[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN116947518A - Fluorescent ceramic and preparation method and application thereof - Google Patents

Fluorescent ceramic and preparation method and application thereof Download PDF

Info

Publication number
CN116947518A
CN116947518A CN202310879771.1A CN202310879771A CN116947518A CN 116947518 A CN116947518 A CN 116947518A CN 202310879771 A CN202310879771 A CN 202310879771A CN 116947518 A CN116947518 A CN 116947518A
Authority
CN
China
Prior art keywords
fluorescent ceramic
ceramic
fluorescent
whisker
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310879771.1A
Other languages
Chinese (zh)
Inventor
何锦华
董嘉
张晓方
梁超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Borui Photoelectric Co ltd
Original Assignee
Jiangsu Borui Photoelectric Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Borui Photoelectric Co ltd filed Critical Jiangsu Borui Photoelectric Co ltd
Priority to CN202310879771.1A priority Critical patent/CN116947518A/en
Publication of CN116947518A publication Critical patent/CN116947518A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44Shaped 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 aluminates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C04B35/505Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium oxide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/597Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3852Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3865Aluminium nitrides
    • C04B2235/3869Aluminium oxynitrides, e.g. AlON, sialon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5276Whiskers, spindles, needles or pins
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646Optical properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention provides fluorescent ceramic and a preparation method and application thereof. The fluorescent ceramic is internally distributed with whisker structures, the whisker length of the whisker structures is 5-20 mu m, and the distribution mass ratio of the whisker structures in the fluorescent ceramic is 2-6%. The whisker structure is at least one of aluminum nitride whisker or aluminum oxide whisker. On one hand, the whisker structure is utilized to effectively improve the heat conducting performance of the fluorescent ceramic, so that the fluorescent ceramic can conduct heat and dissipate heat more rapidly, and the whisker structure also increases the mechanical strength of the fluorescent ceramic; on the other hand, by introducing fine crystal particles, the invention can well exert the refraction and scattering of light, and meanwhile, the whisker structure can be mutually cooperated with the fine crystal particles, so that the refraction and scattering of light in fluorescent ceramics are further improved, the homogenization effect of an optical field is enhanced, and the light efficiency is improved.

