WO2020073811A1 - Fluorescent ceramic and preparation method therefor, light source device and projection device - Google Patents

Fluorescent ceramic and preparation method therefor, light source device and projection device Download PDF

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WO2020073811A1
WO2020073811A1 PCT/CN2019/108005 CN2019108005W WO2020073811A1 WO 2020073811 A1 WO2020073811 A1 WO 2020073811A1 CN 2019108005 W CN2019108005 W CN 2019108005W WO 2020073811 A1 WO2020073811 A1 WO 2020073811A1
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fluorescent
spherical
single crystal
ceramic
crystal particles
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PCT/CN2019/108005
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French (fr)
Chinese (zh)
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李乾
陈雨叁
王艳刚
许颜正
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深圳光峰科技股份有限公司
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B21/00—Projectors or projection-type viewers; Accessories therefor
    • G03B21/14—Details
    • G03B21/20—Lamp housings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B21/00—Projectors or projection-type viewers; Accessories therefor
    • G03B21/14—Details
    • G03B21/20—Lamp housings
    • G03B21/2006—Lamp housings characterised by the light source
    • G03B21/2033—LED or laser light sources
    • G03B21/204—LED or laser light sources using secondary light emission, e.g. luminescence or fluorescence
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof

Definitions

  • the invention relates to a fluorescent ceramic, in particular to a fluorescent ceramic containing spherical fluorescent single crystal particles, a preparation method thereof, a light emitting device and a projection device.
  • the technology of blue laser excitation fluorescent materials to obtain visible light with the development of laser display technology has been continuously paid attention to, the current research direction is mainly to develop new fluorescent materials (wavelength conversion materials) for the characteristics of laser excitation phosphors, the main The requirements are high luminous brightness, ability to withstand high-power laser irradiation, high optical conversion efficiency, and high thermal conductivity.
  • Fluorescent ceramics are ideal for high-power light sources due to their heat resistance and high thermal conductivity.
  • the traditional YAG: Ce pure phase fluorescent ceramics are weaker than the silica gel and glass package wavelength conversion devices in luminous performance.
  • the blue light absorption rate is low and the total reflection of the interface causes a large loss of light efficiency.
  • this irregular surface can easily enter the liquid phase and undergo material migration during the sintering process of preparing fluorescent ceramics (as shown in the circled part of Fig. 2) Shown), destroying the surface integrity of the phosphor particles, which in turn affects the luminescent properties of the phosphor particles; in addition, the phosphor particles that generate the liquid phase and the migration of substances will also affect the growth of the nearby Al 2 O 3 grains, resulting in this The bonding strength is not enough, which seriously affects the reliability of fluorescent ceramics.
  • the present invention aims to provide a high-performance fluorescent ceramic including spherical fluorescent single crystal particles as a light-emitting phase, wherein the spherical fluorescent single crystal particles have a regular shape and a smooth outer surface and can be excited by excitation light Visible light is emitted.
  • a fluorescent ceramic includes an alumina matrix phase and a luminescence center uniformly dispersed in the alumina matrix phase, characterized in that the luminescence center is spherical fluorescent single crystal particles.
  • the spherical fluorescent single crystal particles have a smooth spherical outer surface.
  • the spherical fluorescent single crystal particles have the same particle size, and the spherical fluorescent single crystal particles have a particle size of 30-50um.
  • the spherical fluorescent single crystal particles include phosphors with different particle sizes, and the particle size of the spherical fluorescent single crystal particles is 20-80um.
  • the spherical fluorescent single crystal particles are YAG: Ce crystal grains.
  • the mass of the spherical fluorescent single crystal particles is 15-90 wt% of the total mass of the fluorescent ceramic, preferably 40-60 wt%.
  • the present invention also provides a light source device, including an excitation light source and the above-mentioned fluorescent ceramic, the excitation light source can emit excitation light for exciting the fluorescent ceramic to emit excited light.
  • the invention also provides a projection device for projection imaging, including the above-mentioned light source device.
  • the invention also provides a method for preparing a fluorescent ceramic, including the following steps:
  • step S2 Load the appropriate amount of raw material powder prepared in step S2 into a graphite mold, and perform pre-pressing under a pressure of 5-15 MPa to obtain a ceramic green body;
  • the sintering temperature is 1250-1650 ° C, and the heat holding time is 30min-6h.
  • the sintering pressure is 30-200MPa, preferably 40-60Mpa. After that, the pressure is released and cooled with the furnace to obtain the fluorescent ceramic.
  • the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the content of yttrium oxide is 0.05-1 wt% of alumina, and the content of magnesium oxide is 0.05-1 wt% of alumina.
  • the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the particle size of the yttrium oxide and the magnesium oxide is 0.05-0.1um.
  • a fluorescent ceramic containing spherical fluorescent single crystal particles having a regular shape and a smooth outer surface. Since the spherical fluorescent single crystal particles have a smooth outer surface, the edges are not easy to enter the liquid phase sintering process during sintering, so that their luminous properties can be maintained, and the structural strength of the fluorescent ceramics after sintering is improved.
  • the spherical fluorescent single crystal particles can have a larger particle size coverage than phosphors. Phosphor particles often do not exceed 25-30um in size, while spherical fluorescent single crystal particles can reach 50-80um in size, and the luminous intensity of large particles is higher .
  • FIG. 1 is a schematic diagram showing the microscopic morphology of a conventional phosphor with better sphericity.
  • FIG. 2 is a schematic diagram showing the melting phenomenon at irregular edges of YAG phosphor particles after firing a fluorescent photoceramic in the prior art.
  • FIG. 3 is a schematic diagram of spherical fluorescent single crystal particles prepared using a hydrogen flame single crystal ball manufacturing equipment according to the present invention.
  • Example 4 is a distribution diagram of spherical YAG: Ce fluorescent single crystal particles in the YAG-Al 2 O 3 fluorescent ceramic composite material according to Example 1 and Example 2 of the present invention.
  • FIG. 5 is a distribution diagram of spherical YAG: Ce fluorescent single crystal particles in a YAG-Al 2 O 3 fluorescent ceramic composite material according to Example 3 of the present invention.
  • Figure 6 is a graph showing the performance comparison of different ceramic samples.
  • Fig. 7 is a graph showing the performance comparison of different ceramic samples.
  • Fig. 8 is a graph showing the performance comparison of different ceramic samples.
  • FIG. 9 is a schematic diagram of a hydrogen flame single crystal ball apparatus for preparing spherical fluorescent single crystal particles of the present invention.
  • the invention provides a fluorescent ceramic, which is a high-performance photoluminescent ceramic composite material, and is a fluorescent ceramic that uses a fine-grained alumina phase as a matrix and the matrix is wrapped with spherical fluorescent single crystal particles.
  • the spherical fluorescent single crystal particles can be excited by the excitation light to emit visible light.
  • the dense and fine-grained alumina matrix has good light transmission properties. The excited visible light can pass through the alumina matrix and exit the ceramic.
  • the spherical fluorescent single crystal particles of the present invention are regularly spherical and have a smooth outer surface, so their edges will not resemble irregularly shaped fluorescent particles in the prior art during sintering (as shown in FIGS. 1 and 2) It is easy to enter the liquid phase sintering, but it will maintain the original appearance after sintering, maintain the surface integrity of the fluorescent particles, and will not adversely affect the luminous performance, and Al 2 O 3 grains are in the spherical fluorescent single crystal particles The surface can develop uniformly, ensuring the binding force between the Al 2 O 3 phase and the spherical fluorescent single crystal particle phase.
  • the spherical fluorescent single crystal particles may be YAG: Ce spherical fluorescent single crystal particles.
  • the average particle diameter of the spherical fluorescent single crystal particles may be 20-80um, preferably 30-50um.
  • the fluorescent ceramic contains the above-mentioned spherical fluorescent single crystal particles as the light-emitting phase and Al 2 O 3 as the matrix phase. Since the spherical fluorescent single crystal particles in the fluorescent ceramic are regularly spherical and have a smooth outer surface, compared with the prior art, they will not adversely affect the light emitting performance and the ceramic structural strength.
  • the size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic can be the same, for example, 30-50um, because the size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic is larger than that of ordinary phosphor particles The luminous intensity of this ceramic is higher than that of fluorescent ceramics using ordinary phosphor particles in the prior art.
  • the size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic may also be different, for example, the distribution range of the particle size may be between 20-80um.
  • the distribution range of the particle size may be between 20-80um.
  • the spherical fluorescent single crystal particles have a more uniform light emitting surface and better stacking performance, the spherical single crystal particles of various sizes occupy less volume than the irregularly shaped phosphor particles, that is, the internal fluorescent composite ceramic Containing more luminescent centers, the luminescent performance of fluorescent ceramics is better.
  • the fluorescent ceramic may further contain Y 2 O 3 whose content is 0.05-1wt% of Al 2 O 3 ; MgO whose content is 0.05-1wt% of Al 2 O 3 ; and an appropriate amount of ceramic dispersant
  • the mass of the spherical fluorescent single crystal particles may be 15-90wt% of the total mass of the fluorescent ceramic, preferably 40-60wt%, to achieve a good luminous effect.
  • the preparation method and equipment of the spherical fluorescent single crystal particles of the present invention are described below. Specifically, as shown in FIG. 9, the present invention uses the hydrogen flame melting method to prepare spherical fluorescent single crystal particles.
  • the equipment used includes a barrel and a reaction barrel. It is mainly used to contain raw material powder for phosphor powder.
  • the barrel includes a powder outlet. Specifically, the particle size of the raw material powder for phosphor powder is in the range of 2-20um.
