1200℃～1400℃，例如，1200℃、1300℃或1400℃；退火时间为5小时～20小时，例如，5小时、10小时、15小时或20小时，退火处理在空气气氛下进行。
该荧光陶瓷前驱体粉末在烧结前还可以经过5MPa以上高压预处理，以使荧光陶瓷前驱体粉末保持致密。
请参阅图7，本申请提出一种荧光陶瓷，该荧光陶瓷100包括：纳米氧化铝基质110、钉扎粒子101以及荧光粉102。其中，纳米氧化铝基质110的晶粒103之间存在有晶界104，荧光粉102分散于纳米氧化铝基质110当中，钉扎粒子101分散于晶界104相交处。
具体地，纳米氧化铝基质110可以为石榴石结构的立方晶系的透明陶瓷，荧光粉102可以为石榴石结构的荧光粉，石榴石结构的透明陶瓷 材料可以包括硅酸盐、铝酸盐或硅铝酸盐的石榴石结构材料。荧光粉102和纳米氧化铝基质110同为石榴石结构，能够优化荧光陶瓷100的发光性能和机械性能。首先，两者结构相同，使得荧光粉102与纳米氧化铝基质110直接接触的界面洁净，避免了孔隙的产生，从而避免了光在由纳米氧化铝基质110进入荧光粉102的过程中被反射，这里孔隙的存在使得纳米氧化铝基质110与孔隙的折射率差较大，光由纳米氧化铝基质110进入孔隙时容易全反射，而且纳米氧化铝基质110与荧光粉102的结构相同将导致两者的折射率相近，使得光进入荧光粉102时不易被反射回纳米氧化铝基质110。其次，荧光粉102和纳米氧化铝基质110同属于石榴石结构，两者的硬度相同或相仿，当荧光陶瓷100制备完毕，对荧光陶瓷100表面进行抛光时更为容易。
上述荧光粉102可以为粒径5μm～30μm的镧系元素掺杂的YAG荧光粉颗粒，例如，5μm、10μm、20μm或30μm。掺杂量为1％～5％，例如，1％、2％、3％或5％。镧系元素掺杂的YAG荧光粉颗粒占荧光陶瓷100总质量的40％～50％，例如，40％、42％、45％或50％。
可以理解的是，荧光粉102必须要有足够的量，才能保证荧光陶瓷100发光强度。镧系元素掺杂的YAG荧光粉颗粒占荧光陶瓷100总质量的40％～50％时，由于具有大晶粒粒径的荧光粉102，提高了发光效率，且没有杂相，晶界104纯净，匀光性能好，能够满足激光等大功率光源的使用需求；同时，由于加入了散射颗粒，当入射的激发光照射到散射颗粒上时，激发光被散射；激发光被散射后，激发光在陶瓷中的光程变长，从而提升光转换效率。
区别于现有技术的情况，本申请通过溶胶凝胶法制备出纳米氧化铝溶胶，并混合纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料，并由混合氧化铝浆料得到荧光陶瓷前驱体粉末。在后续烧结过程中，钉扎材料可以均匀地钉扎在氧化铝基质的晶粒之间的晶界处，因此能够在晶界处形成较好的散射中心，提升荧光陶瓷的发光效率。
上述纳米氧化铝基质110的晶粒103的粒径为0.01～5μm，例如 0.01μm、1μm、3μm或5μm，优选为1～5μm。
上述钉扎粒子101的含量为荧光陶瓷100的总质量的0.001％～3％，例如0.001％、1.0％、2.0％或3.0％。
上述荧光粉12的含量为荧光陶瓷100的总质量的40％～60％，例如，40％、45％、50％或60％。
上述钉扎粒子101包括氧化锆、氧化钇、氧化镁、氧化钙、二氧化硅、二氧化钛、氧化钡、氟化钙、氟化钡中的至少一种，氧化锆的含量占钉扎粒子101总质量的0～50％。