Description

Fluorescent ceramic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of illumination materials, and particularly relates to fluorescent ceramic, and a preparation method and application thereof.
Background
Compared with the traditional fluorescent powder packaging, the fluorescent ceramic has obvious heat resistance and heat conduction performance, can replace a fluorescent powder packaging device in a certain application scene, plays a role in stabilizing performance, has wide market application potential especially in the fields of laser illumination and the like, and is a hot spot direction of the development of the current technology. However, the current fluorescent ceramic products are important problems affecting the further application of the current products due to the structure and preparation characteristics of the fluorescent ceramic products.
Disclosure of Invention
The invention aims to improve the high thermal conductivity and the light field uniformity of fluorescent ceramics in the laser illumination application, and provides the fluorescent ceramics, and a preparation method and application thereof.
The invention provides a fluorescent ceramic, whisker structures are distributed in the fluorescent ceramic, the whisker length of the whisker structures is 5-20 mu m, and the distribution mass ratio of the whisker structures in the fluorescent ceramic is 2-6%.
The whisker structure is at least one of aluminum nitride whisker or aluminum oxide whisker.
The fluorescent ceramic also comprises fine crystal particles in the fluorescent ceramic, wherein the size of the fine crystal particles is within +/-15% of the excitation light wavelength of the fluorescent ceramic.
The fine-grain particles are AlO-based fine-grain particles.
The AlO-based fine crystal particles are MgAl 2 O 4 Fine crystal particles formed of at least one of alumina or AlON.
The fluorescent ceramic excitation light is any one of blue light, ultraviolet light, green light, near infrared light and infrared light.
The mass content of the fine crystal particles accounts for 5-15% of the total mass of the fluorescent ceramic.
The fluorescent ceramic can be any one of YAG fluorescent ceramic, gaYAG fluorescent ceramic, CASN fluorescent ceramic, SCASN fluorescent ceramic, LSN fluorescent ceramic, beta-sialon fluorescent ceramic and gamma-AlON fluorescent ceramic.
The preparation method of the fluorescent ceramic comprises the following steps:
(1) Weighing fluorescent ceramic matrix materials and whisker raw materials according to a preset proportion, placing the materials into a ball milling tank together with magnesium oxide, magnesium carbonate and tetraethoxysilane, and sequentially performing ball milling, drying and sieving to obtain ceramic matrix powder for tape casting;
(2) Mixing a dispersing agent and a solvent to prepare a premix;
(3) Adding the ceramic matrix powder prepared in the step (1) into the premix prepared in the step (2) for performing first ball milling, sequentially adding a plasticizer and a binder, and performing second ball milling to prepare ceramic slurry with the solid content of 45-55wt%;
(4) Injecting the ceramic slurry obtained in the step (3) into a trough of a casting machine for casting molding after foam removal by a foam removal machine, drying, solidifying and demolding at room temperature to obtain a casting film, and cutting and laminating the casting film and carrying out temperature isostatic pressing to obtain a biscuit with the thickness of 0.15-0.2 mm;
(5) And (3) performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, calcining at 500-800 ℃ for 10-15 h in an air atmosphere, sintering the biscuit after glue discharging in a vacuum furnace, and finally annealing in the muffle furnace to obtain the fluorescent ceramic.
Preferably, in the step (1), the sintering aid is magnesium oxide and tetraethoxysilane, and the mass ratio of the magnesium oxide to the tetraethoxysilane is 1: (1-5), wherein the addition amount of the sintering aid is 0.1-0.5% of the total mass of the ceramic powder.
Preferably, in the step (2), the dispersing agent is any one or more of herring oil, ammonium acrylate or S502; the content of the dispersing agent is 0.5-1.0% of the content of the raw material powder; the solvent is one or more of water, toluene, alcohol and n-butanol;
preferably, in the step (3), the plasticizer is one or two of polyethylene glycol and glycerol, and the addition amount is 2.0-6.0% of the total mass of the ceramic powder; the binder is polyvinyl alcohol, and the addition amount is 3.0-6.0% of the total mass of the ceramic powder;
preferably, in the step (3), ball milling is carried out for 8-12 hours for the first time; ball milling is carried out for 12-18 h for the second time.
Preferably, in step (4), drying is performed at room temperature for 6 to 10 hours.
Preferably, in the step (4), the film is cut into a round shape with the diameter of 5-8 cm, the temperature isostatic pressing time is 10-20 min, the temperature is 70-80 ℃, and the pressure is 40-60 MPa.
Preferably, in the step (4), the vacuum pressure of the vacuum bubble removing machine is 0.2-1.0 KPa, and the bubble removing time is 1-2 min.
Preferably, in the step (5), the vacuum sintering temperature is 1650-1870 ℃, and the vacuum degree in the vacuum furnace chamber is kept at 10 -3 ~10 -4 Pa, sintering time is 15-20 h; the annealing temperature is 1200-1600 ℃ and the annealing time is 10-20 h.
A light emitting device comprising the fluorescent ceramic of any one of the preceding claims 1-8 and an excitation light source of the fluorescent ceramic.
A lighting device comprising the light emitting device of claim 10.
A projection apparatus comprising the light emitting device of claim 10.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