  • the above reaction barrel includes a powder inlet connected to the powder outlet of the barrel, so that the phosphor powder in the barrel enters through the powder inlet of the barrel; the barrel also includes an oxygen inlet and a hydrogen inlet.
  • Oxygen and hydrogen in the reaction tube react in the combustion zone to provide temperature conditions for the liquefaction of the phosphor powder, so that the phosphor powder entering the reaction tube liquefies instantly in the combustion zone; the reaction tube also includes a powder collection area, which is mainly used for Collect the phosphor falling in free fall after liquefaction in the combustion zone.
  • the above-mentioned phosphor raw material powder is currently commercially available YAG: Ce or alumina, yttrium oxide, cerium oxide and other raw material powders.
  • the reaction gas is introduced into the reaction cylinder through the oxygen inlet and the hydrogen inlet. The introduced oxygen and hydrogen are mixed and ignited in the combustion zone.
  • the temperature in the combustion zone reaches 2000-3000 ° C.
  • the powder outlet blows phosphor powder into the reaction tube, in which the amount of phosphor powder to be blown is 3g each time, and blows once every three minutes.
  • the amount and interval of phosphor powder to be blown are mainly the same as the phosphor powder
  • the reaction process in the reaction cylinder is related. Its purpose is to blow the next time after the raw material powder blown in the last time has been burned and liquefied and solidified, and then blown into the next time; , And fall in the powder collection area by means of free fall.
  • the falling height range is 30cm-80cm.
  • the lifting type powder collection area can be used to adjust the fall height.
  • the liquefied phosphor raw material powder droplets are in the process of falling Solidified into spherical fluorescent single crystal particles; specifically, the temperature of the combustion zone is controlled by the amount of hydrogen gas introduced, and the addition speed of the phosphor powder as the raw material powder is controlled And by controlling the temperature of the combustion zone of the hydrogen flame single crystal ball manufacturing equipment, the spherical fluorescent single crystal particles with a continuously changing particle size and a particle size distribution range of 20-80um can be prepared. It should be noted that not all of the raw material powder entering the combustion zone is liquefied, and some of the raw powder of phosphor powder that has not been liquefied falls directly into the powder collection zone.
  • the spherical fluorescent single crystal particles can be separated by screening to obtain purity Higher phosphor particles with regular shapes.
  • the fluorescent ceramic of the present invention can be prepared by the following method, which includes the following steps:
  • step S2 The appropriate amount of raw material powder prepared in step S2 is loaded into a graphite mold, and pre-compressed under a pressure of 5-15 MPa to obtain a ceramic green body.
  • S4 Ceramic sintering: Put the ceramic green body prepared in step S3 into a hot-press sintering furnace, and sinter it under an argon atmosphere.
  • the sintering temperature is 1250-1650 ° C
  • heat preservation is 30min-6h
  • the sintering pressure is 30-200MPa. It is preferably 40-60 MPa. After the sintering is completed, the pressure is released and the furnace is cooled to obtain the fluorescent ceramic.
  • step S2 Al 2 O 3 powder with a particle size of 0.05-1um, preferably 0.08-0.2um, Y 2 O 3 powder with a particle size of 0.05-0.1um and a particle size of 0.05-0.1um the MgO powder charged in the mill pot polytetrafluoroethylene, wherein the content of Y 2 O 3 wherein the powder is Al 2 O 3 powder 0.05-1wt%, the content of MgO powder accounts for 0.05 Al 2 O 3 powder -1wt%, using ethanol as grinding solvent and ceramic dispersant as dispersant for the first ball milling, the time of the first ball milling is 1-72h, preferably 24-36h, after the first ball milling, the step
  • the spherical fluorescent single crystal particles prepared in S1 are added to a ball mill tank for a second ball milling in a certain proportion, wherein the amount of the spherical fluorescent single crystal particles added is such that the mass of the spherical fluorescent single crystal particles is the total powder mass 15-90wt
  • a fluorescent ceramic with high light-emitting performance can be prepared.
  • the ceramic contains spherical fluorescent single crystal particles with a regular shape and a smooth outer surface, which can exert good luminous properties.
  • the YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
  • the degree of powder liquefaction and the size of droplets can be controlled by controlling the temperature of the combustion zone and the amount and rate of injection of raw material powder into the combustion zone, thereby controlling the spherical fluorescent single crystal particles size.
  • Raw materials high-purity ultrafine Al 2 O 3 nanopowder with a particle size of 0.05-1um, preferably 0.08-0.2um; high-purity ultrafine Y 2 O 3 nanopowder with a particle size of 0.05-0.1um; High-purity ultrafine MgO nano powder with a particle size of 0.05-0.1um; YAG: Ce spherical fluorescent single crystal particles prepared in step S1 are selected, with an average particle size of 20-80um, preferably 30-50um.
  • Al 2 O 3 powder were weighed certain number, Y 2 O 3 powder and MgO powder, wherein the content of Y 2 O 3 powder of Al 2 O 3 powder 0.05-1wt%, the content of MgO powder is Al 2 O 3 powder 0.05-1wt%.
  • YAG Ce spherical fluorescent single crystal particles
  • the mass percentage of YAG: Ce spherical fluorescent single crystal particles is 15-90wt% of the total powder, preferably 40-60wt%
  • the second ball milling is performed at a low speed, and the ball milling time is 10-120 minutes, preferably 40 minutes.
  • the first ball milling time is longer, in order to fully mix Al 2 O 3 powder, Y 2 O 3 powder and MgO powder and other ultrafine powders.
  • Y 2 O 3 powder and MgO powder as sintering aids must be combined with Al 2 O 3
  • the powder is thoroughly mixed to ensure uniform diffusion.
  • the second ball milling time is shorter because the YAG: Ce spherical fluorescent single crystal particles are larger and easier to disperse. If the ball milling time is too long, the crystal surface morphology of the YAG: Ce single crystal sphere is easily damaged by the ball and affects the luminescence performance.
  • dry powder is obtained by vacuum constant temperature drying.
  • the dry powder is calcined in a muffle furnace at 500-650 ° C to remove organic components from the powder for a period of 1-10 hours.
  • the calcined powder is granulated through a 80 mesh, 150 mesh, and 200 mesh sieve to obtain a high fluidity raw material powder, which is a raw material powder for fluorescent ceramics.
  • step S2 Weigh the appropriate amount of raw material powder prepared in step S2, put it into a graphite mold, pre-compress it under a pressure of 5-15MPa, and then put the graphite mold into a hot-press sintering furnace, sinter it under an argon atmosphere, sinter
  • the temperature is 1250-1650 ° C, the temperature is kept for 30min-6h, and the sintering pressure is 30-200MPa, preferably 40-60MPa.
  • the pressure is released and the furnace is cooled to obtain a YAG-Al 2 O 3 fluorescent ceramic composite material, in which the Al 2 O 3 phase is a continuous matrix phase, and spherical YAG: Ce fluorescent single crystal particles are dispersedly distributed therebetween. As shown schematically in FIG. 4.
  • the YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
  • YAG Ce spherical fluorescent single crystal particles are prepared according to the method for preparing spherical fluorescent single crystal particles in step S1 in Example 1, preferably with a particle size of 30-50um.
  • Al 2 O 3 powder preferably high-purity Al 2 O 3 powder with a particle size of 0.05-1um
  • Ce spherical fluorescent single crystal particle powder into the PTFE ball mill pot in proportion, add high-purity alumina sand ball with a particle size of 0.5um for ball milling, the medium is alcohol, and the ball milling time It is 30min-2h, preferably 1h. After ball milling, the slurry is dried, crushed, and sieved to obtain the raw material powder of fluorescent ceramics.
  • step S2 Put the appropriate amount of raw material powder prepared in step S2 into the graphite mold, pre-press at a pressure of 5-15MPa, then put the graphite mold into a hot-press sintering furnace, and sinter it in an argon atmosphere at a sintering temperature of 1250 -1650 ° C, holding time 30min-6h, sintering pressure 30-200MPa, preferably 40-60MPa. After the sintering is completed, the pressure is released and the furnace is cooled, so YAG-Al 2 O 3 fluorescent ceramic composite material is obtained, in which the Al 2 O 3 phase is a continuous matrix phase with spherical YAG: Ce fluorescent single crystal particles dispersed throughout , Also shown schematically in FIG. 4.
  • the YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
  • YAG Ce spherical fluorescent single crystal particles were prepared according to a method similar to the method of preparing spherical fluorescent single crystal particles in step S1 in Example 1, except that by continuously changing the addition speed of the raw material phosphor powder and by controlling At the temperature of the combustion zone, YAG: Ce fluorescent single crystal particles with continuously varying particle size and particle size range distributed in the range of 20-80um were prepared, that is, particles with a gradient change in particle size were obtained.
  • Al 2 O 3 powder preferably high-purity Al 2 O 3 powder with a particle size of 0.05-1um
  • step S2 Put the appropriate amount of raw material powder prepared in step S2 into the graphite mold, weigh the appropriate amount of raw material powder into the graphite mold, pre-press at a pressure of 5-15MPa, and then put the graphite mold into the hot-press sintering furnace. Sintering under argon atmosphere, sintering temperature 1250-1650 ° C, holding temperature 30min-6h, sintering pressure 30-200MPa, preferably 40-60MPa.
  • YAG-Al 2 O 3 fluorescent ceramic composite material in which the Al 2 O 3 phase is a continuous matrix phase, and spherical YAGs with different particle sizes are dispersedly distributed therebetween : Ce fluorescent single crystal particles, as schematically shown in FIG. 5.