优选地，钉扎粒子101包括氧化锆、氧化钇以及氧化镁。其中，氧化锆的含量占钉扎粒子101总质量的50％，氧化钇的含量占钉扎粒子101总质量的25％，氧化镁的含量占钉扎粒子101总质量的25％。
上述荧光粉102为镧系元素掺杂的YAG荧光粉颗粒，掺杂量为1％～5％，荧光粉102的粒径为5μm～30μm。
具体地，本实施例采用的制备方案在YAG纳米氧化铝基质110中掺杂了百分比为1％～5％的Ce，在其他实施方式中可以掺杂Lu，使得YAG纳米氧化铝基质110也可以发光，作为荧光陶瓷100的发光补充。本实施例中，YAG纳米氧化铝基质110做粘结介质粘结大晶粒粒径的YAG荧光粉颗粒，进一步可以通过调节粘结介质中Ce或Lu的掺杂含量，可以在一定范围内实现荧光陶瓷100的色坐标可调；YAG纳米氧化铝基质110和大晶粒粒径的YAG荧光粉颗粒中的掺杂含量不同，荧光光谱范围不同，二者相互补充，提高了受激光的显色性。并且在荧光陶瓷100中均匀分布了高折射率的散射颗粒，当入射的激发光照射到散射颗粒上时，激发光被散射；激发光被散射后，激发光在陶瓷中的光程变长，从而提升光转换效率。
优选地，镧系元素掺杂的YAG荧光粉颗粒为Ce或Lu掺杂的YAG荧光粉颗粒。
下面进一步列举实施例以详细说明本申请。同样应理解，以下实施例只用于对本申请进行进一步说明，不能理解为对本申请保护范围的限 制，本领域的技术人员根据本申请的上述内容做出的一些非本质的改进和调整均属于本申请的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
液相法(溶胶-凝胶工艺段)
步骤一：氧化铝溶胶的制备
将204.24质量份的异丙醇铝、36～180质量份的水和5.1654～17.218质量份的乙酰乙酸乙酯，加入到圆底烧瓶中，在80℃条件下，回流搅拌2小时，即可制备出纯度较高、澄清透明的纳米氧化铝溶胶；
步骤二：氧化锆-氧化钇复合溶胶的制备
将ZrOCl 2 8H 2O按照M(ZrOCl 2 8H 2O)/M(H 2O)＝10质量份/1600质量份，配成溶液，再加入50质量份的尿素为胶凝剂，室温搅拌1小时，即制得锆溶胶；称取3质量份的氯化钇加入到去离子水中，配制成20质量份的溶液，逐滴到锆溶胶中；然后再向此溶液中逐滴加入10mL的聚乙二醇400作为分散剂。室温搅拌1小时后，即可得到透明的稳定的氧化锆-氧化钇复合溶胶。
步骤三：增稠型的氧化铝浆料制备
将上述步骤一和步骤二中的溶胶进行混合；再向混合氧化铝浆料中，加入一定比例气相纳米氧化铝，其添加的质量配比范围是1/1至1/5，更优化范围为1/2～1/3.5之间；初期通过高速剪切分散进行混料；后期采用球磨或砂磨方式进行混料，制备出均匀的混合氧化铝浆料；
固相法工艺段
步骤三：混合氧化铝浆料与荧光粉球磨混料
向步骤二中的氧化铝浆料中添加一定比例的YAG:Ce 3+的荧光粉，其中荧光粉添加量在20％～80％间，更优化为30％～70％。烧结助剂可为氧化镁、氧化钙、氧化钇等中的一种或多种，烧结助剂添加量在0.1％～1.5％。再次进行球磨混料30分钟～60分钟。即可制得混合氧化铝浆料与荧光粉的混合浆料。
步骤四：造粉
将上述浆料分别进行干燥、研磨、过筛等常规造粒工艺，即可制备出待烧结粉料。
烧结工艺段
步骤五：热压烧结及退火处理
将混合后的待烧结粉体充填至石墨模具中，对粉体在小压力下进行预压处理，随后将石墨模具置于SPS热压炉中，在真空/氩气气氛中，1300℃～1550℃下保温烧结0.5小时-2小时，烧结时压力在20MPa-180MPa。烧结后，将热压烧结后的荧光陶瓷于空气气氛中1200℃～1400℃下退火处理5小时～20小时即可制备出YAG-Al 2O 3复相荧光陶瓷。