according to the fluorescent ceramic, the whisker with a certain proportion is introduced into the fluorescent ceramic, so that on one hand, the heat conduction performance of the fluorescent ceramic is effectively improved by utilizing the whisker structure, more rapid heat conduction and heat dissipation can be realized, and the mechanical strength of the fluorescent ceramic is also improved by utilizing the whisker structure; on the other hand, by introducing fine crystal particles, the invention can well exert the refraction and scattering of light, and meanwhile, the whisker structure can be mutually cooperated with the fine crystal particles, so that the refraction and scattering of light in fluorescent ceramics are further improved, the homogenization effect of an optical field is enhanced, and the light efficiency is improved. In addition, the size of fine crystal particles in the fluorescent ceramic is equivalent to the size of the incident light wavelength of the excitation light, so that the refraction and scattering effects of the fine crystal refraction/scattering unit on the incident light are further improved, and the light field homogenization effect and the light efficiency are further improved.
The fluorescent ceramic comprises AlO-based fine crystal particles, and the raw material is preferably nano MgAl 2 O 4 The nanometer alumina or nanometer AlON forms fine crystal particles in the preparation process of the fluorescent ceramic, and the fine crystal particles cooperate with the whisker structure while playing the role of light field homogenization, so that the light field homogenization and the light efficiency are further improved, and the strength of the fluorescent ceramic matrix is simultaneously improved cooperatively. In the preparation process of the fluorescent ceramic, the magnesium oxide and the magnesium carbonate are added to mutually and cooperatively inhibit the rapid movement of the grain boundary in the sintering process, so that the effect of regulating and controlling the grain size is achieved.
The invention is found through researches that the crystal adjusting effect can be well achieved only by adding magnesium oxide and magnesium carbonate at the same time, and the effect is not obvious when one of the magnesium oxide and the magnesium carbonate is added singly.
Description of the embodiments
Example 1
YAG fluorescent ceramics are mainly prepared by the following steps:
(1) Accurately weighing 142.2g of yttrium oxide, 107.3g of aluminum oxide and 0.55g of cerium oxide according to a preset proportion, weighing 12.5g of aluminum nitride whisker and 1.25g of magnesium oxide, placing the accurately weighed components into a ball milling tank, ball milling for 12 hours, drying at 80 ℃ for 12 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for tape casting;
(2) 1.25g of dispersant S502 and 120g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the powder prepared in the step (1) into the premix prepared in the step (2) for carrying out first ball milling for 12 hours, sequentially adding 32g of plasticizer PEG-200 and 40g of binder polyvinyl alcohol, and then carrying out second ball milling for 16 hours to prepare ceramic slurry with the solid content of 55 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.2-1.0 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.18 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 500-800 ℃ for 10-15 h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1780 ℃ and preserving heat for 15 hours; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
Comparative example 1, aluminum nitride whisker was not added, otherwise the same as in example 1
Example 2
YAG fluorescent ceramics are mainly prepared by the following steps:
(1) Accurately weighing 142.2g of yttrium oxide, 107.3g of aluminum oxide and 0.55g of cerium oxide according to a preset proportion, weighing 12.5g of aluminum nitride whisker, 1.25g of magnesium oxide and 0.73g of magnesium carbonate, placing the accurately weighed components into a ball milling tank, ball milling for 12 hours, drying at 80 ℃ for 12 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for tape casting;
(2) 1.25g of dispersant S502 and 120g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the powder prepared in the step (1) into the premix prepared in the step (2) for carrying out first ball milling for 12 hours, sequentially adding 32g of plasticizer PEG-200 and 40g of binder polyvinyl alcohol, and then carrying out second ball milling for 16 hours to prepare ceramic slurry with the solid content of 55 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.2-1.0 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.18 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 500-800 ℃ for 10-15 h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1780 ℃ and preserving heat for 15 hours; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
Comparative example 2 was conducted in the same manner as in example 2 except that no aluminum nitride whisker was added.
Example 3
The LSN fluorescent ceramic is mainly prepared by the following steps:
(1) Accurately weighing 145.6g La according to a predetermined proportion 3 Si 6 N 11 :Ce 3+ The preparation method comprises the steps of (1) placing the fluorescent powder and 102.5g of aluminum oxide, weighing 8.5g of aluminum oxide whisker, 1.31g of magnesium oxide and 0.82g of magnesium carbonate in a ball milling tank, ball milling for 10 hours, drying at 80 ℃ for 11 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for casting molding;
(2) 6.5g of dispersing agent S502 and 220g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the powder prepared in the step (1) into the premix prepared in the step (2) for carrying out first ball milling for 12 hours, sequentially adding 27g of plasticizer PEG-200 and 40g of binder polyvinyl alcohol, and then carrying out second ball milling for 16 hours to prepare ceramic slurry with the solid content of 50 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.5-1.0 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.22 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 600-800 ℃ for 10-15 h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1850 ℃ and preserving heat for 15 hours; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
Comparative example 3 was conducted in the same manner as in example 3 except that no alumina whisker was added.
Example 4
The preparation method of the LuAG fluorescent ceramic comprises the following steps:
(1) 138.6g Lu was precisely weighed in a predetermined ratio 2 O 3 Powder, 102.5g of alumina and 1.17g of cerium oxide, and 10.7g of alumina crystal were weighedPlacing 1.18g of magnesium oxide and 0.72g of magnesium carbonate into a ball milling tank, ball milling for 10 hours, drying at 80 ℃ for 11 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for casting molding;