  • the advantage of this embodiment is that the spherical single crystal particles of different particle size ranges have a higher filling rate of the fluorescent particles, so that the fluorescent ceramic contains more luminescent centers and the luminous efficiency is higher.
  • sample A, sample B and sample C as the luminous flux (lm) value test samples.
  • sample A, sample B and sample C in different lasers
  • the luminous flux (lm) value under current was tested, and three different sets of luminous flux (lm) values were obtained, in which sample A is a conventional fluorescent ceramic of the prior art, and sample B is a spherical fluorescent substance with a single particle diameter according to the present invention.
  • sample C is the fluorescent ceramic of the present invention containing spherical fluorescent single-crystal particles having various particle diameters.
  • Table 1 The test results of the luminous flux (lm) values of these three different samples are shown in Table 1 below.
  • the fluorescent ceramics prepared from different types of phosphor particles have different luminous flux (lm) values at the same laser current.
  • the luminous flux (lm) value of sample A is the smallest and sample B
  • the luminous flux (lm) value is medium
  • the luminous flux (lm) value of sample C is the largest, that is, the luminous performance of sample A is the worst, the luminous performance of sample B is medium, and the luminous performance of sample C is the best.
  • Fig. 7 shows the comparison of the luminescence performance of sample A and sample B
  • Fig. 8 shows the comparison of the luminescence performance of sample A and sample C.
  • Sample A is a fluorescent ceramic sample prepared by ordinary irregular-shaped YAG: Ce particles
  • sample B is a fluorescent ceramic sample prepared by the single-diameter spherical YAG: Ce single-crystal particles of the present invention
  • sample C is a different particle size of the present invention Fluorescent ceramic samples prepared by mixing spherical YAG: Ce single crystal particles.
  • the ordinate in Figures 6-8 is the luminous flux (lm) value
  • the abscissa is the current of the laser, indicating that as the current / power increases, the luminous flux (lm) value of the light emitted by the ceramic under the irradiation of the laser changes,
  • the turning point at 1.8A indicates that thermal quenching has occurred at this time, and the luminous efficiency has suddenly dropped, which is also the stopping point of the test.
  • the fluorescent ceramic samples prepared with spherical YAG: Ce single crystal particles with a single particle size and spherical YAG: Ce single crystal particles with different particle size ratios The luminescence performance of the prepared fluorescent ceramic samples is better than the fluorescent ceramic samples prepared by ordinary irregular-shaped YAG: Ce particles, and the luminescence performance of fluorescent ceramic samples prepared by spherical YAG: Ce particles with different particle size ratios is better than that of a single particle size
  • the fluorescent ceramic samples prepared by the spherical YAG: Ce have better luminous properties.
  • the spherical fluorescent single crystal particles of the present invention have a beneficial effect relative to the irregular fluorescent particles of the prior art.

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Abstract

Disclosed are a fluorescent ceramic and a preparation method therefor, a light source device, and a projection device. The fluorescent ceramic comprises an alumina matrix phase and a luminescence center uniformly dispersed in the alumina matrix phase, characterized in that the luminescence center is composed of spherical fluorescent monocrystal particles with a smooth spherical outer surface. The spherical fluorescent monocrystal particles have a regular spherical shape and a smooth outer surface, so that the original appearance can be maintained after sintering, which is conducive to improving the structural strength of the sintered fluorescent ceramic; moreover, the spherical fluorescent monocrystal particles having a larger particle size range can further improve the luminous efficiency of the fluorescent ceramic.

Description

一种荧光陶瓷及其制备方法、光源装置和投影装置Fluorescent ceramic and preparation method thereof, light source device and projection device 技术领域Technical field
本发明涉及一种荧光陶瓷，特别是涉及一种包含球形荧光单晶颗粒的荧光陶瓷及其制备方法、发光装置和投影装置。The invention relates to a fluorescent ceramic, in particular to a fluorescent ceramic containing spherical fluorescent single crystal particles, a preparation method thereof, a light emitting device and a projection device.
背景技术Background technique
蓝色激光激发荧光材料获得可见光的技术，随着激光显示技术的发展不断获得重视，当前的研究大方向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)，主要的要求是发光亮度高、能够承受大功率激光照射、光学转换效率高、导热性能高等特点。The technology of blue laser excitation fluorescent materials to obtain visible light, with the development of laser display technology has been continuously paid attention to, the current research direction is mainly to develop new fluorescent materials (wavelength conversion materials) for the characteristics of laser excitation phosphors, the main The requirements are high luminous brightness, ability to withstand high-power laser irradiation, high optical conversion efficiency, and high thermal conductivity.
荧光陶瓷由于具有耐热和高热导率等性能，是目前大功率光源的理想选择。传统的YAG:Ce纯相荧光陶瓷在发光性能上弱于硅胶和玻璃封装波长转换装置，特别是荧光陶瓷超薄封装时，蓝光吸收率低、界面全反射等原因造成的光效损失很大。目前为提高荧光陶瓷的发光性能，优先会选择较大尺寸的荧光粉颗粒，由于现有的荧光粉颗粒大多为不规则形状，如图1所示，表面存在较多凸起的尖锐边角(如图1的圆圈所圈起的部分所示)，此种不规则表面在制备荧光陶瓷的烧结过程中，会很容易进入液相和发生物质迁移(如图2的圆圈所圈起的部分所示)，破坏荧光粉颗粒的表面完整性，进而影响荧光粉颗粒的发光性能；另外产生液相和发生物质迁移的荧光粉颗粒也会影响附近的Al 2O 3晶粒的成长，导致此处的粘接强度不够，严重影响了荧光陶瓷的可靠性。 Fluorescent ceramics are ideal for high-power light sources due to their heat resistance and high thermal conductivity. The traditional YAG: Ce pure phase fluorescent ceramics are weaker than the silica gel and glass package wavelength conversion devices in luminous performance. Especially in the ultra-thin fluorescent ceramic packages, the blue light absorption rate is low and the total reflection of the interface causes a large loss of light efficiency. At present, in order to improve the luminous performance of fluorescent ceramics, it is preferred to choose larger-sized phosphor particles. Since the existing phosphor particles are mostly irregular shapes, as shown in FIG. 1, there are more convex sharp corners on the surface ( As shown in the circled part of Fig. 1), this irregular surface can easily enter the liquid phase and undergo material migration during the sintering process of preparing fluorescent ceramics (as shown in the circled part of Fig. 2) Shown), destroying the surface integrity of the phosphor particles, which in turn affects the luminescent properties of the phosphor particles; in addition, the phosphor particles that generate the liquid phase and the migration of substances will also affect the growth of the nearby Al 2 O 3 grains, resulting in this The bonding strength is not enough, which seriously affects the reliability of fluorescent ceramics.
因此，亟需一种新型的荧光陶瓷，来提升目前荧光陶瓷发光效率低的缺陷。Therefore, there is an urgent need for a new type of fluorescent ceramics to improve the defects of the current fluorescent ceramics with low luminous efficiency.
发明内容Summary of the invention
有鉴于此，本发明旨在提供一种包括作为发光相的球形荧光单晶颗粒的高性能荧光陶瓷，其中该球形荧光单晶颗粒具有规则的形状和光滑的外表面并能够被激发光激发而发出可见光。In view of this, the present invention aims to provide a high-performance fluorescent ceramic including spherical fluorescent single crystal particles as a light-emitting phase, wherein the spherical fluorescent single crystal particles have a regular shape and a smooth outer surface and can be excited by excitation light Visible light is emitted.
根据本发明，提供了一种荧光陶瓷，所述荧光陶瓷包括氧化铝基质相及均匀分散于氧化铝基质相中的发光中心，其特征在于，所述发光中心为球形荧光单晶颗粒，所述球形荧光单晶颗粒具有光滑的球形外表面。According to the present invention, a fluorescent ceramic is provided. The fluorescent ceramic includes an alumina matrix phase and a luminescence center uniformly dispersed in the alumina matrix phase, characterized in that the luminescence center is spherical fluorescent single crystal particles. The spherical fluorescent single crystal particles have a smooth spherical outer surface.
进一步地，所述球形荧光单晶颗粒的粒径大小相同，所述球形荧光单晶颗粒的粒径大小为30-50um。Further, the spherical fluorescent single crystal particles have the same particle size, and the spherical fluorescent single crystal particles have a particle size of 30-50um.
进一步地，所述球形荧光单晶颗粒包含有不同粒径大小的荧光粉，所述球形荧光单晶颗粒的粒径大小为20-80um。Further, the spherical fluorescent single crystal particles include phosphors with different particle sizes, and the particle size of the spherical fluorescent single crystal particles is 20-80um.
进一步地，所述球形荧光单晶颗粒为YAG:Ce晶粒。Further, the spherical fluorescent single crystal particles are YAG: Ce crystal grains.
进一步地，所述球形荧光单晶颗粒的质量为所述荧光陶瓷总质量的15-90wt％，优选40-60wt％。Further, the mass of the spherical fluorescent single crystal particles is 15-90 wt% of the total mass of the fluorescent ceramic, preferably 40-60 wt%.
本发明还提供一种光源装置，包括激发光源和上述的荧光陶瓷，所述激发光源能够发出激发光用于激发所述荧光陶瓷发出受激发光。The present invention also provides a light source device, including an excitation light source and the above-mentioned fluorescent ceramic, the excitation light source can emit excitation light for exciting the fluorescent ceramic to emit excited light.
本发明还提供一种投影装置，用于投影成像，包括上述的光源装置。The invention also provides a projection device for projection imaging, including the above-mentioned light source device.