值得注意的是，上述各流程步骤的执行顺序可以根据实际需要进行调整。
实施例2
液相法(溶胶-凝胶工艺段)
步骤一：氧化铝溶胶的制备
将异丙醇铝按照n(异丙醇铝):n(H 2O):n(HNO 3)＝1:4:0.03的摩尔比例，逐滴加入到酸性的水溶液中，并添加整体质量的0.5～3％乙酰乙酸乙酯作为稳定剂，在80℃条件下，回流搅拌2小时，即可制备出纯度较高、澄清透明的纳米氧化铝溶胶；
步骤二：氧化铝溶胶的增稠及其浆料制备
取上述溶胶，向其中添加纳米气相氧化铝，其质量配比为M(氧化铝溶胶)/{M(纳米气相氧化铝)+M(纳米ZrO 2/Y 2O 3/MgO混合粉体)}为1/1至1/5范围，更优化范围为1/2～1/3.5之间；其中M(纳米ZrO 2/Y 2O 3/MgO混合粉体)占M(纳米氧化铝粉)质量的0.1～5％，优选0.5～1.5％，其中M(纳米ZrO 2)/M(纳米Y 2O 3)/M(纳米MgO)＝2/1/1的质量配比，其中根据散射特性需求可适当增多或减少纳米ZrO 2的质量占比，其添加的比例范围占纳米ZrO 2/Y 2O 3/MgO混合粉体总质量 的0～50％；很合添加的顺序为，先将纳米很合粉体添加到氧化铝溶胶中，通过高速剪切分散进行混料；再加入纳米气相纳米氧化铝，继续高速剪切搅拌分散，后期采供球磨或砂磨方式进行混料，制备出氧化铝浆料；
固相法工艺段
步骤三：混合氧化铝浆料与荧光粉球磨混料
向步骤二中的氧化铝浆料中添加一定比例的YAG:Ce 3+的荧光粉，其中荧光粉添加量在20％～80％间，更优化为30％～70％。烧结助剂可为氧化镁、氧化钙、氧化钇等中的一种或多种，烧结助剂添加量在0.1％～1.5％。再次进行球磨混料30分钟～60分钟。即可制得混合氧化铝浆料与荧光粉的混合浆料。
步骤四：造粉
将上述浆料分别进行干燥、研磨、过筛等常规造粒工艺，即可制备出待烧结粉料。
烧结制程工艺段
步骤五：热压烧结及退火处理
将混合后的待烧结粉体充填至石墨模具中，对粉体在小压力下进行预压处理，随后将石墨模具置于SPS热压炉中，在真空/氩气气氛中，1300℃～1550℃下保温烧结0.5小时～2小时，烧结时压力在20MPa～180MPa。烧结后，将热压烧结后的荧光陶瓷于空气气氛中1200℃～1400℃下退火处理5小时～20小时即可制备出YAG-Al 2O 3复相荧光陶瓷。
值得注意的是，上述各流程步骤的执行顺序可以根据实际需要进行调整。
本申请还提供了一种发光装置，包括激发光源和上述荧光陶瓷，其中激发光源为激光光源，通过该激发光源照射荧光陶瓷，产生高亮度的光。该发光装置可以应用于投影、显示系统，例如液晶显示器(LCD，Liquid Crystal Display)或数码光路处理器(DLP，Digital Light Processor)投影机。也可以应用于照明系统，例如汽车照明灯。也可以应用于3D 显示技术领域中。在发光装置中，上述荧光陶瓷还可以制作成为可运动的装置，如色轮，使激发光源发出的激发光入射到旋转运动的色轮上，从而产生受激光。
本申请还提供了一种投影装置，该投影设备可以是教育投影仪、激光电视、微投或者影院机等，该投影设备包括上述实施例的发光装置，该发光装置的具体结构参照上述实施例。