(2) 1.28g of dispersant S502 and 150g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the ceramic powder prepared in the step (1) into the premix prepared in the step (2) for performing first ball milling for 10 hours, sequentially adding 25g of plasticizer PEG-200 and 43g of binder polyvinyl alcohol, and performing second ball milling for 15 hours to prepare ceramic slurry with the solid content of 53 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.2-1.0 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.20 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 760-780 ℃ for 13h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1820 ℃ for 15h; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
Comparative example 4 was conducted in the same manner as in example 4 except that no alumina whisker was added.
Example 5
The preparation method of the CASN fluorescent ceramic comprises the following steps:
(1) 139.7g CaAlSiN is accurately weighed according to a preset proportion 3 :Eu 2+ The preparation method comprises the steps of (1) placing fluorescent powder and 108.6g of aluminum oxide, weighing 8.5g of aluminum nitride whisker, 1.31g of magnesium oxide and 0.82g of magnesium carbonate in a ball milling tank, ball milling for 10 hours, drying at 80 ℃ for 11 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for casting molding;
(2) 7.1g of dispersant S502 and 240g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the powder prepared in the step (1) into the premix prepared in the step (2) for carrying out first ball milling for 12 hours, sequentially adding 33g of plasticizer PEG-200 and 43g of binder polyvinyl alcohol, and then carrying out second ball milling for 15 hours to prepare ceramic slurry with the solid content of 52 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.7-0.8 KPa, the bubble removing time is 3min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out temperature isostatic pressing to obtain a biscuit;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 700-800 ℃ for 10-15 h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1780 ℃ and preserving heat for 15 hours; finally, the ceramic is placed in a muffle furnace to be annealed at 1260 ℃ for 7 hours to obtain the fluorescent ceramic.
Comparative example 5 was conducted in the same manner as in example 5 except that no alumina whisker was added.
Example 6
YAG fluorescent ceramics are mainly prepared by the following steps:
(1) Accurately weighing 145.7g of yttrium oxide, 107.8g of aluminum oxide and 0.58g of cerium oxide according to a preset proportion, weighing 11.8g of aluminum nitride whisker, 1.2g of magnesium oxide and 8.6g of nano aluminum oxide (average particle size of 80 nm), placing the accurately weighed components into a ball milling tank, ball milling for 12 hours, drying at 80 ℃ for 12 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for tape casting;
(2) 1.3g of dispersant S502 and 140g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the powder prepared in the step (1) into the premix prepared in the step (2) for carrying out first ball milling for 12 hours, sequentially adding 35g of plasticizer PEG-200 and 40g of binder polyvinyl alcohol, and then carrying out second ball milling for 16 hours to prepare ceramic slurry with the solid content of 55 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.6-0.8 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.18 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 650-700 ℃ for 13h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1780 ℃ and preserving heat for 15 hours; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
Example 7
The preparation method of the LuAG fluorescent ceramic comprises the following steps:
(1) 138.6g Lu was precisely weighed in a predetermined ratio 2 O 3 102.5g of alumina and 1.17g of cerium oxide, weighing 10.7g of alumina whiskers, 1.18g of magnesium oxide, 0.72g of magnesium carbonate and 6.6g of nano aluminum oxynitride (average particle size of 70 nm), placing the above components in a ball milling tank, ball milling for 10 hours, drying at 80 ℃ for 11 hours, and sieving with a 100-mesh sieve to obtain ceramic powder for tape casting;
(2) 1.28g of dispersant S502 and 150g of solvent deionized water are weighed and mixed to prepare a premix;
(3) Adding the ceramic powder prepared in the step (1) into the premix prepared in the step (2) for performing first ball milling for 10 hours, sequentially adding 25g of plasticizer PEG-200 and 43g of binder polyvinyl alcohol, and performing second ball milling for 15 hours to prepare ceramic slurry with the solid content of 53 wt%;
(4) Removing bubbles from the ceramic slurry obtained in the step (3) by adopting a planetary vacuum bubble removing machine, wherein the vacuum pressure is 0.2-1.0 KPa, the bubble removing time is 2min, casting the ceramic slurry after bubble removal into a casting machine trough for molding, drying for 8h at room temperature, solidifying the slurry, demoulding to obtain a casting film, and cutting and laminating the casting film and carrying out warm isostatic pressing to obtain a biscuit with the thickness of 0.20 mm;
(5) Performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, and calcining at 760-780 ℃ for 13h in an air atmosphere; then placing the biscuit after glue discharging in a vacuum furnace for sintering at 1820 ℃ for 15h; finally, the ceramic is placed in a muffle furnace to be annealed for 10 hours at 1300 ℃ to obtain the fluorescent ceramic.
The resulting fluorescent ceramics were tested for properties as follows, with illuminance uniformity determined with reference to GT 004-2012:
fluorescent ceramic material Power W Light effect (lm/W) Illuminance uniformity (%) Thermal conductivity (w/m.k)
Example 1 6 203 92 17
Comparative example 1 6 191 80 13
Example 2 10 213 92 17
Comparative example 2 10 193 81 13
Example 3 8 199 93 16
Comparative example 3 8 190 80 12
Example 4 12 196 91 17
Comparative example 4 12 188 81 13
Example 5 10 198 93 17
Comparative example 5 10 189 80 14
Example 6 6 208 94 18
Example 7 12 203 93 18
It can be seen from each example and the corresponding comparative example that by adding whiskers, the light efficiency, the illuminance uniformity and the heat conduction performance are remarkably improved.