本发明还提供一种荧光陶瓷的制备方法，包括如下步骤：The invention also provides a method for preparing a fluorescent ceramic, including the following steps:
S1：制备球形荧光单晶颗粒；S1: Preparation of spherical fluorescent single crystal particles;
S2：原料混合，S2: mixing of raw materials,
根据荧光陶瓷的化学计量称取氧化物原料粉，装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行球磨，球磨时间为1-72h，优选为24-36h，干燥获得原料粉；Weigh oxide raw material powder according to the stoichiometry of fluorescent ceramics, put it into a PTFE ball mill pot, add an appropriate amount of ethanol as a grinding solvent, add an appropriate amount of ceramic dispersant as a dispersant, and use ultra-low wear rate zirconia Ball milling, ball milling time is 1-72h, preferably 24-36h, dried to obtain raw material powder;
S3：压片成型，S3: tablet forming,
将步骤S2中制备得到的适量原料粉末装入石墨模具中，在5-15MPa压强下进行预压制，得到陶瓷生坯；Load the appropriate amount of raw material powder prepared in step S2 into a graphite mold, and perform pre-pressing under a pressure of 5-15 MPa to obtain a ceramic green body;
S4：陶瓷烧结，S4: ceramic sintering,
将S3得到的陶瓷生坯放入热压烧结炉内，在氩气气氛下进行烧结，烧结温度1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60Mpa，烧结完成后，卸除压力并随炉冷却，得到所述荧光陶瓷。Put the ceramic green body obtained by S3 into a hot-press sintering furnace, and sinter it under an argon atmosphere. The sintering temperature is 1250-1650 ° C, and the heat holding time is 30min-6h. The sintering pressure is 30-200MPa, preferably 40-60Mpa. After that, the pressure is released and cooled with the furnace to obtain the fluorescent ceramic.
进一步地，所述氧化物原料粉包括氧化钇和氧化镁，其中氧化钇含量为氧化铝的0.05-1wt％，氧化镁含量为氧化铝的0.05-1wt％。Further, the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the content of yttrium oxide is 0.05-1 wt% of alumina, and the content of magnesium oxide is 0.05-1 wt% of alumina.
进一步地，所述氧化物原料粉包括氧化钇和氧化镁，其中所述氧化钇和所述氧化镁的粒径为0.05-0.1um。Further, the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the particle size of the yttrium oxide and the magnesium oxide is 0.05-0.1um.
有益效果Beneficial effect
根据本发明，提供了一种包含具有规则形状和光滑的外表面的球形荧光单晶颗粒的荧光陶瓷。由于所述球形荧光单晶颗粒具有光滑的外表面，烧结过程中边缘不易进入液相烧结，从而能够保持其发光性能，并且有利于烧结后的荧光陶瓷的结构强度的提高。此外，球形荧光单晶颗粒的粒径覆盖范围可以比荧光粉更大，荧光粉颗粒往往不超过25-30um大小，而球形荧光单晶颗粒可达到50-80um大小，大颗粒的发光强度更高。According to the present invention, there is provided a fluorescent ceramic containing spherical fluorescent single crystal particles having a regular shape and a smooth outer surface. Since the spherical fluorescent single crystal particles have a smooth outer surface, the edges are not easy to enter the liquid phase sintering process during sintering, so that their luminous properties can be maintained, and the structural strength of the fluorescent ceramics after sintering is improved. In addition, the spherical fluorescent single crystal particles can have a larger particle size coverage than phosphors. Phosphor particles often do not exceed 25-30um in size, while spherical fluorescent single crystal particles can reach 50-80um in size, and the luminous intensity of large particles is higher .
附图说明BRIEF DESCRIPTION
附图表示本文所述的非限制性示例性实施例。本领域技术人员将要理解的是，附图不一定按比例绘制，而是用于重点说明本发明的原理。在附图中：The drawings represent non-limiting exemplary embodiments described herein. Those skilled in the art will understand that the drawings are not necessarily drawn to scale, but are used to highlight the principles of the present invention. In the drawings:
图1是示出了现有的球形度较好的荧光粉的显微形貌的示意图。FIG. 1 is a schematic diagram showing the microscopic morphology of a conventional phosphor with better sphericity.
图2是示出了现有技术中的荧光光陶瓷烧成后YAG荧光粉颗粒的不规则边缘处的熔融现象的示意图。FIG. 2 is a schematic diagram showing the melting phenomenon at irregular edges of YAG phosphor particles after firing a fluorescent photoceramic in the prior art.
图3是根据本发明的使用氢焰单晶球制造设备制备的球形荧光单晶颗粒的示意图。3 is a schematic diagram of spherical fluorescent single crystal particles prepared using a hydrogen flame single crystal ball manufacturing equipment according to the present invention.
图4是根据本发明实施例1和实施例2的YAG-Al 2O 3荧光陶瓷复合材料中的球形YAG:Ce荧光单晶颗粒的分布图。 4 is a distribution diagram of spherical YAG: Ce fluorescent single crystal particles in the YAG-Al 2 O 3 fluorescent ceramic composite material according to Example 1 and Example 2 of the present invention.
图5是根据本发明实施例3的YAG-Al 2O 3荧光陶瓷复合材料中的球形YAG:Ce荧光单晶颗粒的分布图。 5 is a distribution diagram of spherical YAG: Ce fluorescent single crystal particles in a YAG-Al 2 O 3 fluorescent ceramic composite material according to Example 3 of the present invention.
图6是示出了不同陶瓷样品的性能对比的图。Figure 6 is a graph showing the performance comparison of different ceramic samples.
图7是示出了不同陶瓷样品的性能对比的图。Fig. 7 is a graph showing the performance comparison of different ceramic samples.
图8是示出了不同陶瓷样品的性能对比的图。Fig. 8 is a graph showing the performance comparison of different ceramic samples.
图9是本发明的用于制备球形荧光单晶颗粒的氢焰单晶球设备的示意图。FIG. 9 is a schematic diagram of a hydrogen flame single crystal ball apparatus for preparing spherical fluorescent single crystal particles of the present invention.
具体实施方式detailed description
以下，参照附图更全面地说明本发明的一个或多个示例性实施例，在附图中，本领域技术人员能够容易地确定本发明的一个或多个示例性实施例。如本领域技术人员应认识到的，只要不脱离本发明的精神或范围，可以以各种不同的方式对所述示例性实施例进行修改，本发明的精神或范围不限于本文所述的示例性实施例。Hereinafter, one or more exemplary embodiments of the present invention will be described more fully with reference to the accompanying drawings. In the drawings, those skilled in the art can easily determine one or more exemplary embodiments of the present invention. As those skilled in the art should realize, the exemplary embodiments can be modified in various different ways as long as they do not depart from the spirit or scope of the present invention. The spirit or scope of the present invention is not limited to the examples described herein性 实施 例。 Sex embodiments.
本发明提供了一种荧光陶瓷，其是一种高性能光致荧光陶瓷复合材料，是一种以晶粒细小的氧化铝相为基质，基质包裹着球形荧光单晶颗粒的荧光陶瓷，陶瓷中的球形荧光单晶颗粒可以受到激发光激发而发出可见光，致密且晶粒细小的氧化铝基质具有良好的透光性能，被激发的可见光可以穿过氧化铝基质出射到陶瓷外面。The invention provides a fluorescent ceramic, which is a high-performance photoluminescent ceramic composite material, and is a fluorescent ceramic that uses a fine-grained alumina phase as a matrix and the matrix is wrapped with spherical fluorescent single crystal particles. The spherical fluorescent single crystal particles can be excited by the excitation light to emit visible light. The dense and fine-grained alumina matrix has good light transmission properties. The excited visible light can pass through the alumina matrix and exit the ceramic.
本发明的球形荧光单晶颗粒为规则的球形，具有光滑的外表面，因此在烧结过程中其边缘不会像现有技术中的不规则形状的荧光颗粒(如图1和图2所示)那样易于进入液相烧结，而是会在烧结后保持原有样貌，保持了荧光颗粒的表面完整性，不会对发光性能产生不利影响，并且Al 2O 3晶粒在球形荧光单晶颗粒表面能够均匀发育，保证了Al 2O 3相与球形荧光单晶颗粒相的结合力。例如，上述球形荧光单晶颗粒可以为YAG:Ce球形荧光单晶颗粒。根据本发明，该球形荧光单晶颗粒的平均粒径可以为20-80um，优选为30-50um。 The spherical fluorescent single crystal particles of the present invention are regularly spherical and have a smooth outer surface, so their edges will not resemble irregularly shaped fluorescent particles in the prior art during sintering (as shown in FIGS. 1 and 2) It is easy to enter the liquid phase sintering, but it will maintain the original appearance after sintering, maintain the surface integrity of the fluorescent particles, and will not adversely affect the luminous performance, and Al 2 O 3 grains are in the spherical fluorescent single crystal particles The surface can develop uniformly, ensuring the binding force between the Al 2 O 3 phase and the spherical fluorescent single crystal particle phase. For example, the spherical fluorescent single crystal particles may be YAG: Ce spherical fluorescent single crystal particles. According to the present invention, the average particle diameter of the spherical fluorescent single crystal particles may be 20-80um, preferably 30-50um.