区别于现有技术的情况，本申请通过溶胶凝胶法制备出纳米氧化铝溶胶，并混合纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料，并由混合氧化铝浆料得到荧光陶瓷前驱体粉末。在后续烧结过程中，钉扎材料可以均匀地钉扎在氧化铝基质的晶粒之间的晶界处，因此能够在晶界处形成较好的散射中心，提升荧光陶瓷的发光效率。
以上仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (19)

  1. 一种荧光陶瓷的制备方法，其特征在于，包括以下步骤：
    制备纳米氧化铝溶胶；
    以预设比例混合所述纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料；
    由所述混合氧化铝浆料制备得到荧光陶瓷前驱体粉末；
    将所述荧光陶瓷前驱体粉末烧结，得到荧光陶瓷。
  2. 根据权利要求1所述的制备方法，其特征在于，所述以预设比例混合所述纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料的步骤包括：
    提供所述钉扎材料，所述钉扎材料为复合溶胶；
    混合所述纳米氧化铝溶胶和所述复合溶胶，得到第一混合溶胶；
    向1质量份的所述第一混合溶胶中加入1～5质量份的所述气相纳米氧化铝，分散处理后，得到所述混合氧化铝浆料。
  3. 根据权利要求2所述的制备方法，其特征在于，所述复合溶胶为氧化锆-氧化钇复合溶胶，所述方法还包括：
    制备所述复合溶胶；
    其中，所述制备所述复合溶胶的步骤包括：
    配置第一溶液和第二溶液，其中，所述第一溶液包括10质量份八水合氯氧化锆和1600质量份水，所述第二溶液包括3质量份氯化钇和17质量份去离子水；
    向所述第一溶液中加入50质量份尿素，混匀，制得氧化锆溶胶；
    向所述氧化锆溶胶中加入所述第二溶液和17质量份聚乙二醇400，混匀，制得所述复合溶胶。
  4. 根据权利要求1所述的制备方法，其特征在于，所述以预设比例混合所述纳米氧化铝溶胶、气相纳米氧化铝以及钉扎材料，以得到混合氧化铝浆料的步骤包括：
    向1质量份纳米氧化铝溶胶中加入0.01～0.25质量份混合粉体，分 散处理后，得到第二混合溶胶；
    向所述第二混合溶胶中加入1～5质量份气相纳米氧化铝，分散处理后，得到所述混合氧化铝浆料。
  5. 根据权利要求4所述的制备方法，其特征在于，所述混合粉体包括三氧化二钇、氧化镁、氧化钙、二氧化硅、二氧化钛、氧化钡、氟化钙、氟化钡、氧化锆中的至少两种，所述氧化锆的含量占所述烧结助剂总质量的0～50％。
  6. 根据权利要求5所述的制备方法，
    所述混合粉体包括氧化锆、氧化钇以及氧化镁；
    所述氧化锆的含量占所述混合粉体总质量的50％；
    所述氧化钇的含量占所述混合粉体总质量的25％；
    所述氧化镁的含量占所述混合粉体总质量的25％。
  7. 根据权利要求1所述的制备方法，其特征在于，
    所述钉扎材料为助剂或含有所述助剂的溶胶，其中，所述助剂为氧化锆、氧化钇、氧化镁、氧化钙、二氧化硅、二氧化钛、氧化钡、氟化钙、氟化钡中的至少一种。
  8. 根据权利要求1所述的制备方法，其特征在于，所述制备纳米氧化铝溶胶的步骤包括：
    将异丙醇铝加入水与硝酸的混合溶液当中，其中异丙醇铝、水与硝酸的摩尔比为1:4～10:0.03～0.1，得到第三溶液；