Claims (14)

1. A fluorescent ceramic is characterized in that whisker structures are distributed in the fluorescent ceramic, the whisker length of the whisker structures is 5-20 mu m, and the distribution mass ratio of the whisker structures in the fluorescent ceramic is 2-6%.
2. The fluorescent ceramic of claim 1, wherein the whisker structure is at least one of aluminum nitride whiskers or aluminum oxide whiskers.
3. The fluorescent ceramic of claim 1, further comprising fine-grain particles within the fluorescent ceramic, wherein the fine-grain particles have a size within + -15% of the wavelength of the excitation light of the fluorescent ceramic.
4. A fluorescent ceramic as claimed in claim 3, wherein the fine-grained particles are AlO-based fine-grained particles.
5. The fluorescent ceramic of claim 4, wherein the AlO-based fine crystal particles are nano MgAl 2 O 4 At least one of nano aluminum oxide or nano AlONFine-grain particles of (3).
6. The fluorescent ceramic of claim 4, wherein nano MgAl 2 O 4 The average particle size of the nano aluminum oxide or the nano AlON is smaller than 100nm.
7. The fluorescent ceramic according to claim 3, wherein the excitation light of the fluorescent ceramic is any one of blue light, ultraviolet light, green light, near infrared light, and infrared light.
8. A fluorescent ceramic according to claim 3, wherein the mass content of the fine crystal particles is 5% -15% of the total mass of the fluorescent ceramic.
9. The fluorescent ceramic according to claim 1, wherein the fluorescent ceramic is any one of YAG fluorescent ceramic, gaYAG fluorescent ceramic, CASN fluorescent ceramic, SCASN fluorescent ceramic, LSN fluorescent ceramic, β -sialon fluorescent ceramic, γ -AlON fluorescent ceramic.
10. The method for preparing a fluorescent ceramic according to any one of the preceding claims 1-9, characterized by comprising the steps of:
(1) Weighing fluorescent ceramic matrix materials and whisker raw materials according to a preset proportion, placing the materials into a ball milling tank together with magnesium oxide, magnesium carbonate and tetraethoxysilane, and sequentially performing ball milling, drying and sieving to obtain ceramic matrix powder for tape casting;
(2) Mixing a dispersing agent and a solvent to prepare a premix;
(3) Adding the ceramic matrix powder prepared in the step (1) into the premix prepared in the step (2) for performing first ball milling, sequentially adding a plasticizer and a binder, and performing second ball milling to prepare ceramic slurry with the solid content of 45-55wt%;
(4) Injecting the ceramic slurry obtained in the step (3) into a trough of a casting machine for casting molding after foam removal by a foam removal machine, drying, solidifying and demolding at room temperature to obtain a casting film, and cutting and laminating the casting film and carrying out temperature isostatic pressing to obtain a biscuit with the thickness of 0.15-0.2 mm;
(5) And (3) performing glue discharging treatment on the biscuit obtained in the step (4) in a muffle furnace, calcining at 500-800 ℃ for 10-15 h in an air atmosphere, sintering the biscuit after glue discharging in a vacuum furnace, and finally annealing in the muffle furnace to obtain the fluorescent ceramic.
11. The method for preparing fluorescent ceramics according to claim 10, wherein in the step (1), the mass ratio of magnesium oxide, magnesium carbonate and ethyl orthosilicate is 1 (0.5-0.8): 1-5), and the addition amount of the three is 0.1-0.5% of the total mass of the ceramic powder.
12. A light emitting device comprising the fluorescent ceramic of any one of the preceding claims 1-8 and an excitation light source of the fluorescent ceramic.
13. A lighting device comprising the light emitting device of claim 12.
14. A projection apparatus comprising the light emitting device of claim 12.
CN202310879771.1A 2023-07-18 2023-07-18 Fluorescent ceramic and preparation method and application thereof Pending CN116947518A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310879771.1A CN116947518A (en) 2023-07-18 2023-07-18 Fluorescent ceramic and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310879771.1A CN116947518A (en) 2023-07-18 2023-07-18 Fluorescent ceramic and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116947518A true CN116947518A (en) 2023-10-27