如上所述，荧光陶瓷包含作为发光相的上述球形荧光单晶颗粒和作为基质相的Al 2O 3。由于该荧光陶瓷中的球形荧光单晶颗粒为规则的球形，具有光滑的外表面，因而与现有技术相比不会对发光性能和陶瓷结构强度产生不利影响。该荧光陶瓷中所包含的球形荧光单晶颗粒的粒径大小可以相同，例如为30-50um，由于该荧光陶瓷中所包含的球形荧光单晶颗粒的粒径比普通荧光粉颗粒的粒径要大，所以该陶瓷的发光强度比现有技术中使用普通荧光粉颗粒的荧光陶瓷的发光强度更高。另一方面，该荧光陶瓷中所包含的球形荧光单晶颗粒的粒径大小也可以不同，例如粒 径的分布范围可以为在20-80um之间。当将不同粒径的球形荧光单晶颗粒混合搭配时，可以在荧光陶瓷内部获得与单一粒径的球形荧光单晶颗粒相比更高的荧光颗粒填充率，因而可以达到更高的发光效率。由于球形荧光单晶颗粒的发光面更均匀，而且堆叠性能更好，所以多种尺寸的球形单晶颗粒所占体积比形状不规则的荧光粉颗粒更少，即，可以使复合荧光陶瓷内部所含的发光中心更多，因而荧光陶瓷的发光性能更好。 As described above, the fluorescent ceramic contains the above-mentioned spherical fluorescent single crystal particles as the light-emitting phase and Al 2 O 3 as the matrix phase. Since the spherical fluorescent single crystal particles in the fluorescent ceramic are regularly spherical and have a smooth outer surface, compared with the prior art, they will not adversely affect the light emitting performance and the ceramic structural strength. The size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic can be the same, for example, 30-50um, because the size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic is larger than that of ordinary phosphor particles The luminous intensity of this ceramic is higher than that of fluorescent ceramics using ordinary phosphor particles in the prior art. On the other hand, the size of the spherical fluorescent single crystal particles contained in the fluorescent ceramic may also be different, for example, the distribution range of the particle size may be between 20-80um. When spherical fluorescent single crystal particles of different particle diameters are mixed and matched, a higher filling rate of fluorescent particles can be obtained inside the fluorescent ceramic compared with spherical fluorescent single crystal particles of a single particle diameter, and thus higher luminous efficiency can be achieved. Since the spherical fluorescent single crystal particles have a more uniform light emitting surface and better stacking performance, the spherical single crystal particles of various sizes occupy less volume than the irregularly shaped phosphor particles, that is, the internal fluorescent composite ceramic Containing more luminescent centers, the luminescent performance of fluorescent ceramics is better.
可选择地，上述荧光陶瓷中还可以包含Y 2O 3，其含量为Al 2O 3的0.05-1wt％；MgO，其含量为Al 2O 3的0.05-1wt％；和适量的陶瓷分散剂，其中，所述球形荧光单晶颗粒的质量可以为所述荧光陶瓷总质量的15-90wt％，优选40-60wt％，以达到良好的发光效果。 Alternatively, the fluorescent ceramic may further contain Y 2 O 3 whose content is 0.05-1wt% of Al 2 O 3 ; MgO whose content is 0.05-1wt% of Al 2 O 3 ; and an appropriate amount of ceramic dispersant Wherein, the mass of the spherical fluorescent single crystal particles may be 15-90wt% of the total mass of the fluorescent ceramic, preferably 40-60wt%, to achieve a good luminous effect.
下面对本发明的球形荧光单晶颗粒的制备方法及设备进行说明，具体如图9所示，本发明采用氢焰熔融法制备球形荧光单晶颗粒，采用的设备包括料筒及反应筒，料筒主要用于容纳用于荧光粉原料粉，料筒包括粉末出料口，具体的，荧光粉原料粉的粒径范围为2-20um。上述反应筒包括与料筒的粉末出料口对接的的粉末进料口，以使得料筒内的荧光粉原料粉通过反应筒粉末进料口进入；反应筒还包括氧气进口及氢气进口，进入反应筒的氧气和氢气在燃烧区发生反应，为荧光粉原料粉的液化提供温度条件，使得在进入反应筒的荧光粉原料粉在燃烧区瞬间液化；反应筒还包括粉末收集区，主要用于收集在燃烧区液化后以自由落体方式坠落的荧光粉。进一步，上述的荧光粉原料粉为目前已商用的YAG:Ce或氧化铝、氧化钇和氧化铈等原料粉体。具体的制备过程，首先通过氧气进口和氢气进口向反应筒通入反应气体，通入的氧气和氢气在燃烧区混合并点火，待燃烧区的温度达到2000-3000℃，此时通过料筒的粉末出口向反应筒吹入荧光粉原料粉，其中吹入的荧光粉原料粉量为每次3g，每三分钟吹1次，荧光粉原料粉吹入的量和间隔时间主要和荧光粉原料粉在反应筒中的反应过程有关，其目的是在上一次吹入的原料粉已燃烧液化并凝固完成后，再吹入下一次；吹入的荧光粉原料粉在燃烧区短时间发生液化形成液滴，并通过自由落体的方式坠落在粉末收集区，其中坠落的高度范围为30cm-80cm，可采用升降式的粉末收集区来调节坠落高度，液化后的荧光粉原料粉液滴在下落的过程中凝固成球形的荧光单晶 颗粒；具体的，通过通入的氢气的量来控制燃烧区的温度，通过控制作为原料粉的荧光粉的添加速度以及通过控制氢焰单晶球制造设备的燃烧区的温度，可以制备出粒径连续变化的、粒径分布范围在20-80um之间的所述球形荧光单晶颗粒。需要说明的是，通入燃烧区的原料粉并非全部液化，部分未发生液化的荧光粉原料粉直接坠入粉末收集区，可通过筛分的方式对球形荧光单晶颗粒进行分离，以获得纯度较高，具有规则形状的荧光粉颗粒。The preparation method and equipment of the spherical fluorescent single crystal particles of the present invention are described below. Specifically, as shown in FIG. 9, the present invention uses the hydrogen flame melting method to prepare spherical fluorescent single crystal particles. The equipment used includes a barrel and a reaction barrel. It is mainly used to contain raw material powder for phosphor powder. The barrel includes a powder outlet. Specifically, the particle size of the raw material powder for phosphor powder is in the range of 2-20um. The above reaction barrel includes a powder inlet connected to the powder outlet of the barrel, so that the phosphor powder in the barrel enters through the powder inlet of the barrel; the barrel also includes an oxygen inlet and a hydrogen inlet. Oxygen and hydrogen in the reaction tube react in the combustion zone to provide temperature conditions for the liquefaction of the phosphor powder, so that the phosphor powder entering the reaction tube liquefies instantly in the combustion zone; the reaction tube also includes a powder collection area, which is mainly used for Collect the phosphor falling in free fall after liquefaction in the combustion zone. Further, the above-mentioned phosphor raw material powder is currently commercially available YAG: Ce or alumina, yttrium oxide, cerium oxide and other raw material powders. In the specific preparation process, firstly, the reaction gas is introduced into the reaction cylinder through the oxygen inlet and the hydrogen inlet. The introduced oxygen and hydrogen are mixed and ignited in the combustion zone. The temperature in the combustion zone reaches 2000-3000 ° C. The powder outlet blows phosphor powder into the reaction tube, in which the amount of phosphor powder to be blown is 3g each time, and blows once every three minutes. The amount and interval of phosphor powder to be blown are mainly the same as the phosphor powder The reaction process in the reaction cylinder is related. Its purpose is to blow the next time after the raw material powder blown in the last time has been burned and liquefied and solidified, and then blown into the next time; , And fall in the powder collection area by means of free fall. The falling height range is 30cm-80cm. The lifting type powder collection area can be used to adjust the fall height. The liquefied phosphor raw material powder droplets are in the process of falling Solidified into spherical fluorescent single crystal particles; specifically, the temperature of the combustion zone is controlled by the amount of hydrogen gas introduced, and the addition speed of the phosphor powder as the raw material powder is controlled And by controlling the temperature of the combustion zone of the hydrogen flame single crystal ball manufacturing equipment, the spherical fluorescent single crystal particles with a continuously changing particle size and a particle size distribution range of 20-80um can be prepared. It should be noted that not all of the raw material powder entering the combustion zone is liquefied, and some of the raw powder of phosphor powder that has not been liquefied falls directly into the powder collection zone. The spherical fluorescent single crystal particles can be separated by screening to obtain purity Higher phosphor particles with regular shapes.
进一步，本发明的荧光陶瓷可以通过以下方法来制备，所述方法包括以下步骤：Further, the fluorescent ceramic of the present invention can be prepared by the following method, which includes the following steps:
S1：制备上述球形荧光单晶颗粒。S1: The above spherical fluorescent single crystal particles are prepared.
S2：原料混合：S2: Raw material mixing:
根据荧光陶瓷的化学计量称取氧化物原料粉末，装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行球磨，球磨时间为1-72h，优选为24-36h，干燥获得原料粉；Weigh oxide raw material powder according to the stoichiometry of fluorescent ceramics, put it into a PTFE ball mill jar, add an appropriate amount of ethanol as a grinding solvent, add an appropriate amount of ceramic dispersant as a dispersant, and use ultra-low wear rate zirconia Ball milling, ball milling time is 1-72h, preferably 24-36h, dried to obtain raw material powder;
S3：压片成型：S3: Compression molding:
将步骤S2中制备得到的适量原料粉装入石墨模具中，在5-15MPa的压强下进行预压制，得到陶瓷生坯。The appropriate amount of raw material powder prepared in step S2 is loaded into a graphite mold, and pre-compressed under a pressure of 5-15 MPa to obtain a ceramic green body.
S4：陶瓷烧结：将步骤S3中制备得到的陶瓷生坯放入热压烧结炉内，在氩气气氛下进行烧结，烧结温度1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60Mpa，烧结完成后，卸除压力并随炉冷却，从而获得所述荧光陶瓷。S4: Ceramic sintering: Put the ceramic green body prepared in step S3 into a hot-press sintering furnace, and sinter it under an argon atmosphere. The sintering temperature is 1250-1650 ° C, heat preservation is 30min-6h, and the sintering pressure is 30-200MPa. It is preferably 40-60 MPa. After the sintering is completed, the pressure is released and the furnace is cooled to obtain the fluorescent ceramic.
可选择地，在步骤S2中：也可以首先将粒径为0.05-1um，优选为0.08-0.2um的Al 2O 3粉末、粒径为0.05-0.1um的Y 2O 3粉末和粒径为0.05-0.1um的MgO粉末装入聚四氟乙烯球磨罐中，其中其中Y 2O 3粉末的含量为Al 2O 3粉末的0.05-1wt％，MgO粉末的含量占Al 2O 3粉末的0.05-1wt％，以乙醇作为研磨溶剂，以陶瓷分散剂作为分散剂，进行第一次球磨，第一次球磨的时间为1-72h，优选为24-36h，第一次球磨结束后再将步骤S1中制备得到的所述球形荧光单晶颗粒按一定比例添加到球磨 罐中以进行第二次球磨，其中球形荧光单晶颗粒的添加量为使得球形荧光单晶颗粒的质量为总粉料质量的15-90wt％，优选40-60wt％，第二次球磨的时间为10-120min，优选为40min，将两次球磨结束后的浆料干燥粉碎，过筛后获得荧光陶瓷的原料粉末。 Alternatively, in step S2: Al 2 O 3 powder with a particle size of 0.05-1um, preferably 0.08-0.2um, Y 2 O 3 powder with a particle size of 0.05-0.1um and a particle size of 0.05-0.1um the MgO powder charged in the mill pot polytetrafluoroethylene, wherein the content of Y 2 O 3 wherein the powder is Al 2 O 3 powder 0.05-1wt%, the content of MgO powder accounts for 0.05 Al 2 O 3 powder -1wt%, using ethanol as grinding solvent and ceramic dispersant as dispersant for the first ball milling, the time of the first ball milling is 1-72h, preferably 24-36h, after the first ball milling, the step The spherical fluorescent single crystal particles prepared in S1 are added to a ball mill tank for a second ball milling in a certain proportion, wherein the amount of the spherical fluorescent single crystal particles added is such that the mass of the spherical fluorescent single crystal particles is the total powder mass 15-90wt%, preferably 40-60wt%, the second ball milling time is 10-120min, preferably 40min, the slurry after the two ball milling is dried and crushed, and the raw material powder of fluorescent ceramic is obtained after sieving.
根据本发明的荧光陶瓷的制备方法，可以制备出具有高的发光性能的荧光陶瓷。该陶瓷含有具有规则形状和光滑外表面的球形荧光单晶颗粒，能够发挥良好的发光性能。According to the preparation method of the fluorescent ceramic of the present invention, a fluorescent ceramic with high light-emitting performance can be prepared. The ceramic contains spherical fluorescent single crystal particles with a regular shape and a smooth outer surface, which can exert good luminous properties.
下面参照具体实施例来对本发明进行详细说明。The present invention will be described in detail below with reference to specific embodiments.
实施例1Example 1
按照以下步骤制备本实施例的YAG-Al 2O 3荧光陶瓷。 The YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
S1：制备球形荧光单晶颗粒S1: Preparation of spherical fluorescent single crystal particles
需要说明的是，可以通过控制燃烧区的温度大小以及通过控制原料粉的到燃烧区的注入数量和注入速度来控制粉末液化的程度和液滴的大小，以此来控制球形荧光单晶颗粒的大小。It should be noted that the degree of powder liquefaction and the size of droplets can be controlled by controlling the temperature of the combustion zone and the amount and rate of injection of raw material powder into the combustion zone, thereby controlling the spherical fluorescent single crystal particles size.
S2：制备荧光陶瓷的原料粉末S2: Raw material powder for preparing fluorescent ceramics
原料：选用高纯度超细Al 2O 3纳米粉末，粉末粒径为0.05-1um，优选为0.08-0.2um；选用高纯度超细Y 2O 3纳米粉末，粒径为0.05-0.1um；选用高纯度超细MgO纳米粉末，粒径为0.05-0.1um；选用步骤S1中制备得到的YAG:Ce球形荧光单晶颗粒，平均粒径为20-80um，优选为30-50um。 Raw materials: high-purity ultrafine Al 2 O 3 nanopowder with a particle size of 0.05-1um, preferably 0.08-0.2um; high-purity ultrafine Y 2 O 3 nanopowder with a particle size of 0.05-0.1um; High-purity ultrafine MgO nano powder with a particle size of 0.05-0.1um; YAG: Ce spherical fluorescent single crystal particles prepared in step S1 are selected, with an average particle size of 20-80um, preferably 30-50um.
称取一定数量的Al 2O 3粉末、Y 2O 3粉末和MgO粉末，其中Y 2O 3粉末的含量为Al 2O 3粉末的0.05-1wt％，MgO粉末的含量为Al 2O 3粉末的0.05-1wt％。将三种粉末装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行第一次球磨，球磨时间为1-72h，优选为24-36h。 Al 2 O 3 powder were weighed certain number, Y 2 O 3 powder and MgO powder, wherein the content of Y 2 O 3 powder of Al 2 O 3 powder 0.05-1wt%, the content of MgO powder is Al 2 O 3 powder 0.05-1wt%. Put the three kinds of powder into the PTFE ball mill pot, add the appropriate amount of ethanol as the grinding solvent, add the appropriate amount of ceramic dispersant as the dispersant, use the ultra-low wear rate zirconia ball for the first ball mill, ball mill time It is 1-72h, preferably 24-36h.
第一次球磨结束后，添加YAG:Ce球形荧光单晶颗粒到球磨罐中，YAG:Ce球形荧光单晶颗粒的质量百分比为占总粉料的15-90wt％，优选 40-60wt％，然后低速进行第二次球磨，球磨时间为10-120min，优选为40min。After the first ball milling, add YAG: Ce spherical fluorescent single crystal particles to the ball milling tank, the mass percentage of YAG: Ce spherical fluorescent single crystal particles is 15-90wt% of the total powder, preferably 40-60wt%, then The second ball milling is performed at a low speed, and the ball milling time is 10-120 minutes, preferably 40 minutes.
第一次球磨时间较长，是为了充分混合Al 2O 3粉末、Y 2O 3粉末和MgO粉末等超细粉，Y 2O 3粉末和MgO粉末作为烧结助剂，必须和Al 2O 3粉末进行充分的混合，保证扩散均匀。第二次球磨时间较短，是因为YAG:Ce球形荧光单晶颗粒较大，较易于分散，如果球磨时间过长，YAG:Ce单晶球体的晶粒表面形态容易被磨球破坏，影响发光性能。 The first ball milling time is longer, in order to fully mix Al 2 O 3 powder, Y 2 O 3 powder and MgO powder and other ultrafine powders. Y 2 O 3 powder and MgO powder as sintering aids must be combined with Al 2 O 3 The powder is thoroughly mixed to ensure uniform diffusion. The second ball milling time is shorter because the YAG: Ce spherical fluorescent single crystal particles are larger and easier to disperse. If the ball milling time is too long, the crystal surface morphology of the YAG: Ce single crystal sphere is easily damaged by the ball and affects the luminescence performance.
两次球磨结束后，采用真空恒温干燥获得干粉。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1-10小时。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末，即为荧光陶瓷的原料粉末。After the two ball mills are finished, dry powder is obtained by vacuum constant temperature drying. The dry powder is calcined in a muffle furnace at 500-650 ° C to remove organic components from the powder for a period of 1-10 hours. The calcined powder is granulated through a 80 mesh, 150 mesh, and 200 mesh sieve to obtain a high fluidity raw material powder, which is a raw material powder for fluorescent ceramics.
S3：进行热压烧结S3: Hot press sintering
称取步骤S2中制备的适量原料粉末，将其装入石墨模具中，在5-15MPa的压强下进行预压制，然后将石墨模具放入热压烧结炉内，在氩气气氛下烧结，烧结温度1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60MPa。烧结完成后，卸除压力并随炉冷却，获得YAG-Al 2O 3荧光陶瓷复合材料，其中Al 2O 3相为连续的基质相，其间弥散分布着球形的YAG:Ce荧光单晶颗粒，如图4中示意性示出的。 Weigh the appropriate amount of raw material powder prepared in step S2, put it into a graphite mold, pre-compress it under a pressure of 5-15MPa, and then put the graphite mold into a hot-press sintering furnace, sinter it under an argon atmosphere, sinter The temperature is 1250-1650 ° C, the temperature is kept for 30min-6h, and the sintering pressure is 30-200MPa, preferably 40-60MPa. After the sintering is completed, the pressure is released and the furnace is cooled to obtain a YAG-Al 2 O 3 fluorescent ceramic composite material, in which the Al 2 O 3 phase is a continuous matrix phase, and spherical YAG: Ce fluorescent single crystal particles are dispersedly distributed therebetween. As shown schematically in FIG. 4.
实施例2：Example 2:
按照以下步骤制备本实施例的YAG-Al 2O 3荧光陶瓷。 The YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
S1：按照实施例1中的步骤S1中的制备球形荧光单晶颗粒的方法制备YAG:Ce球形荧光单晶颗粒，优选粒径为30-50um。S1: YAG: Ce spherical fluorescent single crystal particles are prepared according to the method for preparing spherical fluorescent single crystal particles in step S1 in Example 1, preferably with a particle size of 30-50um.
S2：制备荧光陶瓷的原料粉末S2: Raw material powder for preparing fluorescent ceramics
称取Al 2O 3粉末，优选粒径为0.05-1um的高纯Al 2O 3粉末，在本实施例中可选用粒径为0.1-0.2um的牌号为TM-DAR的商用Al 2O 3粉末，选用步骤S1中制备得到的YAG:Ce球形荧光单晶颗粒，其中Al 2O 3粉末与YAG:Ce球形荧光单晶颗粒的体积比为Al 2O 3:YAG＝6:4。将Al 2O 3粉末与YAG:Ce球形荧光单晶颗粒粉末按比例放入聚四氟乙烯球磨罐中， 加入粒径为0.5um的高纯氧化铝砂球进行球磨，介质为酒精，球磨时间为30min-2h，优选为1h，球磨后将浆料干燥，粉碎，过筛后获得荧光陶瓷的原料粉末。 Weigh Al 2 O 3 powder, preferably high-purity Al 2 O 3 powder with a particle size of 0.05-1um, in this embodiment, commercial Al 2 O 3 with a particle size of 0.1-0.2um and a TM-DAR brand can be used powder, prepared in step S1, selection obtained YAG: Ce single crystal spherical phosphor particles, wherein the Al 2 O 3 powder and YAG: Ce phosphor crystal particles spherical volume ratio of Al 2 O 3: YAG = 6 : 4. Put the Al 2 O 3 powder and YAG: Ce spherical fluorescent single crystal particle powder into the PTFE ball mill pot in proportion, add high-purity alumina sand ball with a particle size of 0.5um for ball milling, the medium is alcohol, and the ball milling time It is 30min-2h, preferably 1h. After ball milling, the slurry is dried, crushed, and sieved to obtain the raw material powder of fluorescent ceramics.
S3：进行热压烧结S3: Hot press sintering
将步骤S2中制备得到的适量原料粉末装入石墨模具中，在5-15MPa的压强下进行预压制，然后将石墨模具放入热压烧结炉内，在氩气气氛下烧结，烧结温度为1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60MPa。烧结完成后，卸除压力并随炉冷却，于是获得YAG-Al 2O 3荧光陶瓷复合材料，其中Al 2O 3相为连续的基质相，其间弥散分布着球形的YAG:Ce荧光单晶颗粒，同样如图4中示意性示出的。 Put the appropriate amount of raw material powder prepared in step S2 into the graphite mold, pre-press at a pressure of 5-15MPa, then put the graphite mold into a hot-press sintering furnace, and sinter it in an argon atmosphere at a sintering temperature of 1250 -1650 ° C, holding time 30min-6h, sintering pressure 30-200MPa, preferably 40-60MPa. After the sintering is completed, the pressure is released and the furnace is cooled, so YAG-Al 2 O 3 fluorescent ceramic composite material is obtained, in which the Al 2 O 3 phase is a continuous matrix phase with spherical YAG: Ce fluorescent single crystal particles dispersed throughout , Also shown schematically in FIG. 4.
实施例3：Example 3:
按照以下步骤制备本实施例的YAG-Al 2O 3荧光陶瓷。 The YAG-Al 2 O 3 fluorescent ceramic of this example was prepared according to the following steps.
S1：制备球形荧光单晶颗粒S1: Preparation of spherical fluorescent single crystal particles
按照与实施例1中的步骤S1中的制备球形荧光单晶颗粒的方法类似的方法制备YAG:Ce球形荧光单晶颗粒，不同之处在于，通过连续改变原料荧光粉粉末的添加速度以及通过控制燃烧区的温度，制备出粒径连续变化的、粒径范围分布在20-80um区间的YAG:Ce荧光单晶颗粒，也就是说，获得粒径大小具有梯度变化的颗粒。YAG: Ce spherical fluorescent single crystal particles were prepared according to a method similar to the method of preparing spherical fluorescent single crystal particles in step S1 in Example 1, except that by continuously changing the addition speed of the raw material phosphor powder and by controlling At the temperature of the combustion zone, YAG: Ce fluorescent single crystal particles with continuously varying particle size and particle size range distributed in the range of 20-80um were prepared, that is, particles with a gradient change in particle size were obtained.
S2：制备荧光陶瓷的原料粉末S2: Raw material powder for preparing fluorescent ceramics
称取Al 2O 3粉末，优选粒径为0.05-1um的高纯Al 2O 3粉末，在本实施例中可以选用粒径为0.1-0.2um的牌号为TM-DAR的商用Al 2O 3粉末，选用步骤S1中制备得到的YAG:Ce球形荧光单晶颗粒，其中Al 2O 3粉末与YAG:Ce球形荧光单晶颗粒的体积比为Al 2O 3:YAG＝6:4。将Al 2O 3粉末与YAG:Ce球形荧光单晶颗粒粉末按比例放入聚四氟乙烯球磨罐中，加入粒径为0.5um的高纯氧化铝砂球进行球磨，介质为酒精，球磨时间30min-2h，优选为1h，球磨后将浆料干燥，粉碎，过筛后获得荧光陶瓷的原料粉末。 Weighing Al 2 O 3 powder, preferably high-purity Al 2 O 3 powder with a particle size of 0.05-1um, in this embodiment, commercial Al 2 O 3 with a particle size of 0.1-0.2um and a brand of TM-DAR can be used powder, prepared in step S1, selection obtained YAG: Ce single crystal spherical phosphor particles, wherein the Al 2 O 3 powder and YAG: Ce phosphor crystal particles spherical volume ratio of Al 2 O 3: YAG = 6 : 4. Put the Al 2 O 3 powder and YAG: Ce spherical fluorescent single crystal particle powder into the PTFE ball mill pot in proportion, add high-purity alumina sand balls with a particle size of 0.5um for ball milling, the medium is alcohol, and the ball milling time 30min-2h, preferably 1h. After ball milling, the slurry is dried, crushed, and sieved to obtain the raw material powder of fluorescent ceramics.
S3：进行热压烧结S3: Hot press sintering
将步骤S2中制备得到的适量原料粉末装入石墨模具中，称取适量原料粉末装入石墨模具中，在5-15MPa压强下进行预压制，然后将石墨模具放入热压烧结炉内，在氩气气氛下烧结，烧结温度1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60MPa。烧结完成后，卸除压力并随炉冷却，于是获得YAG-Al 2O 3荧光陶瓷复合材料，其中Al 2O 3相为连续的基质相，其间弥散分布着具有不同粒径大小的球形的YAG:Ce荧光单晶颗粒，如图5中示意性示出的。本实施方式的优势在于不同粒径范围的球形单晶颗粒具有更高的荧光颗粒填充率，使得荧光陶瓷内部包含更多的发光中心，发光效率更高。 Put the appropriate amount of raw material powder prepared in step S2 into the graphite mold, weigh the appropriate amount of raw material powder into the graphite mold, pre-press at a pressure of 5-15MPa, and then put the graphite mold into the hot-press sintering furnace. Sintering under argon atmosphere, sintering temperature 1250-1650 ° C, holding temperature 30min-6h, sintering pressure 30-200MPa, preferably 40-60MPa. After the sintering is completed, the pressure is released and the furnace is cooled, so YAG-Al 2 O 3 fluorescent ceramic composite material is obtained, in which the Al 2 O 3 phase is a continuous matrix phase, and spherical YAGs with different particle sizes are dispersedly distributed therebetween : Ce fluorescent single crystal particles, as schematically shown in FIG. 5. The advantage of this embodiment is that the spherical single crystal particles of different particle size ranges have a higher filling rate of the fluorescent particles, so that the fluorescent ceramic contains more luminescent centers and the luminous efficiency is higher.
以下参照表1和图6-8对本发明的效果进行说明。The effects of the present invention will be described below with reference to Table 1 and FIGS. 6-8.
为了对本发明的荧光陶瓷的发光性能进行验证，本发明的发明人采用了样品A、样品B和样品C作为光通量(lm)值的测试试样，对样品A、样品B和样品C在不同激光器电流下的光通量(lm)值进行了测试，获得了三组不同的光通量(lm)值，其中样品A为现有技术的普通荧光陶瓷，样品B为本发明的包含具有单一粒径的球形荧光单晶颗粒的荧光陶瓷，样品C为本发明的包含具有多种粒径的球形荧光单晶颗粒的荧光陶瓷，这三种不同样品的光通量(lm)值的测试结果如下表1所示。In order to verify the luminous performance of the fluorescent ceramic of the present invention, the inventors of the present invention adopted sample A, sample B and sample C as the luminous flux (lm) value test samples. For sample A, sample B and sample C in different lasers The luminous flux (lm) value under current was tested, and three different sets of luminous flux (lm) values were obtained, in which sample A is a conventional fluorescent ceramic of the prior art, and sample B is a spherical fluorescent substance with a single particle diameter according to the present invention. For single-crystal particles of fluorescent ceramics, sample C is the fluorescent ceramic of the present invention containing spherical fluorescent single-crystal particles having various particle diameters. The test results of the luminous flux (lm) values of these three different samples are shown in Table 1 below.
表1.不同陶瓷样品在不同激光器电流下的测试光通量(lm)值Table 1. Test luminous flux (lm) values of different ceramic samples under different laser currents
Figure PCTCN2019108005-appb-000001
Figure PCTCN2019108005-appb-000001
由上表可以看出，由不同形态荧光粉颗粒制备的荧光陶瓷在相同的激光器电流下的光通量(lm)值不同，在相同的激光器电流下，样品A的光通量(lm)值最小，样品B的光通量(lm)值中等，样品C的光通量(lm)值最大，也就是说样品A的发光性能最差，样品B的发光性能中等，样品C的发光性能最好。It can be seen from the table above that the fluorescent ceramics prepared from different types of phosphor particles have different luminous flux (lm) values at the same laser current. Under the same laser current, the luminous flux (lm) value of sample A is the smallest and sample B The luminous flux (lm) value is medium, and the luminous flux (lm) value of sample C is the largest, that is, the luminous performance of sample A is the worst, the luminous performance of sample B is medium, and the luminous performance of sample C is the best.
同时，在本申请的附图6-8中以直观的方式示出了上述不同形态荧光粉颗粒制备的荧光陶瓷的发光性能的对比图，其中图6示出了样品A、样品B和样品C的发光性能的对比图；图7示出了样品A和样品B的发光性能对比图；图8示出了样品A和样品C的发光性能对比图。样品A是普通不规则形状的YAG:Ce颗粒制备的荧光陶瓷样品，样品B是本发明的单一粒径的球形YAG:Ce单晶颗粒制备的荧光陶瓷样品，样品C是本发明的不同粒径配比的球形YAG:Ce单晶颗粒制备的荧光陶瓷样品。附图6-8中的纵坐标为光通量(lm)值，横坐标是激光器的电流，表示随着电流/功率的增大，陶瓷在激光器的照射下发出的光的光通量(lm)值变化，1.8A时的转折表明此时发生了热焠灭，发光效率出现突然的下降，此时也是测试的停止点。At the same time, the comparison graphs of the luminous properties of the fluorescent ceramics prepared by the phosphor particles of different forms described above are shown intuitively in the attached drawings 6-8 of the present application. Fig. 7 shows the comparison of the luminescence performance of sample A and sample B; Fig. 8 shows the comparison of the luminescence performance of sample A and sample C. Sample A is a fluorescent ceramic sample prepared by ordinary irregular-shaped YAG: Ce particles, sample B is a fluorescent ceramic sample prepared by the single-diameter spherical YAG: Ce single-crystal particles of the present invention, and sample C is a different particle size of the present invention Fluorescent ceramic samples prepared by mixing spherical YAG: Ce single crystal particles. The ordinate in Figures 6-8 is the luminous flux (lm) value, and the abscissa is the current of the laser, indicating that as the current / power increases, the luminous flux (lm) value of the light emitted by the ceramic under the irradiation of the laser changes, The turning point at 1.8A indicates that thermal quenching has occurred at this time, and the luminous efficiency has suddenly dropped, which is also the stopping point of the test.
根据上表1的数据以及附图6-8的发光性能曲线可以看出，单一粒径的球形YAG:Ce单晶颗粒制备的荧光陶瓷样品和不同粒径配比的球形YAG:Ce单晶颗粒制备的荧光陶瓷样品的发光性能都比普通不规则形状的YAG:Ce颗粒制备的荧光陶瓷样品要好，并且不同粒径配比的球形YAG:Ce颗粒制备的荧光陶瓷样品的发光性能比单一粒径的球形YAG:Ce制备的荧光陶瓷样品的发光性能要好。According to the data in Table 1 above and the luminescence performance curve in Figures 6-8, it can be seen that the fluorescent ceramic samples prepared with spherical YAG: Ce single crystal particles with a single particle size and spherical YAG: Ce single crystal particles with different particle size ratios The luminescence performance of the prepared fluorescent ceramic samples is better than the fluorescent ceramic samples prepared by ordinary irregular-shaped YAG: Ce particles, and the luminescence performance of fluorescent ceramic samples prepared by spherical YAG: Ce particles with different particle size ratios is better than that of a single particle size The fluorescent ceramic samples prepared by the spherical YAG: Ce have better luminous properties.
由此可以看出，本发明的球形荧光单晶颗粒相对于现有技术的不规则荧光颗粒具有有益效果。It can be seen from this that the spherical fluorescent single crystal particles of the present invention have a beneficial effect relative to the irregular fluorescent particles of the prior art.
本发明所列举的各原料，以及本发明各原料的上下限、工艺参数的上下限、区间取值都能实现本发明，在此不一一列举实施例；凡是依据本发明的技术实质对以上实施例所作的任何简单修改或等同变化，均仍属于本发明的技术方案的范围之内。The raw materials listed in the present invention, as well as the upper and lower limits of each raw material of the present invention, the upper and lower limits of the process parameters, and the value of the interval can realize the present invention, and the embodiments are not enumerated here; Any simple modifications or equivalent changes made in the embodiments still fall within the scope of the technical solution of the present invention.

Claims (10)

  1. 一种荧光陶瓷，所述荧光陶瓷包括氧化铝基质相及均匀分散于氧化铝基质相中的发光中心，其特征在于，所述发光中心为球形荧光单晶颗粒，所述球形荧光单晶颗粒具有光滑的球形外表面。A fluorescent ceramic comprising an alumina matrix phase and a luminescent center uniformly dispersed in the alumina matrix phase, characterized in that the luminescent center is spherical fluorescent single crystal particles, and the spherical fluorescent single crystal particles have Smooth spherical outer surface.
  2. 根据权利要求1所述的荧光陶瓷，其特征在于，所述球形荧光单晶颗粒的粒径大小相同，所述球形荧光单晶颗粒的粒径大小为30-50um。The fluorescent ceramic according to claim 1, wherein the spherical fluorescent single crystal particles have the same particle size, and the spherical fluorescent single crystal particles have a particle size of 30-50um.
  3. 根据权利要求1所述的荧光陶瓷，其特征在于，所述球形荧光单晶颗粒的粒径大小不同，所述球形荧光单晶颗粒的粒径大小为20-80um。The fluorescent ceramic according to claim 1, wherein the spherical fluorescent single crystal particles have different particle sizes, and the spherical fluorescent single crystal particles have a particle size of 20-80um.
  4. 根据权利要求1-3任一所述的荧光陶瓷，其特征在于，所述球形荧光单晶颗粒为YAG:Ce晶粒。The fluorescent ceramic according to any one of claims 1 to 3, wherein the spherical fluorescent single crystal particles are YAG: Ce crystal grains.
  5. 根据权利要求1所述的荧光陶瓷，其特征在于，所述球形荧光单晶颗粒的质量为所述荧光陶瓷总质量的15-90wt％，优选40-60wt％。The fluorescent ceramic according to claim 1, characterized in that the mass of the spherical fluorescent single crystal particles is 15-90 wt% of the total mass of the fluorescent ceramic, preferably 40-60 wt%.
  6. 一种光源装置，其特征在于，包括激发光源和权利要求1～6任一所述的荧光陶瓷，所述激发光源能够发出激发光用于激发所述荧光陶瓷发出受激发光。A light source device, comprising an excitation light source and the fluorescent ceramic according to any one of claims 1 to 6, wherein the excitation light source can emit excitation light for exciting the fluorescent ceramic to emit excited light.
  7. 一种投影装置，用于投影成像，其特征在于，包括权利要求6所述的光源装置。A projection device for projection imaging is characterized by comprising the light source device according to claim 6.
  8. 一种荧光陶瓷的制备方法，其特征在于，包括如下步骤：A method for preparing fluorescent ceramics, characterized in that it includes the following steps:
    S1：制备球形荧光单晶颗粒；S1: Preparation of spherical fluorescent single crystal particles;
    S2：原料混合，S2: mixing of raw materials,
    根据荧光陶瓷的化学计量称取氧化物原料粉，装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散 剂，用超低磨失率的氧化锆球进行球磨，球磨时间为1-72h，优选为24-36h，干燥获得原料粉；Weigh oxide raw material powder according to the stoichiometry of fluorescent ceramics, put it into a PTFE ball mill pot, add an appropriate amount of ethanol as a grinding solvent, add an appropriate amount of ceramic dispersant as a dispersant, and use ultra-low wear rate zirconia Ball milling, ball milling time is 1-72h, preferably 24-36h, dried to obtain raw material powder;
    S3：压片成型，S3: tablet forming,
    将步骤S2中制备得到的适量原料粉末装入石墨模具中，在5-15MPa压强下进行预压制，得到陶瓷生坯；Load the appropriate amount of raw material powder prepared in step S2 into a graphite mold, and perform pre-pressing under a pressure of 5-15 MPa to obtain a ceramic green body;
    S4：陶瓷烧结，S4: ceramic sintering,
    将S3得到的陶瓷生坯放入热压烧结炉内，在氩气气氛下进行烧结，烧结温度1250-1650℃，保温30min-6h，烧结压力为30-200MPa，优选为40-60Mpa，烧结完成后，卸除压力并随炉冷却，得到所述荧光陶瓷。Put the ceramic green body obtained by S3 into a hot-press sintering furnace, and sinter it under an argon atmosphere. The sintering temperature is 1250-1650 ° C, and the temperature is 30min-6h. After that, the pressure is released and cooled with the furnace to obtain the fluorescent ceramic.
  9. 根据权利要求8所述的制备方法，其特征在于，所述氧化物原料粉包括氧化钇和氧化镁，其中氧化钇含量为氧化铝的0.05-1wt％，氧化镁含量为氧化铝的0.05-1wt％。The preparation method according to claim 8, characterized in that the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the yttrium oxide content is 0.05-1wt% of aluminum oxide, and the magnesium oxide content is 0.05-1wt of aluminum oxide %.
  10. 根据权利要求8所述的制备方法，其特征在于，所述氧化物原料粉包括氧化钇和氧化镁，其中所述氧化钇和所述氧化镁的粒径为0.05-0.1um。The preparation method according to claim 8, wherein the oxide raw material powder includes yttrium oxide and magnesium oxide, wherein the particle size of the yttrium oxide and the magnesium oxide is 0.05-0.1um.
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