    向所述第三溶液中加入乙酰乙酸乙酯，得到第四溶液，其中，所述乙酰乙酸乙酯的添加量为所述第四溶液的总质量的0.5～3％；
    对所述第四溶液进行回流处理，得到所述纳米氧化铝溶胶。
  9. 根据权利要求1所述的制备方法，其特征在于，所述由所述混合氧化铝浆料制备得到荧光陶瓷前驱体粉末的步骤包括：
    向所述混合氧化铝浆料中加入荧光粉和烧结助剂，混匀并球磨混料30分钟～60分钟，得到所述荧光陶瓷前驱体粉末；
    其中，所述荧光粉的添加量为所述荧光陶瓷前驱体浆料的总质量的20％～80％，所述烧结助剂的添加量为所述荧光陶瓷前驱体浆料的总质量 的0.1％～1.5％；
    其中，所述荧光粉为镧系元素掺杂的YAG荧光粉，掺杂量为1％～5％；
    所述烧结助剂为氧化镁、氧化钙、氧化钇中的至少一种。
  10. 根据权利要求9所述的制备方法，其特征在于，
    所述荧光粉的添加量为所述荧光陶瓷前驱体浆料的总质量的30％～70％。
  11. 根据权利要求1所述的制备方法，其特征在于，所述将所述荧光陶瓷前驱体粉末烧结，得到荧光陶瓷的步骤包括：
    将所述荧光陶瓷前驱体粉末烧结处理，烧结温度为1300～1550℃，烧结时间为0.5小时～2小时，烧结压力为20～180MPa，烧结在无氧气氛下进行；
    将热压烧结后的所述荧光陶瓷前驱体粉末进行退火处理，得到荧光陶瓷，退火温度为1200℃～1400℃，退火时间为5小时～20小时，退火处理在空气气氛下进行；
    其中，该荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压预处理，以使所述荧光陶瓷前驱体粉末保持致密。
  12. 一种荧光陶瓷，其特征在于，所述荧光陶瓷包括：
    纳米氧化铝基质，其中，所述纳米氧化铝基质的晶粒之间存在有晶界；
    分散于所述纳米氧化铝基质中的荧光粉；
    钉扎于所述晶界相交处的钉扎粒子。
  13. 根据权利要求12所述的荧光陶瓷，其特征在于，
    所述纳米氧化铝基质的晶粒粒径为0.01～5μm。
  14. 根据权利要求12所述的荧光陶瓷，其特征在于，
    所述钉扎粒子的含量为所述荧光陶瓷的总质量的0.001％～3％；
    所述荧光粉的含量为所述荧光陶瓷的总质量的40％～60％。
  15. 根据权利要求12所述的荧光陶瓷，其特征在于，
    所述钉扎粒子包括氧化锆、氧化钇、氧化镁、氧化钙、二氧化硅、 二氧化钛、氧化钡、氟化钙、氟化钡中的至少一种，所述氧化锆的含量占所述钉扎粒子总质量的0～50％。
  16. 根据权利要求15所述的荧光陶瓷，其特征在于，
    所述钉扎粒子包括氧化锆、氧化钇以及氧化镁。
  17. 根据权利要求16所述的荧光陶瓷，其特征在于，
    所述氧化锆的含量占所述钉扎粒子总质量的50％；
    所述氧化钇的含量占所述钉扎粒子总质量的25％；
    所述氧化镁的含量占所述钉扎粒子总质量的25％。
  18. 根据权利要求10所述的荧光陶瓷，其特征在于，
    所述荧光粉为镧系元素掺杂的YAG荧光粉颗粒，掺杂量为1％～5％；
    所述荧光粉的粒径为5μm～30μm。
  19. 根据权利要求18所述的荧光陶瓷，其特征在于，
    所述镧系元素掺杂的YAG荧光粉颗粒为Ce或Lu掺杂的YAG荧光粉颗粒。
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