Family

ID=88454209

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310879771.1A Pending CN116947518A (en) 2023-07-18 2023-07-18 Fluorescent ceramic and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116947518A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108728097A (en) * 2017-04-14 2018-11-02 中国科学院宁波材料技术与工程研究所 A kind of fluorescent media and the light-emitting component comprising it
CN109896852A (en) * 2017-12-07 2019-06-18 上海航空电器有限公司 Complex phase fluorescence ceramics, preparation method and light supply apparatus for blue light activated white-light illuminating
US20190363507A1 (en) * 2016-11-15 2019-11-28 Appotronics Corporation Limited Light-emitting ceramic and light-emitting device
CN110627356A (en) * 2019-11-01 2019-12-31 吴俊楠 A kind of preparation method of high temperature resistant fluorescent glass for LED
WO2020017526A1 (en) * 2018-07-19 2020-01-23 パナソニックIpマネジメント株式会社 Wavelength conversion member

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190363507A1 (en) * 2016-11-15 2019-11-28 Appotronics Corporation Limited Light-emitting ceramic and light-emitting device
CN108728097A (en) * 2017-04-14 2018-11-02 中国科学院宁波材料技术与工程研究所 A kind of fluorescent media and the light-emitting component comprising it
CN109896852A (en) * 2017-12-07 2019-06-18 上海航空电器有限公司 Complex phase fluorescence ceramics, preparation method and light supply apparatus for blue light activated white-light illuminating
WO2020017526A1 (en) * 2018-07-19 2020-01-23 パナソニックIpマネジメント株式会社 Wavelength conversion member
CN110627356A (en) * 2019-11-01 2019-12-31 吴俊楠 A kind of preparation method of high temperature resistant fluorescent glass for LED

Similar Documents

Publication Publication Date Title
CN109467453B (en) Fluorescent ceramic with characteristic microstructure and preparation method and application thereof
US9287106B1 (en) Translucent alumina filaments and tape cast methods for making
CN102782088B (en) luminescent ceramic converter and preparation method thereof
Hu et al. 3D printed ceramic phosphor and the photoluminescence property under blue laser excitation
CN108863317B (en) A kind of fluorescent composite ceramic and its preparation method and application
KR101952138B1 (en) Light emitting composite with phosphor components
CN109592978B (en) Warm white high CRI fluorescent ceramic for high power LED/LD lighting and its preparation method and application
CN112939578B (en) Fluorescent ceramic, preparation method thereof, light-emitting device and projection device
CN106145922A (en) A kind of preparation method of LED YAG transparent fluorescent ceramic
WO2018028265A1 (en) Wavelength conversion device and preparation method therefor, light-emitting device and projection device
CN110240468B (en) Fluorescent ceramic and preparation method thereof
CN109896851B (en) Ceramic composite with concentration gradient, preparation method and light source device
CN107200589B (en) A kind of preparation method of aluminum nitride-based fluorescent ceramics and related fluorescent ceramics
JP5189712B2 (en) AlN substrate and manufacturing method thereof
DE112019001280T5 (en) Wavelength conversion element and light-emitting device using the same
CN111995398A (en) Fluorescent ceramic for high-color-rendering-index laser illumination and preparation method thereof
JP7410928B2 (en) Method for manufacturing a conversion element, conversion element, and light emitting device having the conversion element
US20150298424A1 (en) Layer composite, method for the production thereof as well as uses thereof
CN116947518A (en) Fluorescent ceramic and preparation method and application thereof
WO2021248445A1 (en) Transparent complex-phase fluorescent ceramic and preparation method therefor
CN107266046A (en) A kind of aluminum oxide fluorescence ceramics piece and its preparation method and application
CN116177995B (en) Preparation method of fluorescent ceramic based on 3D printing composite structure
CN104909741B (en) Preparation method of garnet type aluminate fluorescent ceramic and prepared fluorescent ceramic
CN116262660B (en) Fluorescent powder-loaded magnesium oxide complex-phase ceramic and preparation method and application thereof
CN112340982B (en) A kind of composite glass material and its preparation and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination